WO2020213413A1 - Water-based liquid ink and laminate - Google Patents
Water-based liquid ink and laminate Download PDFInfo
- Publication number
- WO2020213413A1 WO2020213413A1 PCT/JP2020/015166 JP2020015166W WO2020213413A1 WO 2020213413 A1 WO2020213413 A1 WO 2020213413A1 JP 2020015166 W JP2020015166 W JP 2020015166W WO 2020213413 A1 WO2020213413 A1 WO 2020213413A1
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- WIPO (PCT)
- Prior art keywords
- ink
- pigment
- water
- printing
- pigment red
- Prior art date
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M1/00—Inking and printing with a printer's forme
- B41M1/26—Printing on other surfaces than ordinary paper
- B41M1/30—Printing on other surfaces than ordinary paper on organic plastics, horn or similar materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/023—Emulsion inks
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
Definitions
- the present invention relates to a water-based gravure ink for laminating for flexible packaging, a water-based liquid ink such as a water-based flexo ink, and a laminate using the water-based liquid ink.
- a water-based liquid ink having excellent viscosity stability, adhesion of a cured coating film to a substrate, and various coating film strengths, and a laminate using the water-based liquid ink.
- the present invention also relates to a water-based liquid ink having excellent viscosity stability, adhesion to the base material of the cured coating film, and various coating film strengths even in a system to which a curing agent is added, and a laminate using the water-based liquid ink. ..
- Gravure inks and flexographic inks are widely used for the purpose of imparting cosmeticity and functionality to the printed material of the flexible packaging film.
- the gravure- or flexographic-printed object is used as a flexible packaging material for foods and hygiene products among packaging materials, it is generally laminated.
- various printed materials and laminating processes are used depending on the type of contents and the purpose of use. Then, by laminating the printed matter and various films with an adhesive, it is possible to maintain the film surface strength, storage stability, boil / retort suitability, etc., which cannot be obtained only with the printed matter.
- the printed matter itself is often intended to protect the contents.
- the printing ink layer does not come into direct contact with the contents, but the laminating suitability is required. .. Then, in order to maintain the laminating suitability, it is usual practice to improve the adhesion between the thermoplastic resin film of the base material and the printing ink layer by providing an anchor coat layer under the printing ink layer.
- the substrate of the cured coating film is maintained in a constant viscosity for at least 6 hours after the addition of the curing agent in consideration of the workability. It cannot be said that it is easy to have both adhesion and various coating film strengths.
- An object of the present invention is to provide a water-based liquid ink having excellent viscosity stability, adhesion of a cured coating film to a substrate, and various coating film strengths, and a laminate using the water-based liquid ink. Further, even in a system to which a curing agent is added, a water-based liquid ink having excellent viscosity stability, adhesion of a cured coating film to a substrate, and various coating film strengths, and a laminate using the water-based liquid ink can be obtained. To provide.
- the aqueous liquid ink of the present invention is formed from a (meth) acrylate-based monomer and / or a vinyl-based monomer, and is a copolymer having an acid value having a glass transition temperature of 0 ° C. to 55 ° C., an acetylene-based surfactant and / or It was found that it is effective to solve the problem by using an appropriate amount of alcohol alkoxylate-based surfactant and wax.
- the present invention is formed from one or more (meth) acrylate-based monomers and / or one or more vinyl-based monomers and has an acid value having a glass transition temperature of 0 ° C. to 55 ° C.
- a water-based liquid containing a copolymer, an acetylene-based surfactant and / or an alcohol alkoxylate-based surfactant in an amount of 0.1 to 1% by mass based on the total amount of ink, and a wax containing 0.5 to 5% by mass based on the total amount of ink. Provide ink.
- the present invention is a laminate having one or a plurality of printing layers on a base material, and at least one of the printing layers is a printing layer of the water-based liquid ink according to any one of claims 1 to 5. Provides a laminate that is.
- a water-based liquid ink having excellent viscosity stability, adhesion of a cured coating film to a substrate, and various coating film strengths, and a laminate using the water-based liquid ink it is possible to provide a water-based liquid ink having excellent viscosity stability, adhesion of a cured coating film to a substrate, and various coating film strengths, and a laminate using the water-based liquid ink. Further, even in a system to which a curing agent is added, a water-based liquid ink having excellent viscosity stability, adhesion of a cured coating film to a substrate, and various coating film strengths, and a laminate using the water-based liquid ink can be obtained. Can be provided.
- the water-based liquid ink of the present invention is an acid formed from one or more (meth) acrylate-based monomers and / or one or more vinyl-based monomers and having a glass transition temperature of 0 ° C. to 55 ° C.
- a copolymer having a value hereinafter sometimes referred to as a copolymer (A)
- a copolymer having a value hereinafter sometimes referred to as a copolymer (A)
- an acetylene-based surfactant and / or an alcohol alkoxylate-based surfactant in an amount of 0.1 to 1% by mass based on the total amount of the ink, and a wax in the ink. It is essential to contain 0.5 to 5% by mass based on the total amount.
- the copolymer (A) is a polymer or copolymer of one or more (meth) acrylate monomers, or a polymer or copolymer of one or more vinyl-based monomers, or one or more. It is a copolymer of the (meth) acrylate monomer and the vinyl-based monomer.
- the "(meth) acrylate” refers to either or both of acrylate and methacrylate
- (meth) acrylic refers to either or both of acrylic and methacrylic.
- the (meth) acrylate monomer is not particularly limited, and for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2 -Ethylhexyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, di Cyclopentanyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,
- vinyl monomer examples include vinyl acetate, vinyl propionate, vinyl versatic acid, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, (meth) acrylonitrile, styrene, ⁇ -methylstyrene, divinylstyrene, isoprene, and chloroprene.
- examples thereof include butadiene, ethylene, tetrafluoroethylene, vinylidene fluoride, N-vinylpyrrolidone and the like.
- styrene-based monomers such as styrene, ⁇ -methylstyrene, and divinylstyrene. Each of these may be used alone, or two or more types may be used in combination.
- one or more acidic groups selected from the group consisting of a carboxyl group and a carboxylate group in which the carboxyl group is neutralized with a basic compound, (meth) acrylic acid, crotonic acid, itaconic acid, It can be obtained by copolymerizing a (meth) acrylic monomer having a carboxyl group such as maleic acid, fumaric acid, ⁇ - (meth) acryloyloxyethyl hydrogen succinate, ⁇ - (meth) acryloyloxyethyl hydrogen phthalate.
- an acidic group is introduced, it is preferable to appropriately adjust the amount of the monomer so that the acid value is in a desired range, which will be described in detail later.
- the copolymer (A) a copolymer of two or more kinds of (meth) acrylate monomers or a copolymer of one or more kinds of (meth) acrylate monomers and a vinyl-based monomer is preferable.
- a copolymer of (meth) acrylate monomer having two or more kinds of carboxyl groups and (meth) acrylate monomer having a carboxyl group such as (meth) acrylic acid, having an acid value (meth).
- Acrylic copolymer (2) A copolymer of a (meth) acrylate monomer having two or more kinds of carboxyl groups, a styrene-based monomer, and a (meth) acrylate monomer having a carboxyl group such as (meth) acrylic acid.
- a styrene (meth) acrylic copolymer having an acid value is preferable.
- the (meth) acrylic monomer having no carboxyl group used in (1) and (2) is methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and iso-butyl.
- An aliphatic chain (meth) acrylate such as (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and hexyl (meth) acrylate is preferable.
- the copolymer (A) can be produced, for example, by polymerizing various monomers in a temperature range of 50 ° C. to 180 ° C. in the presence of a polymerization initiator, and more if it is in a temperature range of 80 ° C. to 150 ° C. preferable.
- the polymerization method include a massive polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method.
- examples of the polymerization mode include random copolymers, block copolymers, graft copolymers, and the like.
- the copolymer (A) used in the present invention may be an emulsion forming a core-shell type.
- the core-shell type emulsion refers to a state in which the polymer (a2) is dispersed in an aqueous medium by the polymer (a1), and usually, the polymer (a1) is present on the outermost side of the resin particles to form a shell. In many cases, a portion is formed and a part or all of the polymer (a2) forms a core portion.
- the resin forming the shell portion will be referred to as a polymer (a1)
- the resin forming the core portion will be referred to as a polymer (a2).
- the core-shell emulsion used in the present invention is one or more hydrophilic groups selected from the group consisting of a carboxyl group and a carboxylate group formed by neutralizing the carboxyl group (a1) constituting the shell portion. It is preferably composed of one containing an acrylic copolymer having.
- the acid value of the shell portion is preferably in the range of 40 mgKOH / g or more and 250 mgKOH / g or less, and more preferably 120 mgKOH / g or less.
- the carboxyl group of the polymer (a1) constituting the shell portion is neutralized with a basic compound to form a carboxylate group.
- ammonia, triethylamine, morpholine, monoethanolamine, diethylethanolamine and the like can be used, and it is possible to use ammonia and triethylamine for the temperature resistance of the coating film. , It is preferable to further improve the corrosion resistance and the chemical resistance.
- the monomers having a polymerizable unsaturated double bond it is preferable to use a monomer obtained by polymerizing a (meth) acrylic monomer containing a (meth) acrylic monomer having a carboxyl group.
- a monomer obtained by polymerizing a (meth) acrylic monomer containing a (meth) acrylic monomer having a carboxyl group methyl (meth) acrylate, butyl (meth) acrylate, in order to adjust the glass transition temperature (Tg1) of the polymer (a1) in the range of 20 ° C. to 100 ° C.
- Tg1 glass transition temperature
- the weight average molecular weight of the core portion is preferably in the range of 200,000 to 3,000,000, and more preferably 800,000 or more.
- Tg is preferably in the range of ⁇ 30 ° C. to 30 ° C.
- a copolymer such as an acrylic monomer similar to the above-mentioned acrylic resin can be used, but among them, it is preferably produced in an aqueous medium. Specifically, it can be produced by collectively supplying or sequentially supplying the monomer and the polymerization initiator or the like to a reaction vessel containing an aqueous medium for polymerization. At that time, a pre-emulsion is produced by mixing the monomer, an aqueous medium, and a reactive surfactant or the like in advance, and the polymerization initiator or the like is supplied to a reaction vessel containing the aqueous medium. It may be polymerized.
- Examples of the polymerization initiator that can be used in producing the polymer (a2) include radical polymerization initiators such as persulfate, organic peroxide, and hydrogen peroxide, and 4,4'-azobis (4-cyano). Azo initiators such as valerate) and 2,2'-azobis (2-amidinopropane) dihydrochloride can be used.
- the radical polymerization initiator may be used as a redox polymerization initiator in combination with a reducing agent described later.
- persulfate for example, potassium persulfate, sodium persulfate, ammonium persulfate and the like can be used.
- organic peroxide include benzoyl peroxide, lauroyl peroxide, decanoyyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, t-butyl peroxylaurate, and t-butyl peroxybenzoate.
- Kumen hydroperoxide, paramentan hydroperoxide, t-butyl hydroperoxide and the like can be used.
- reducing agent examples include ascorbic acid and its salt, erythorbic acid and its salt (sodium salt, etc.), tartrate acid and its salt, citric acid and its salt, formaldehyde sulfoxylate metal salt, sodium thiosulfate, and the like.
- Sodium bicarbonate, ferric chloride, etc. can be used.
- the amount of the polymerization initiator used may be an amount that allows the polymerization to proceed smoothly, but it is preferable that the amount used is as small as possible from the viewpoint of maintaining the excellent corrosion resistance of the obtained coating film, and is used for producing the vinyl polymer (a2). It is preferably 0.01% by mass to 0.5% by mass with respect to the total amount of the monomers used.
- the total amount of the polymerization initiator used is preferably within the above range.
- a reactive surfactant an anionic surfactant, a nonionic surfactant, a cationic surfactant, a zwitterionic surfactant and the like are used. May be good.
- the acid value of the copolymer (A) is preferably 20 mgKOH / g or more, 120 mgKOH / g or less, and more preferably 25 mgKOH or more.
- the acid value referred to here indicates the number of milligrams of potassium hydroxide required to neutralize the acidic component contained in 1 g of the resin.
- the weight average molecular weight of the copolymer (A) is preferably in the range of 5,000 to 100,000.
- the weight average molecular weight is 5,000 or more, the heat resistance of the resin film does not decrease, and the friction resistance and the water friction resistance of the laminate tend to be maintained. If it is 100,000 or less, the laminate tends to have both substrate adhesion and scratch resistance.
- the glass transition temperature (sometimes referred to as Tg) of the copolymer (A) is preferably in the range of 0 ° C. to 55 ° C.
- Tg glass transition temperature
- the glass transition temperature (Tg) refers to a so-called calculated glass transition temperature, and refers to a value calculated by the following method.
- Tg (° C.) Tg (K) -273 W1, W2, ... Wn in the formula 1 represent the mass% of each monomer with respect to the total mass of the monomers used for producing the polymer, and T1, T2, ... Tn are the homopolymers of each monomer. Represents the glass transition temperature (K).
- T1, T2, ... Tn the values described in Polymer Handbook (Fourth Edition, J. Brandrup, E.H. Immunogut, EA Grulke) are used.
- the glass transition temperature of the homopolymer of each monomer is not described in the Polymer Hand Book, the glass transition temperature is based on JIS K7121 using a differential scanning calorimeter "DSC Q-100" (manufactured by TA Instrument). It was measured by the method described above. Specifically, the polymer from which the solvent has been completely removed by vacuum suction is measured for a change in calorific value in the range of -100 ° C to + 200 ° C at a heating rate of 20 ° C./min, and a straight line extending each baseline. The point where the straight line equidistant from the vertical axis direction and the curve of the stepwise change portion of the glass transition intersect was defined as the glass transition temperature.
- the copolymer (A) is preferably contained in the aqueous liquid ink of the present invention in an amount of 5 to 50% by mass in terms of solid content.
- the content of the copolymer (A) is 5% by mass or more, the strength of the ink coating film does not decrease, and the substrate adhesion, water friction resistance, and the like are kept good.
- it is 50% by mass or less, the decrease in coloring power can be suppressed, the high viscosity can be avoided, and the workability does not decrease.
- an acetylene-based surfactant and / or an alcohol alkoxylate-based surfactant is preferable.
- the acetylene-based surfactant used in the present invention 2,5-dimethyl-3-hexyne-2,5-diol, 3,6-dimethyl-4-octyne-3,6-diol, 2, 4,7,9-Tetramethyl-5-decine-4,7-diol, 3,5-dimethyl-1-hexyne-3-ol, 3-methyl-1-butyne-3-ol, 3-methyl-1 -Pentyne-3-ol, 3-hexyne-2,5-diol, 2-butyne-1,4-diol and the like can be mentioned.
- Commercially available products include alkylene oxide-non-modified acetylene glycol-based surfactants such as Surfinol 61, 82,
- an alkylene oxide-modified acetylene glycol-based surfactant is preferable.
- Specific examples of the alcohol alkoxylate-based surfactant used in the present invention include alcohol ethoxylate and alcohol polyethoxylate, and commercially available products include DYNWET800 (manufactured by Big Chemie Japan). These acetylene-based surfactants and alcohol alkoxylate-based surfactants may be used alone or in combination of two or more.
- the total amount of the acetylene-based surfactant and / or the alcohol alkoxylate-based surfactant added is preferably 0.1 to 1% by mass of the total amount of the ink.
- These acetylene-based surfactants may be used alone or in combination of two or more, and the total amount of the acetylene-based surfactant and / or the alcohol alkoxylate-based surfactant added is When it is 0.1% by mass or more of the total amount of ink, the coatability with the base material is improved and the adhesion with the base material can be maintained.
- the total amount of the acetylene-based surfactant and / or the alcohol alkoxylate-based surfactant added is 1% by mass or less of the total amount of the ink, the abrasion resistance, the water abrasion resistance, and the scratch resistance may decrease. Absent. Further, if necessary, other acrylic polymer-based surfactants (for example, Polyflow WS-314 Kyoeisha Chemical Co., Ltd.) and modified silicone-based surfactants (for example, Polyflow KL-401 Kyoeisha Chemical Co., Ltd.) are used. You may. For the above reasons, the total amount of the surfactant used is preferably 0.1 to 1% by mass of the total amount of the ink.
- a hydrocarbon wax is preferable. Specific examples thereof include liquid paraffin, natural paraffin, synthetic paraffin, microcrystalline wax, polyethylene wax, fluorocarbon wax, ethylene-propylene copolymer wax, tetrafluoride ethylene resin wax, Fisher Tropsch wax and the like. Of these, polyethylene wax is preferable. These waxes may be used alone or in combination of two or more, and the total amount of these waxes added is preferably 0.5 to 5% by mass of the total amount of the ink. When the total amount of wax added is 0.5% by mass or more of the total amount of ink, abrasion resistance, water abrasion resistance, and scratch resistance can be maintained. When the total amount of wax added is 5% by mass or less of the total amount of ink, adhesion to the substrate, abrasion resistance, water abrasion resistance, and scratch resistance can be maintained.
- a curing agent capable of reacting with an acid may be used in combination.
- the curing agent capable of reacting with the acid is not particularly limited, and a known curing agent that can be used in an aqueous medium can be used.
- a known curing agent that can be used in an aqueous medium can be used.
- an epoxy-based curing agent, a carbodiimide-based curing agent, an oxazoline-based curing agent, and the like can be mentioned.
- the epoxy-based curing agent is not particularly limited as long as it is a compound having at least one epoxy group.
- examples of the epoxy-based curing agent include epoxy resins such as bisphenol A diglycidyl ether, modified bisphenol A diglycidyl ether, novolak glycidyl ether, glycerin polyglycidyl ether, and polyglycerin polyglycidyl ether.
- a polycarbodiimide compound having at least two or more carbodiimide groups is preferable.
- the oxazoline-based curing agent is not particularly limited as long as it is a compound having an oxazoline skeleton.
- Specific examples of the oxazoline-based curing agent include the Epocross series manufactured by Nippon Shokubai Co., Ltd.
- Examples of the epoxy compound include bisphenol A diglycidyl ether and its oligomer, hydride bisphenol A diglycidyl ether and its oligomer, orthophthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, and p-oxybenzoic acid.
- Diglycidyl ester tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, succinic acid diglycidyl ester, adipate diglycidyl ester, sebacic acid diglycidyl ester, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether , 1,4-Butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether and polyalkylene glycol diglycidyl ethers, trimeric acid triglycidyl ester, triglycidyl isocyanurate, 1,4-diglycidyloxybenzene, Examples thereof include diglycidyl propylene urea, glycerol triglycidyl ether, trimethylol ethane triglycidyl ether, trimethylol propane triglycidyl
- the amount of the curing agent added in the present invention is preferably 0.1 to 10.0% by mass, more preferably 0.5 to 9.0% by mass in terms of solid content of the total amount of ink. If the amount added is 0.1% by mass or more, the effect as a curing agent can be obtained, while if it is 10.0% by mass or less, the substrate adhesion, abrasion resistance, and water friction resistance tend to be maintained. Become.
- solvent As the solvent contained in the aqueous liquid ink of the present invention, water alone or an organic solvent miscible with water can be used.
- organic solvent include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol and n-propyl alcohol, polyhydric alcohols such as propylene glycol and glycerin, propylene glycol monomethyl ether, propylene glycol monoethyl ether and propylene glycol mono n.
- -Ethers such as propyl ether and ethyl carbitol can be mentioned.
- the water-based liquid ink of the present invention becomes a transparent film after printing if it does not contain a coloring material, and is a colorless transparent ink (in the present technical field, it is used for the purpose of solid printing on the outermost layer of a color printing layer to protect the color printing layer. Therefore, it is also commonly referred to as overcoat varnish or OP varnish. In the present invention, it may be referred to as OP varnish). Of course, it also contains a coloring material and is used as an ink for so-called white, black, and color printing. Specific examples of the coloring material include inorganic pigments and organic pigments used in general inks, paints, recording agents and the like.
- Organic pigments include soluble azo-based, insoluble azo-based, azo-based, phthalocyanine-based, halogenated phthalocyanine-based, anthraquinone-based, anthraslon-based, dianthraquinone-based, anthrapyrimidine-based, perylene-based, perinone-based, quinacridone-based, Pigments such as thioindigo-based, dioxazine-based, isoindolinone-based, quinophthalone-based, azomethine-azo-based, flavanthlon-based, diketopyrrolopyrrole-based, isoindoline-based, indanslon-based, and carbon black-based pigments can be mentioned.
- Carmin 6B Lake Red C, Permanent Red 2B, Disazo Yellow, Pyrazolone Orange
- Carmin FB Chromophtal Yellow, Chromophtal Red, Phthalocyanine Blue, Phthalocyanine Green, Dioxazine Violet, Quinacridone Magenta, Quinacridone Red, Indance.
- Examples thereof include lonblue, pyrimidine yellow, thioindigo bordeaux, thioindigo magenta, perylene red, perinone orange, isoindolinone yellow, aniline black, diketopyrrolopyrrole red, and daylight fluorescent pigment.
- both unacidified treated pigments and acidic treated pigments can be used. Specific examples of preferable organic pigments are given below.
- black pigment examples include C.I. I. Pigment Black 1, C.I. I. Pigment Black 6, C.I. I. Pigment Black 7, C.I. I. Pigment Black 9, C.I. I. Pigment Black 20 and the like.
- Examples of the indigo pigment include C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 1, C.I. I. Pigment Blue 15: 2, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 15: 5, C.I. I. Pigment Blue 15: 6, C.I. I. Pigment Blue 16, C.I. I. Pigment Blue 17: 1, C.I. I. Pigment Blue 22, C.I. I. Pigment Blue 24: 1, C.I. I. Pigment Blue 25, C.I. I. Pigment Blue 26, C.I. I. Pigment Blue 60, C.I. I. Pigment Blue 61, C.I. I.
- Pigment Blue 62 C.I. I. Pigment Blue 63, C.I. I. Pigment Blue 64, C.I. I. Pigment Blue 75, C.I. I. Pigment Blue 79, C.I. I. Pigment Blue 80 and the like.
- green pigments examples include C.I. I. Pigment Green 1, C.I. I. Pigment Green 4, C.I. I. Pigment Green 7, C.I. I. Pigment Green 8, C.I. I. Pigment Green 10, C.I. I. Pigment Green 36 and the like.
- red pigment examples include C.I. I. Pigment Red 1, C.I. I. Pigment Red 2, C.I. I. Pigment Red 3, C.I. I. Pigment Red 4, C.I. I. Pigment Red 5, C.I. I. Pigment Red 6, C.I. I. Pigment Red 7, C.I. I. Pigment Red 8, C.I. I. Pigment Red 9, C.I. I. Pigment Red 10, C.I. I. Pigment Red 11, C.I. I. Pigment Red 12, C.I. I. Pigment Red 15, C.I. I. Pigment Red 16, C.I. I. Pigment Red 17, C.I. I. Pigment Red 18, C.I. I. Pigment Red 19, C.I. I. Pigment Red 20, C.I. I.
- Pigment Red 112 C.I. I. Pigment Red 114, C.I. I. Pigment Red 119, C.I. I. Pigment Red 122, C.I. I. Pigment Red 123, C.I. I. Pigment Red 136, C.I. I. Pigment Red 144, C.I. I. Pigment Red 146, C.I. I. Pigment Red 147, C.I. I. Pigment Red 149, C.I. I. Pigment Red 150, C.I. I. Pigment Red 164, C.I. I. Pigment Red 166, C.I. I. Pigment Red 168, C.I. I. Pigment Red 169, C.I. I. Pigment Red 170, C.I. I.
- Pigment Red 220 C.I. I. Pigment Red 221 and C.I. I. Pigment Red 223, C.I. I. Pigment Red 224, C.I. I. Pigment Red 226, C.I. I. Pigment Red 237, C.I. I. Pigment Red 238, C.I. I. Pigment Red 239, C.I. I. Pigment Red 240, C.I. I. Pigment Red 242, C.I. I. Pigment Red 245, C.I. I. Pigment Red 247, C.I. I. Pigment Red 248, C.I. I. Pigment Red 251 and C.I. I. Pigment Red 253, C.I. I. Pigment Red 254, C.I. I.
- Examples of purple pigments include C.I. I. Pigment Violet 1, C.I. I. Pigment Violet 2, C.I. I. Pigment Violet 3, C.I. I. Pigment Violet 3: 1, C.I. I. Pigment Violet 3: 3, C.I. I. Pigment Violet 5: 1, C.I. I. Pigment Violet 13, C.I. I. Pigment Violet 19 ( ⁇ type, ⁇ type), C.I. I. Pigment Violet 23, C.I. I. Pigment Violet 25, C.I. I. Pigment Violet 27, C.I. I. Pigment Violet 29, C.I. I. Pigment Violet 31, C.I. I. Pigment Violet 32, C.I. I. Pigment Violet 36, C.I. I. Pigment Violet 37, C.I. I. Pigment Violet 38, C.I. I. Pigment Violet 42, C.I. I. Pigment Violet 50 and the like.
- yellow pigment examples include C.I. I. Pigment Yellow 1, C.I. I. Pigment Yellow 3, C.I. I. Pigment Yellow 12, C.I. I. Pigment Yellow 13, C.I. I. Pigment Yellow 14, Pigment Yellow 17, C.I. I. Pigment Yellow 24, C.I. I. Pigment Yellow 42, C.I. I. Pigment Yellow 55, C.I. I. Pigment Yellow 62, C.I. I. Pigment Yellow 65, C.I. I. Pigment Yellow 74, C.I. I. Pigment Yellow 83, C.I. I. Pigment Yellow 86, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 94, C.I. I. Pigment Yellow 95, C.I. I.
- Pigment Yellow 109 C.I. I. Pigment Yellow 110, C.I. I. Pigment Yellow 117, C.I. I. Pigment Yellow 120, Pigment Yellow 125, C.I. I. Pigment Yellow 128, C.I. I. Pigment Yellow 129, C.I. I. Pigment Yellow 137, C.I. I. Pigment, Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 147, C.I. I. Pigment Yellow 148, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 151, C.I. I. Pigment Yellow 153, C.I. I. Pigment Yellow 154, C.I. I.
- Pigment Yellow 155 C.I. I. Pigment Yellow 166, C.I. I. Pigment Yellow 168, C.I. I. Pigment Yellow 174, C.I. I. Pigment Yellow 180, C.I. I. Pigment Yellow 185 and C.I. I. Pigment Yellow 213 and the like.
- orange pigment examples include C.I. I. Pigment Orange 5, C.I. I. Pigment Orange 13, C.I. I. Pigment Orange 16, C.I. I. Pigment Orange 34, C.I. I. Pigment Orange 36, C.I. I. Pigment Orange 37, C.I. I. Pigment O Orange 38, C.I. I. Pigment Orange 43, C.I. I. Pigment Orange 51, C.I. I. Pigment range 55, C.I. I. Pigment Orange 59, C.I. I. Pigment Orange 61, C.I. I. Pigment Orange 64, C.I. I. Pigment Orange 71, or C.I. I. Pigment Orange 74 and the like.
- brown pigments examples include C.I. I. Pigment Brown 23, C.I. I. Pigment Brown 25, or C.I. I. Pigment Brown 26 and the like.
- C.I. I. Pigment Black 7 As an indigo pigment, C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 1, C.I. I. Pigment Blue 15: 2, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 15: 6, As a green pigment, C.I. I. Pigment Green 7, As a red pigment, C.I. I. Pigment Red 57: 1, C.I. I. Pigment Red 48: 1, C.I. I. Pigment Red 48: 2, C.I. I. Pigment Red 48: 3, C.I. I. Pigment Red 146, C.I.
- inorganic pigments examples include white inorganic pigments such as titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silica, lithobon, antimony white, and gypsum.
- white inorganic pigments such as titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silica, lithobon, antimony white, and gypsum.
- titanium oxide has a white color and is preferable from the viewpoints of coloring power, hiding power, chemical resistance and weather resistance, and from the viewpoint of printing performance, the titanium oxide is preferably treated with silica and / or alumina.
- non-white inorganic pigments examples include aluminum particles, mica (mica), bronze powder, chrome vermilion, chrome yellow, cadmium yellow, cadmium red, ultramarine, dark blue, red iron oxide, yellow iron oxide, iron black, and zircon.
- aluminum is in the form of powder or paste, it is preferably used in the form of paste from the viewpoint of handleability and safety, and whether chrome yellow or non-leafing is used is appropriately selected from the viewpoint of brightness and density.
- the average particle size of the pigment is preferably in the range of 1 to 300 nm, more preferably about 50 to 150 nm.
- the amount of the pigment is sufficient to secure the concentration and coloring power of the water-based liquid printing ink, that is, 1 to 60% by weight based on the total weight of the ink composition, and 10 to 10 to 60% by weight of the solid content in the ink composition. It is preferably contained in a proportion of 90% by weight.
- these pigments can be used alone or in combination of two or more.
- the water-based liquid ink of the present invention may be used as a general-purpose resin other than the copolymer (A), a extender pigment, a pigment dispersant, a leveling agent, a defoaming agent, a plasticizer, an infrared absorber, an ultraviolet absorber, as required. It can contain a fragrance, a flame retardant, and the like. Among them, fatty acid amides such as oleic acid amide, stearic acid amide, and erucic acid amide for imparting abrasion resistance and slipperiness, and silicon-based and non-silicon-based defoamers for suppressing foaming during printing. It often contains various pigment dispersants and the like that improve the wetting of pigments.
- a pigment, water alone, or a mixture containing water and an organic solvent mixed with water, a pigment dispersant, a defoaming agent, etc. is dispersed by a disperser to obtain a pigment dispersion.
- the aqueous liquid ink of the present invention can be obtained by adding an additive such as a resin, water, or an organic solvent miscible with water, and if necessary, a leveling agent, to the obtained pigment dispersion, and stirring and mixing.
- a bead mill, an Eiger mill, a sand mill, a gamma mill, an attritor, or the like which are generally used for manufacturing gravure and flexographic printing inks, are used.
- the water-based liquid ink of the present invention When used as a flexo ink, its viscosity may be 7 to 25 seconds at 25 ° C., more preferably 10 to 20 seconds, using Zahn Cup # 4 manufactured by Rigosha.
- the surface tension of the obtained flexographic ink at 25 ° C. is preferably 25 to 50 mN / m, more preferably 33 to 43 mN / m.
- the lower the surface tension of the ink the better the wettability of the ink to the substrate such as a film.
- the surface tension is less than 25 mN / m, the ink spreads and the halftone dots are adjacent to each other. Tend to be easily connected, which tends to cause stains on the printed surface called dot bridge.
- the surface tension exceeds 50 mN / m the wettability of the ink to a base material such as a film is lowered, which tends to cause repelling.
- the water-based liquid ink of the present invention when used as a gravure ink, its viscosity may be 7 to 25 seconds at 25 ° C. using Zahn Cup # 3 manufactured by Rigosha, more preferably 10 to 20 seconds. is there.
- the surface tension of the obtained gravure ink at 25 ° C. is preferably 25 to 50 mN / m, more preferably 33 to 43 mN / m, as with flexographic ink.
- the lower the surface tension of the ink the better the wettability of the ink to the substrate such as a film.
- the surface tension is less than 25 mN / m, the ink spreads and the halftone dots are adjacent to each other.
- a printed matter is obtained by printing the water-based liquid ink of the present invention on a substrate and providing a printed layer.
- a printing layer is obtained by applying an ink to a base material using a gravure method or a flexographic printing method, drying the ink by drying in an oven, and fixing the ink.
- the drying temperature is usually about 40 to 60 ° C.
- Flexographic printing is a type of letterpress printing, in which a rubber plate is mainly used as a printing plate (letter plate), and a fine mesh engraving roll called anilox roll is used for a portion that supplies ink to the printing plate.
- Anilox roll receives ink from a chamber type doctor and applies ink on the printing plate, and has an advantage that the ink can be uniformly transferred to the printing plate via the anilox roll.
- ink is applied to the bulkhead and the surface of the anilox roll having many openings surrounded by the bulkhead, and the doctor is pressed against the surface of the anilox roll to scrape off the ink existing on the top surface of the bulkhead of the anilox roll. , Fill the recesses, which are the openings, with ink. Subsequently, the flexographic plate is pressed against the anilox roll to transfer the ink existing in the concave portion of the anilox roll to the convex portion (pattern portion) of the printing plate, and then the plate is brought into contact with the substrate and exists in the pattern portion of the plate. The ink to be used is transferred to a substrate to obtain a printed matter.
- a rotary printing method may be combined.
- rotary printing is performed on the surface of a wound thermoplastic resin film using a water-based liquid ink.
- processes such as laminating, slitting (cutting unnecessary parts in the width portion), and bag making (cutting and heat-sealing to make a bag) can be performed.
- High-speed printing is possible and productivity is excellent by winding the liquid printing ink and rotating it on a thermoplastic resin film.
- the rotary printing means gravure rotary printing and flexographic rotary printing, and does not include ink jet printing and silk screen printing, which are other printing methods.
- ink is supplied directly from a container for storing liquid printing ink or via an ink supply pump or the like to an Anirox roller having an uneven shape on the surface, and the ink supplied to the Anirox roller is used on the plate surface.
- the contact with the convex portion transfers to the plate surface, and the contact between the plate surface and the thermoplastic resin film finally transfers to the thermoplastic resin film to form a pattern and / or characters.
- the ink drying property is slightly inferior to that of the solvent-based flexographic printing ink, so that the ink film thickness is preferably as thin as possible. From this point of view, it is preferable that the amount of ink supplied to the Aronix roller is as small as possible.
- the print density tends to decrease as the film thickness decreases, so the pigment concentration of the water-based flexographic printing ink used may be appropriately controlled. Specifically, when the pigment concentration of the water-based flexographic printing ink is 1 to 5% by weight higher than the concentration of the solvent-type flexographic printing ink, an appropriate printing density can be obtained.
- the take-up thermoplastic resin film is a roll-shaped thermoplastic resin film having a specified width, which is different from the sheet paper in which each sheet is separated in advance, and is a film for rotary printing. Is.
- the width of the film is appropriately selected based on the plate width of the rotary printing press to be used and the width of the image (picture) portion of the gravure plate.
- the printing order thereof is not particularly limited.
- the color ink in the case of back printing, it is common to print the color ink on the take-up thermoplastic resin film first, and then print the white ink.
- the color ink has a plurality of colors, for example, black, cyan, magenta, and yellow can be printed in this order, but the printing is not particularly limited.
- special colors and the like can be used in addition to the basic colors. That is, the large-sized printing machine has a plurality of printing units corresponding to 5 to 10 colors, one printing unit is provided with one color of ink, and 5 to 10 colors can be overprinted at one time.
- the printed matter obtained by back printing may be used as it is, or an anchor coating agent, an adhesive or the like may be applied to the printed surface of the rotary printed matter obtained by the above method, and if necessary, after drying, a film or the like may be used. It can also be laminated with.
- the printed matter of the water-based liquid ink (A) of the present invention is excellent in coating film strength, particularly abrasion resistance and scratch resistance, and is therefore suitable for a form in which the printed layer is the outermost layer.
- a printed matter having a printed layer of the water-based liquid ink (A) in the present invention on the surface that becomes the outermost layer at the time of distribution is preferable because the effect of the present invention can be maximized.
- the laminate of the present invention may be a laminate that includes a printed matter having a printed layer of the water-based liquid ink of the present invention on a substrate by a printing method using a plate.
- the base material examples include paper, synthetic paper, thermoplastic resin film, steel plate, aluminum foil, wood, woven cloth, knitted cloth, non-woven fabric, gypsum board, wood board and the like. Of these, paper, synthetic paper, thermoplastic resin film and the like are preferable. Further, a base material obtained by combining a plurality of types of these base materials may be used, for example, a base material in which paper and a thermoplastic resin film are laminated, or a base material in which a thermoplastic resin film and an aluminum foil are laminated.
- the laminating method is not particularly limited, and a general-purpose one-component adhesive, a two-component adhesive, or the like may be used for bonding, or if there are a plurality of thermoplastic resin films, the laminated body is bonded by extrusion molding. It may be.
- the thermoplastic resin film is not particularly limited, and for example, polyamide resins such as nylon 6, nylon 66, and nylon 46, polyethylene phthalate (PET), polyethylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, and polybutylene.
- PET polyethylene phthalate
- Biodegradable resins typified by polyester resins such as terephthalate and polybutylene naphthalate, polyhydroxycarboxylic acids such as polylactic acid, and aliphatic polyester resins such as poly (ethylene succinate) and poly (butylene succinate).
- Examples thereof include films made of polyolefin resins such as polypropylene (PP) and polyethylene, polyimide resins, polyarylate resins or thermoplastic resins such as mixtures thereof, and laminates thereof.
- polyester, polyamide, polyethylene and polypropylene are used.
- a film can be preferably used. These films may be unstretched films or stretched films, and the production method thereof is not limited.
- the thickness of the base film is not particularly limited, but usually it may be in the range of 1 to 500 ⁇ m. Further, if the printed surface of the film is subjected to a corona discharge treatment, the adhesion to the base material can be further improved, which is preferable. Further, silica, alumina or the like may be vapor-deposited, or a gas barrier coat layer such as an oxygen gas barrier layer may be laminated. I.
- the base paper When paper is used as the base material, examples of the base paper include kraft paper, liner paper, art paper, coated paper, and carton paper. Moreover, you may use synthetic paper.
- the structure of the synthetic paper is not particularly limited and may be a single-layer structure or a multi-layer structure.
- the multilayer structure for example, there are a two-layer structure of a base material layer and a surface layer, a three-layer structure in which the base material layer and the front and back surfaces are present, and another resin film layer between the base material layer and the surface layer.
- a multi-layer structure can be exemplified. Further, each layer may or may not contain an inorganic or organic filler. Further, a microporous synthetic paper having a large number of fine voids can also be used.
- a printing layer using the water-based liquid ink of the present invention is provided on the base material, and the printing layer may be one layer or a plurality of layers.
- white, process color black (also referred to as black, blackish color), red (also referred to as magenta, reddish color), indigo (also referred to as cyan, bluish color) ), Yellow (also referred to as yellow, which is a yellowish color), and special color inks other than these basic colors are appropriately combined for printing.
- the water-based liquid of the present invention is applied to each of these color inks.
- An ink can be used, or a general-purpose water-based or oil-based liquid ink other than the water-based liquid ink of the present invention and the water-based liquid ink of the present invention, or an overcoat varnish can be used in combination.
- a commercially available overcoat varnish can be used, but as described above, it can also be used as an overcoat varnish in a form that does not contain a coloring material in the water-based liquid ink of the present invention.
- the printing layer using the water-based liquid ink of the present invention is referred to as "the present printing layer (color)".
- “General-purpose printing layer (color)” is the printing layer using general-purpose water-based liquid ink.
- the water-based liquid ink overcoat varnish of the present invention is referred to as "this OP”.
- the printing layer using the water-based liquid ink of the present invention is adjacent to the base material ( (Other than white) is provided, and the water-based liquid ink overcoat varnish of the present invention is provided adjacent to the print layer (other than white). It means that.
- the base material is preferably a thermoplastic resin film.
- the thermoplastic film having a printed matter having a print layer other than white and a white print layer, preferable visibility can be obtained.
- a general-purpose water-based liquid ink is more preferably a printing ink containing a polyurethane resin or an acrylic polyurethane resin and a pigment.
- a printing ink containing a polyurethane resin or an acrylic polyurethane resin and a pigment may be referred to as a printing ink (B).
- the coating film is more flexible than the acrylic resin. This is preferable because it has high adhesion to the thermoplastic resin film and high followability due to deformation of the film base material.
- the polyurethane resin or acrylic polyurethane resin has the same or better performance as the acrylic resin in terms of pigment dispersibility, resolubility during printing, and color development when the pigment is dispersed, and is compatible with the pigment. ..
- a printing ink containing an acrylic polyurethane resin is more preferable than a printing ink containing a polyurethane resin because it has better color development and resolubility and is less likely to cause stringing during printing.
- both the polyurethane resin and the acrylic polyurethane resin may be mixed and used, or if necessary, the acrylic resin may be appropriately mixed and used.
- the polyurethane resin used in the printing ink (B) preferably has a weight average molecular weight of 20,000 to 2,000,000 and an acid value of 10 to 50 mgKOH / g, more preferably a weight average molecular weight of 30, It is 000 to 1,500,000 and 20 to 50 mgKOH / g. If the weight average molecular weight is 20,000 or more, the friction resistance and the water friction resistance do not decrease, and if the weight average molecular weight is 2,000,000 or less, the decrease in substrate adhesion is suppressed. Can be done.
- the acid value when the acid value is 10 mgKOH / g or more, the resolubility of the ink film in the aqueous solvent in printing is deteriorated, and the tone reproducibility of the printed matter is not deteriorated, and the image when the liquid printing ink laminate is formed. It is also possible to suppress a decrease in reproducibility.
- the acid value when the acid value is 50 mgKOH / g or less, the water resistance of the resin does not decrease, and the deterioration of the substrate adhesion and the water friction resistance of the printed layer can be suppressed.
- the acid value referred to here indicates the number of milligrams of potassium hydroxide required to neutralize the acidic component contained in 1 g of the resin.
- the acrylic polyurethane resin used in the printing ink (B) preferably has a weight average molecular weight of 20,000 to 2,000,000 and an acid value of 10 to 60 mgKOH / g, more preferably a weight average molecular weight of 30. It is 000 to 1,500,000 and 20 to 50 mgKOH / g. If the weight average molecular weight is 20,000 or more, the friction resistance and the water friction resistance do not decrease, and if the weight average molecular weight is 2,000,000 or less, the decrease in substrate adhesion is suppressed. Can be done. Further, when the acid value is 10 mgKOH / g or more, the image reproducibility as a liquid printing ink laminate can be well maintained without deteriorating the tone reproducibility of the printed matter. On the other hand, when the acid value is 60 mgKOH / g or less, the water resistance of the resin does not decrease, and the substrate adhesion and water friction resistance of the laminate can be kept good.
- the printing layer of the water-based liquid ink (A) of the present invention is excellent in coating film strength, particularly abrasion resistance and scratch resistance, and is therefore the farthest from the outermost layer of the laminate, that is, the thermoplastic resin film which is the base material.
- the strength of the laminated body becomes more sufficient, and basic coatings such as substrate adhesion, abrasion resistance, water friction resistance, and scratch resistance are applied.
- the film strength tends to be more retained.
- the printing layer at this time may be appropriately applied as a color ink containing a color material or as an overcoat varnish containing no color material depending on the desired design.
- the most commonly applied color ink containing a coloring material is a white ink containing a white pigment.
- a print layer in which a plurality of layers of the same color (for example, white ink again on the white ink) are laminated may be.
- a printing layer may be formed in which a plurality of layers of overcoat varnish containing no coloring material are laminated on a color ink (for example, white ink).
- the viscosity stability of the ink is slightly lowered by the increase in the curing speed, but the substrate adhesion and resistance to the substrate. It is possible to obtain a tougher laminate having abrasion resistance, water friction resistance, and scratch resistance.
- the laminate having the print layer of the water-based liquid ink (A) of the present invention is suitable for a form in which the print layer is the outermost layer because the print layer is excellent in coating film strength, particularly abrasion resistance and scratch resistance.
- a printed matter having a printed layer of the water-based liquid ink (A) in the present invention on the surface that becomes the outermost layer at the time of distribution is preferable because the effect of the present invention can be maximized. It can be applied to various applications such as plastic labels (corresponding to shrink labels and body-wrap labels) applied to beverage and food bottles, integrated packaging, and exterior packaging.
- the weight average molecular weight (in terms of polystyrene) measured by GPC (gel permeation chromatography) in the present invention was measured using an HLC8220 system manufactured by Toso Co., Ltd. under the following conditions. Separation column: Uses 4 TSKgelGMH HR- N manufactured by Tosoh Corporation. Column temperature: 40 ° C. Moving layer: Tetrahydrofuran manufactured by Wako Pure Chemical Industries, Ltd. Flow velocity: 1.0 ml / min. Sample concentration: 1.0% by mass. Sample injection volume: 100 microliters. Detector: Differential refractometer.
- the acid value of the acrylic resin indicates the number of milligrams of potassium hydroxide required to neutralize the acidic component contained in 1 g of the resin, and each dried water-soluble resin was prepared according to JIS K2501. It was calculated from potentiometric titration with a potassium hydroxide / ethanol solution.
- the glass transition temperature (Tg) refers to the so-called calculated glass transition temperature, and refers to a value calculated by the following method.
- Equation 1) 1 / Tg (K) (W1 / T1) + (W2 / T2) + ... (Wn / Tn)
- Tg (° C.) Tg (K) -273 W1, W2, ...
- Wn in the formula 1 represent the mass% of each monomer with respect to the total mass of the monomers used for producing the polymer, and T1, T2, ... Tn are the homopolymers of each monomer.
- T1, T2, ... Tn the values described in Polymer Handbook (Fourth Edition, J. Brandrup, E.H. Immersut, EA Grulke) are used.
- the glass transition temperature of the homopolymer of each monomer is not described in the Polymer Hand Book, the glass transition temperature is based on JIS K7121 using a differential scanning calorimeter "DSC Q-100" (manufactured by TA Instrument). It was measured by the method described above.
- the polymer from which the solvent has been completely removed by vacuum suction is measured for a change in calorific value in the range of -100 ° C to + 200 ° C at a heating rate of 20 ° C./min, and an extended straight line of each baseline.
- the point where the straight line equidistant from the vertical axis direction and the curve of the stepwise change portion of the glass transition intersect was defined as the glass transition temperature.
- the reaction was carried out for another 6 hours. After completion of the reaction, the mixture was cooled and neutralized by adding 20.0 parts of 30% aqueous ammonia to the obtained acrylic resin solution. Further, ion-exchanged water was added and solvent substitution was carried out while heating to obtain an aqueous solution of an acrylic resin having a solid content of 30%.
- the acid value was 250 mgKOH / g, Tg was 61 ° C., and the weight average molecular weight was 10,200.
- the reaction was carried out for another 6 hours. After completion of the reaction, the mixture was cooled and neutralized by adding 20.0 parts of 30% aqueous ammonia to the obtained acrylic resin solution. Further, ion-exchanged water was added and solvent substitution was carried out while heating to obtain a copolymer (B) which is an aqueous solution of an acrylic resin having a solid content of 30%.
- the acid value was 220 mgKOH / g, Tg was 60 ° C., and the weight average molecular weight was 10,000.
- Burnock DN-980S manufactured by DIC, hexamethylene diisocyanate polyisocyanate, NCO content 20%
- the mixture was further reacted for 6 hours.
- the mixture was cooled and neutralized by adding 4.0 parts of 30% aqueous ammonia to the obtained acrylic resin solution.
- ion-exchanged water was added and solvent substitution was carried out while heating to obtain an aqueous solution of acrylic urethane resin (Au) having a solid content of 25%.
- the acid value was 62 mgKOH / g, the Tg was 30 ° C., and the weight average molecular weight was 600,000.
- Example 1 Production of OP varnish
- Surfinol 420 (Cas No .: 9014-)
- 85-1 Nisshin Kagaku Kogyo Co., Ltd.) 0.1 parts, polyethylene wax 5 parts, normal propanol 4 parts, defoamer 0.1 parts, ammonia water 1.2 parts, water 54.6 parts are stirred.
- the meat was kneaded with a bead mill to prepare an OP varnish. It was confirmed that the viscosity of the obtained aqueous varnish was 16 seconds (25 ° C.) with Zahn Cup # 4 (manufactured by Rigosha).
- Example 25 Production of water-based liquid ink
- Aqueous liquid ink was obtained by the formulation shown in Table 4.
- -Copolymer (A1) A core-shell acrylic emulsion (A1) having the copolymer prepared in Synthesis Example 2.
- -Copolymer (A2) A core-shell acrylic emulsion (A2) having the copolymer prepared in Synthesis Example 3.
- -Copolymer (A3) Core-shell type styrene acrylic emulsion (A3) having the copolymer prepared in Synthesis Example 5.
- -Acrylic urethane (Au): Acrylic urethane resin (Au) prepared in Synthesis Example 8 -Pigment dispersion resin: Styrene-maleic acid-based pigment dispersion resin-Titanium oxide (IV): JR-800 (manufactured by TAYCA) -Indigo pigment: FASTPGEN BLUE LA5380 (manufactured by DIC Corporation)
- Tables 1 to 7 show examples of each ink and varnish.
- the hollow column in the table indicates that the mixture is not blended.
- the indigo inks of Reference Examples 1 and 2 shown in Table 7 indicate the printing ink B and the like used for the general-purpose printing layer described in the detailed description.
- ⁇ Scratch resistance> The ink-coated surface of the obtained printed ink laminate was scratched with a nail, and the scratch resistance was visually evaluated from the degree of damage to the coating film.
- the practical level is ⁇ ⁇ or higher.
- Tables 8 to 47 show the composition of the obtained printing ink laminate and the evaluation results.
- blanks in "first print layer, second print layer, third print layer, fourth print layer” indicate that there is no print layer.
- indigo ink PU-indigo was printed as the first printing layer and then OP varnish A1-OP1 was printed as the second printing layer on the corona-treated polypropylene biaxially stretched film. It is a laminated body.
- indigo ink PU-indigo is printed as the first printing layer on the corona-treated polypropylene biaxially stretched film, and then white ink A1-white 1 is printed as the second printing layer. It is a laminate obtained by printing and then printing OP varnish A1-OP1 as a third printing layer.
- the substrate adhesion, frictional property, and scratch property are particularly excellent.
- the white ink containing the pigment of the present invention is excellent in adhesion, friction, and scratch property regardless of whether or not it has a cross-linking agent.
- the water-based liquid ink of the present invention can provide a laminate having excellent viscosity stability, substrate adhesion of a cured coating film, and various coating film strengths. Further, even in a system to which a curing agent is added, it is possible to provide a laminate having a viscosity stability comparable to that of the cured coating film, which further enhances the adhesion of the cured coating film to the substrate and the strength of various coating films.
- the liquid printing ink laminate of the present invention can be widely used as various gravure and flexographic printed matter for industrial products such as food packaging materials, sanitary products, cosmetics, and electronic parts.
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Abstract
The present invention addresses the problem of providing: a water-based liquid ink which has outstanding viscosity stability and which has both substrate adhesion as a cured coating and various types of coating strength; and a laminate that uses this water-based liquid ink. The present invention pertains to a water-based liquid ink characterized by comprising: a copolymer which is formed from one or more types of (meth)acrylate monomer and/or one or more types of vinyl monomer, and has an acid value constituting a glass transition temperature of 0-55°C; 0.1-1 mass% of an acetylene surfactant and/or an alcohol-alkoxylate surfactant relative to the total ink amount; and 0.5-5 mass% of wax relative to the total ink amount.
Description
本発明は、軟包装用ラミネート用途の水性グラビアインキ、水性フレキソインキ等の水性リキッドインキ、及び該水性リキッドインキを用いた積層体に関する。
特に、粘度安定性に優れ、硬化塗膜の基材密着性、各種塗膜強度をも兼備する水性リキッドインキ、及び該水性リキッドインキを用いた積層体に関する。
更に、硬化剤を添加した系でも同様に、粘度安定性に優れ、硬化塗膜の基材密着性、各種塗膜強度をも兼備する水性リキッドインキ、及び該水性リキッドインキを用いた積層体に関する。 The present invention relates to a water-based gravure ink for laminating for flexible packaging, a water-based liquid ink such as a water-based flexo ink, and a laminate using the water-based liquid ink.
In particular, the present invention relates to a water-based liquid ink having excellent viscosity stability, adhesion of a cured coating film to a substrate, and various coating film strengths, and a laminate using the water-based liquid ink.
Further, the present invention also relates to a water-based liquid ink having excellent viscosity stability, adhesion to the base material of the cured coating film, and various coating film strengths even in a system to which a curing agent is added, and a laminate using the water-based liquid ink. ..
特に、粘度安定性に優れ、硬化塗膜の基材密着性、各種塗膜強度をも兼備する水性リキッドインキ、及び該水性リキッドインキを用いた積層体に関する。
更に、硬化剤を添加した系でも同様に、粘度安定性に優れ、硬化塗膜の基材密着性、各種塗膜強度をも兼備する水性リキッドインキ、及び該水性リキッドインキを用いた積層体に関する。 The present invention relates to a water-based gravure ink for laminating for flexible packaging, a water-based liquid ink such as a water-based flexo ink, and a laminate using the water-based liquid ink.
In particular, the present invention relates to a water-based liquid ink having excellent viscosity stability, adhesion of a cured coating film to a substrate, and various coating film strengths, and a laminate using the water-based liquid ink.
Further, the present invention also relates to a water-based liquid ink having excellent viscosity stability, adhesion to the base material of the cured coating film, and various coating film strengths even in a system to which a curing agent is added, and a laminate using the water-based liquid ink. ..
軟包装フィルムの被印刷体に美粧性、機能性を付与させる目的で、グラビアインキ、フレキソインキが広く用いられている。グラビア、フレキソ印刷された被印刷体が、包装材料の中でも特に食品向けや衛生用品向け軟包材として用いられる場合、ラミネート加工が加えられるのが一般的である。この場合、内容物の種類や使用目的に応じて様々な被印刷体やラミネート加工が利用される。そして印刷物と各種フィルムを接着剤により貼り合わせるラミネート加工により、印刷物のみでは得られない、膜面強度、保存安定性、ボイル・レトルト適性などを保持する事ができる。
一方で印刷物にラミネート加工を加える場合、印刷物そのものが内容物保護を目的とする場合が多い。この場合、基材のプラスチックと印刷インキ層からなる印刷物と、シーラントフィルムとを接着剤を用いてラミネートするため、直接、印刷インキ層が内容物に触れることはない反面、ラミネート適性を必要とする。そして、ラミネート適性を保持すべく、印刷インキ層の下にアンカーコート層を設けることで、基材の熱可塑性樹脂フィルムと印刷インキ層との密着性を向上させる事が通常行われている。 Gravure inks and flexographic inks are widely used for the purpose of imparting cosmeticity and functionality to the printed material of the flexible packaging film. When the gravure- or flexographic-printed object is used as a flexible packaging material for foods and hygiene products among packaging materials, it is generally laminated. In this case, various printed materials and laminating processes are used depending on the type of contents and the purpose of use. Then, by laminating the printed matter and various films with an adhesive, it is possible to maintain the film surface strength, storage stability, boil / retort suitability, etc., which cannot be obtained only with the printed matter.
On the other hand, when laminating a printed matter, the printed matter itself is often intended to protect the contents. In this case, since the printed matter consisting of the base plastic and the printing ink layer and the sealant film are laminated using an adhesive, the printing ink layer does not come into direct contact with the contents, but the laminating suitability is required. .. Then, in order to maintain the laminating suitability, it is usual practice to improve the adhesion between the thermoplastic resin film of the base material and the printing ink layer by providing an anchor coat layer under the printing ink layer.
一方で印刷物にラミネート加工を加える場合、印刷物そのものが内容物保護を目的とする場合が多い。この場合、基材のプラスチックと印刷インキ層からなる印刷物と、シーラントフィルムとを接着剤を用いてラミネートするため、直接、印刷インキ層が内容物に触れることはない反面、ラミネート適性を必要とする。そして、ラミネート適性を保持すべく、印刷インキ層の下にアンカーコート層を設けることで、基材の熱可塑性樹脂フィルムと印刷インキ層との密着性を向上させる事が通常行われている。 Gravure inks and flexographic inks are widely used for the purpose of imparting cosmeticity and functionality to the printed material of the flexible packaging film. When the gravure- or flexographic-printed object is used as a flexible packaging material for foods and hygiene products among packaging materials, it is generally laminated. In this case, various printed materials and laminating processes are used depending on the type of contents and the purpose of use. Then, by laminating the printed matter and various films with an adhesive, it is possible to maintain the film surface strength, storage stability, boil / retort suitability, etc., which cannot be obtained only with the printed matter.
On the other hand, when laminating a printed matter, the printed matter itself is often intended to protect the contents. In this case, since the printed matter consisting of the base plastic and the printing ink layer and the sealant film are laminated using an adhesive, the printing ink layer does not come into direct contact with the contents, but the laminating suitability is required. .. Then, in order to maintain the laminating suitability, it is usual practice to improve the adhesion between the thermoplastic resin film of the base material and the printing ink layer by providing an anchor coat layer under the printing ink layer.
しかし、近年の省資源化、包装形態の簡素化の取り組みに答え、石油資源由来のフィルムの使用量削減、後加工の簡素化を目的とし、グラビア・フレキソ印刷物そのものを包材に使用する要望が増加しつつあり、これに応じて、印刷インキ層そのものにフィルム密着性、耐摩擦性、耐水性、耐ブロッキング性といった高い塗膜特性が要求されつつある。
また、軟包装フィルム包材における印刷デザインの優劣は、内容物の良し悪しを連想させるまでに影響が大であり、美粧性を意識した高度なデザインに対応可能な高い画像再現性が要求される。 However, in response to recent efforts to save resources and simplify packaging forms, there is a demand to use gravure flexo printed matter itself as packaging material for the purpose of reducing the amount of film derived from petroleum resources and simplifying post-processing. The number is increasing, and in response to this, the printing ink layer itself is required to have high coating film characteristics such as film adhesion, abrasion resistance, water resistance, and blocking resistance.
In addition, the superiority or inferiority of the print design in the flexible packaging film packaging material has a great influence to the extent that it reminds us of the quality of the contents, and high image reproducibility that can correspond to advanced designs that are conscious of cosmetics is required. ..
また、軟包装フィルム包材における印刷デザインの優劣は、内容物の良し悪しを連想させるまでに影響が大であり、美粧性を意識した高度なデザインに対応可能な高い画像再現性が要求される。 However, in response to recent efforts to save resources and simplify packaging forms, there is a demand to use gravure flexo printed matter itself as packaging material for the purpose of reducing the amount of film derived from petroleum resources and simplifying post-processing. The number is increasing, and in response to this, the printing ink layer itself is required to have high coating film characteristics such as film adhesion, abrasion resistance, water resistance, and blocking resistance.
In addition, the superiority or inferiority of the print design in the flexible packaging film packaging material has a great influence to the extent that it reminds us of the quality of the contents, and high image reproducibility that can correspond to advanced designs that are conscious of cosmetics is required. ..
そして近年、VOCによる大気汚染の悪化、地球温暖化など全地球規模の拡大を背景としたサステナビティの観点を根底に、労働安全衛生、更に引火爆発性も加え、脱石油資源への転換する動きに応じ、インキ中の有機溶剤を水に置き換えた水性インキへの置き換えが期待されつつある。例えば水性アクリル樹脂系の色インキ皮膜層と水性ポリウレタン樹脂系の白インキ皮膜層を組み合わせることで、これまで得ることが出来なかった塗膜物性、インキ物性を得ることが出来るようになっている。しかし、これらのインキ皮膜層の組み合わせ構成は、揮発性有機化合物を使用したオーバープリントワニス層、又は水性ポリウレタン系アンカーコートワニス層を必須とするため、印刷時の生産性に関して十分であるとは言えない(例えば、特許文献1)。
また、熱可塑性樹脂フィルムに隣接する印刷インキにアクリル樹脂又はポリウレタン樹脂を使用した印刷インキ積層体の発明が成されているが、フィルム密着性、耐水性を要求される胴巻きシュリンクラベル等の用途では、性能面でまだまだ十分であるとは言えない(例えば、特許文献2)。
更に、印刷作業直前に水性インキに硬化剤を添加したい場合、その作業性を考慮して硬化剤添加から少なくとも6時間は一定粘度が持続する粘度安定性を維持しつつ、硬化塗膜の基材密着性、各種塗膜強度を兼備することは、何れ容易であるとは言えない。 In recent years, based on the perspective of sustainability against the backdrop of global expansion such as worsening air pollution due to VOCs and global warming, occupational safety and health, as well as flammability and explosiveness, have been added to the shift to de-oil resources. Therefore, it is expected to replace the organic solvent in the ink with water-based ink. For example, by combining a water-based acrylic resin-based color ink film layer and a water-based polyurethane resin-based white ink film layer, it is possible to obtain coating material properties and ink physical properties that could not be obtained so far. However, since the combination structure of these ink film layers requires an overprint varnish layer using a volatile organic compound or an aqueous polyurethane anchor coat varnish layer, it can be said that the productivity at the time of printing is sufficient. None (for example, Patent Document 1).
Further, although a printing ink laminate in which an acrylic resin or a polyurethane resin is used as a printing ink adjacent to a thermoplastic resin film has been invented, it is used in applications such as a body-wrapped shrink label that requires film adhesion and water resistance. , It cannot be said that the performance is still sufficient (for example, Patent Document 2).
Furthermore, when it is desired to add a curing agent to the water-based ink immediately before the printing operation, the substrate of the cured coating film is maintained in a constant viscosity for at least 6 hours after the addition of the curing agent in consideration of the workability. It cannot be said that it is easy to have both adhesion and various coating film strengths.
また、熱可塑性樹脂フィルムに隣接する印刷インキにアクリル樹脂又はポリウレタン樹脂を使用した印刷インキ積層体の発明が成されているが、フィルム密着性、耐水性を要求される胴巻きシュリンクラベル等の用途では、性能面でまだまだ十分であるとは言えない(例えば、特許文献2)。
更に、印刷作業直前に水性インキに硬化剤を添加したい場合、その作業性を考慮して硬化剤添加から少なくとも6時間は一定粘度が持続する粘度安定性を維持しつつ、硬化塗膜の基材密着性、各種塗膜強度を兼備することは、何れ容易であるとは言えない。 In recent years, based on the perspective of sustainability against the backdrop of global expansion such as worsening air pollution due to VOCs and global warming, occupational safety and health, as well as flammability and explosiveness, have been added to the shift to de-oil resources. Therefore, it is expected to replace the organic solvent in the ink with water-based ink. For example, by combining a water-based acrylic resin-based color ink film layer and a water-based polyurethane resin-based white ink film layer, it is possible to obtain coating material properties and ink physical properties that could not be obtained so far. However, since the combination structure of these ink film layers requires an overprint varnish layer using a volatile organic compound or an aqueous polyurethane anchor coat varnish layer, it can be said that the productivity at the time of printing is sufficient. None (for example, Patent Document 1).
Further, although a printing ink laminate in which an acrylic resin or a polyurethane resin is used as a printing ink adjacent to a thermoplastic resin film has been invented, it is used in applications such as a body-wrapped shrink label that requires film adhesion and water resistance. , It cannot be said that the performance is still sufficient (for example, Patent Document 2).
Furthermore, when it is desired to add a curing agent to the water-based ink immediately before the printing operation, the substrate of the cured coating film is maintained in a constant viscosity for at least 6 hours after the addition of the curing agent in consideration of the workability. It cannot be said that it is easy to have both adhesion and various coating film strengths.
本発明の課題は、粘度安定性に優れ、硬化塗膜の基材密着性、各種塗膜強度をも兼備する水性リキッドインキ、及び該水性リキッドインキを用いた積層体を提供することにある。
更に、硬化剤を添加した系でも同様に、粘度安定性に優れ、硬化塗膜の基材密着性、各種塗膜強度をも兼備する水性リキッドインキ、及び該水性リキッドインキを用いた積層体を提供することにある。 An object of the present invention is to provide a water-based liquid ink having excellent viscosity stability, adhesion of a cured coating film to a substrate, and various coating film strengths, and a laminate using the water-based liquid ink.
Further, even in a system to which a curing agent is added, a water-based liquid ink having excellent viscosity stability, adhesion of a cured coating film to a substrate, and various coating film strengths, and a laminate using the water-based liquid ink can be obtained. To provide.
更に、硬化剤を添加した系でも同様に、粘度安定性に優れ、硬化塗膜の基材密着性、各種塗膜強度をも兼備する水性リキッドインキ、及び該水性リキッドインキを用いた積層体を提供することにある。 An object of the present invention is to provide a water-based liquid ink having excellent viscosity stability, adhesion of a cured coating film to a substrate, and various coating film strengths, and a laminate using the water-based liquid ink.
Further, even in a system to which a curing agent is added, a water-based liquid ink having excellent viscosity stability, adhesion of a cured coating film to a substrate, and various coating film strengths, and a laminate using the water-based liquid ink can be obtained. To provide.
本発明の水性リキッドインキは、(メタ)アクリレート系モノマー及び/又はビニル系モノマーから形成され、ガラス転移温度が0℃~55℃である酸価を有するコポリマーに、アセチレン系界面活性剤及び/又はアルコールアルコキシレート系界面活性剤、及びワックスを適量用いる事で課題解決に有効であることを見出した。
The aqueous liquid ink of the present invention is formed from a (meth) acrylate-based monomer and / or a vinyl-based monomer, and is a copolymer having an acid value having a glass transition temperature of 0 ° C. to 55 ° C., an acetylene-based surfactant and / or It was found that it is effective to solve the problem by using an appropriate amount of alcohol alkoxylate-based surfactant and wax.
すなわち本発明は、1種又は2種以上の(メタ)アクリレート系モノマー及び/又は1種又は2種以上のビニル系モノマーから形成され、ガラス転移温度が0℃~55℃である酸価を有するコポリマーと、アセチレン系界面活性剤及び/又はアルコールアルコキシレート系界面活性剤をインキ全量に対し0.1~1質量%と、ワックスをインキ全量に対し0.5~5質量%を含有する水性リキッドインキを提供する。
That is, the present invention is formed from one or more (meth) acrylate-based monomers and / or one or more vinyl-based monomers and has an acid value having a glass transition temperature of 0 ° C. to 55 ° C. A water-based liquid containing a copolymer, an acetylene-based surfactant and / or an alcohol alkoxylate-based surfactant in an amount of 0.1 to 1% by mass based on the total amount of ink, and a wax containing 0.5 to 5% by mass based on the total amount of ink. Provide ink.
また本発明は、基材上に1層または複数層の印刷層を有する積層体であって、前記印刷層の少なくとも1つが、請求項1~5のいずれかに記載の水性リキッドインキの印刷層である積層体を提供する。
Further, the present invention is a laminate having one or a plurality of printing layers on a base material, and at least one of the printing layers is a printing layer of the water-based liquid ink according to any one of claims 1 to 5. Provides a laminate that is.
本発明により、粘度安定性に優れ、硬化塗膜の基材密着性、各種塗膜強度をも兼備する水性リキッドインキ、及び該水性リキッドインキを用いた積層体を提供することが出来る。
更に、硬化剤を添加した系でも同様に、粘度安定性に優れ、硬化塗膜の基材密着性、各種塗膜強度をも兼備する水性リキッドインキ、及び該水性リキッドインキを用いた積層体を提供することが出来る。 INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a water-based liquid ink having excellent viscosity stability, adhesion of a cured coating film to a substrate, and various coating film strengths, and a laminate using the water-based liquid ink.
Further, even in a system to which a curing agent is added, a water-based liquid ink having excellent viscosity stability, adhesion of a cured coating film to a substrate, and various coating film strengths, and a laminate using the water-based liquid ink can be obtained. Can be provided.
更に、硬化剤を添加した系でも同様に、粘度安定性に優れ、硬化塗膜の基材密着性、各種塗膜強度をも兼備する水性リキッドインキ、及び該水性リキッドインキを用いた積層体を提供することが出来る。 INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a water-based liquid ink having excellent viscosity stability, adhesion of a cured coating film to a substrate, and various coating film strengths, and a laminate using the water-based liquid ink.
Further, even in a system to which a curing agent is added, a water-based liquid ink having excellent viscosity stability, adhesion of a cured coating film to a substrate, and various coating film strengths, and a laminate using the water-based liquid ink can be obtained. Can be provided.
本発明について詳細に説明する。なお以下の説明で用いる「インキ」とは全て「水性リキッドインキ」を示す。また「部」とは全て「質量部」を、「%」とは全て「質量%」を示す。
The present invention will be described in detail. The "inks" used in the following description all refer to "water-based liquid inks". Further, "parts" mean "parts by mass", and "%" means "% by mass".
本発明の水性リキッドインキは、1種又は2種以上の(メタ)アクリレート系モノマー及び/又は1種又は2種以上のビニル系モノマーから形成され、ガラス転移温度が0℃~55℃である酸価を有するコポリマー(以後コポリマー(A)と称する場合がある)と、アセチレン系界面活性剤及び/又はアルコールアルコキシレート系界面活性剤をインキ全量に対し0.1~1質量%と、ワックスをインキ全量に対し0.5~5質量%を含有することを必須とする。
The water-based liquid ink of the present invention is an acid formed from one or more (meth) acrylate-based monomers and / or one or more vinyl-based monomers and having a glass transition temperature of 0 ° C. to 55 ° C. A copolymer having a value (hereinafter sometimes referred to as a copolymer (A)), an acetylene-based surfactant and / or an alcohol alkoxylate-based surfactant in an amount of 0.1 to 1% by mass based on the total amount of the ink, and a wax in the ink. It is essential to contain 0.5 to 5% by mass based on the total amount.
コポリマー(A)は、1種又は2種以上の(メタ)アクリレートモノマーの重合体または共重合体、1種又は2種以上のビニル系モノマーの重合体または共重合体、1種又は2種以上の(メタ)アクリレートモノマーとビニル系モノマーとの共重合体である。
尚、前記「(メタ)アクリレート」はアクリレート及びメタクリレートのいずれか一方または両方を指し、「(メタ)アクリル」はアクリル及びメタクリルのいずれか一方または両方を指す。 The copolymer (A) is a polymer or copolymer of one or more (meth) acrylate monomers, or a polymer or copolymer of one or more vinyl-based monomers, or one or more. It is a copolymer of the (meth) acrylate monomer and the vinyl-based monomer.
The "(meth) acrylate" refers to either or both of acrylate and methacrylate, and "(meth) acrylic" refers to either or both of acrylic and methacrylic.
尚、前記「(メタ)アクリレート」はアクリレート及びメタクリレートのいずれか一方または両方を指し、「(メタ)アクリル」はアクリル及びメタクリルのいずれか一方または両方を指す。 The copolymer (A) is a polymer or copolymer of one or more (meth) acrylate monomers, or a polymer or copolymer of one or more vinyl-based monomers, or one or more. It is a copolymer of the (meth) acrylate monomer and the vinyl-based monomer.
The "(meth) acrylate" refers to either or both of acrylate and methacrylate, and "(meth) acrylic" refers to either or both of acrylic and methacrylic.
前記(メタ)アクリレートモノマーは特に限定されず、例えばメチル(メタ)アクリレート、エチル(メタ)アクリレート、n-ブチル(メタ)アクリレート、iso-ブチル(メタ)アクリレート、tert-ブチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、ヘキシル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、オクチル(メタ)アクリレート、ノニル(メタ)アクリレート、ドデシル(メタ)アクリレート、ステアリル(メタ)アクリレート、イソボルニル(メタ)アクリレート、ジシクロペンタニル(メタ)アクリレート、フェニル(メタ)アクリレート、ベンジル(メタ)アクリレート、2,2,2-トリフルオロエチル(メタ)アクリレート、2,2,3,3-ペンタフルオロプロピル(メタ)アクリレート、パーフルオロシクロヘキシル(メタ)アクリレート、グリシジル(メタ)アクリレート、アリルグリシジルエーテル、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、ポリエチレングリコールモノ(メタ)アクリレート、(メタ)アクリルアミド、N-モノアルキル(メタ)アクリルアミド、N,N-ジアルキル(メタ)アクリルアミド、N-メチロール(メタ)アクリルアミド、N-イソプロポキシメチル(メタ)アクリルアミド、N-ブトキシメチル(メタ)アクリルアミド、N-イソブトキシメチル(メタ)アクリルアミド、2-アジリジニルエチル(メタ)アクリレート、ジシクロペンテニル(メタ)アクリレート、アクロレイン、ジアセトン(メタ)アクリルアミド、アセトアセトキシエチル(メタ)アクリレート等の(メタ)アクリルモノマーを使用することができる。これらはそれぞれ単独で用いても良いし、二種類以上を併用しても良い。
The (meth) acrylate monomer is not particularly limited, and for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2 -Ethylhexyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, di Cyclopentanyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-pentafluoropropyl (meth) acrylate, Perfluorocyclohexyl (meth) acrylate, glycidyl (meth) acrylate, allyl glycidyl ether, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, (meth) acrylamide, N -Monoalkyl (meth) acrylamide, N, N-dialkyl (meth) acrylamide, N-methylol (meth) acrylamide, N-isopropoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-isobutoxymethyl Use (meth) acrylic monomers such as (meth) acrylamide, 2-aziridinyl ethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, achlorine, diacetone (meth) acrylamide, and acetoacetoxyethyl (meth) acrylate. Can be done. Each of these may be used alone, or two or more types may be used in combination.
前記ビニル系モノマーは、例えば、酢酸ビニル、プロピオン酸ビニル、バーサチック酸ビニル、メチルビニルエーテル、エチルビニルエーテル、プロピルビニルエーテル、ブチルビニルエーテル、(メタ)アクリロニトリル、スチレン、α-メチルスチレン、ジビニルスチレン、イソプレン、クロロプレン、ブタジエン、エチレン、テトラフルオロエチレン、フッ化ビニリデン、N-ビニルピロリドン等が挙げられる。中でもスチレン、α-メチルスチレン、ジビニルスチレン等のスチレン系モノマーを使用することが好ましい。これらはそれぞれ単独で用いても良いし、二種類以上を併用しても良い。
Examples of the vinyl monomer include vinyl acetate, vinyl propionate, vinyl versatic acid, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, (meth) acrylonitrile, styrene, α-methylstyrene, divinylstyrene, isoprene, and chloroprene. Examples thereof include butadiene, ethylene, tetrafluoroethylene, vinylidene fluoride, N-vinylpyrrolidone and the like. Of these, it is preferable to use styrene-based monomers such as styrene, α-methylstyrene, and divinylstyrene. Each of these may be used alone, or two or more types may be used in combination.
また、カルボキシル基及びカルボキシル基が塩基性化合物によって中和されたカルボキシレート基からなる群より選ばれる1種以上の酸性基を導入することを目的として(メタ)アクリル酸、クロトン酸、イタコン酸、マレイン酸、フマル酸、β-(メタ)アクリロイルオキシエチルハイドロゲンサクシネート、β-(メタ)アクリロイルオキシエチルハイドロゲンフタレート等のカルボキシル基を有する(メタ)アクリルモノマーを共重合させることで得ることができる。
酸性基を導入する場合は、後述で詳細に述べるが酸価が所望の範囲となるようにモノマー量を適宜調整することが好ましい。 Further, for the purpose of introducing one or more acidic groups selected from the group consisting of a carboxyl group and a carboxylate group in which the carboxyl group is neutralized with a basic compound, (meth) acrylic acid, crotonic acid, itaconic acid, It can be obtained by copolymerizing a (meth) acrylic monomer having a carboxyl group such as maleic acid, fumaric acid, β- (meth) acryloyloxyethyl hydrogen succinate, β- (meth) acryloyloxyethyl hydrogen phthalate.
When an acidic group is introduced, it is preferable to appropriately adjust the amount of the monomer so that the acid value is in a desired range, which will be described in detail later.
酸性基を導入する場合は、後述で詳細に述べるが酸価が所望の範囲となるようにモノマー量を適宜調整することが好ましい。 Further, for the purpose of introducing one or more acidic groups selected from the group consisting of a carboxyl group and a carboxylate group in which the carboxyl group is neutralized with a basic compound, (meth) acrylic acid, crotonic acid, itaconic acid, It can be obtained by copolymerizing a (meth) acrylic monomer having a carboxyl group such as maleic acid, fumaric acid, β- (meth) acryloyloxyethyl hydrogen succinate, β- (meth) acryloyloxyethyl hydrogen phthalate.
When an acidic group is introduced, it is preferable to appropriately adjust the amount of the monomer so that the acid value is in a desired range, which will be described in detail later.
中でもコポリマー(A)としては、2種以上の(メタ)アクリレートモノマーの共重合体、または1種又は2種以上の(メタ)アクリレートモノマーとビニル系モノマーとの共重合体が好ましい。例えば
(1)2種以上のカルボキシル基を有さない(メタ)アクリレートモノマーと(メタ)アクリル酸等のカルボキシル基を有する(メタ)アクリレートモノマーとの共重合体である、酸価を有する(メタ)アクリルコポリマー
(2)2種以上のカルボキシル基を有さない(メタ)アクリレートモノマーとスチレン系モノマーと(メタ)アクリル酸等のカルボキシル基を有する(メタ)アクリレートモノマーとの共重合体である、酸価を有するスチレン(メタ)アクリルコポリマー
が好ましい。
(1)や(2)で使用されるカルボキシル基を有さない(メタ)アクリルモノマーとしてより好ましくは、メチル(メタ)アクリレート、エチル(メタ)アクリレート、n-ブチル(メタ)アクリレート、iso-ブチル(メタ)アクリレート、tert-ブチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、ヘキシル(メタ)アクリレート等の脂肪族鎖状の(メタ)アクリレートが好ましい。 Among them, as the copolymer (A), a copolymer of two or more kinds of (meth) acrylate monomers or a copolymer of one or more kinds of (meth) acrylate monomers and a vinyl-based monomer is preferable. For example, (1) a copolymer of (meth) acrylate monomer having two or more kinds of carboxyl groups and (meth) acrylate monomer having a carboxyl group such as (meth) acrylic acid, having an acid value (meth). ) Acrylic copolymer (2) A copolymer of a (meth) acrylate monomer having two or more kinds of carboxyl groups, a styrene-based monomer, and a (meth) acrylate monomer having a carboxyl group such as (meth) acrylic acid. A styrene (meth) acrylic copolymer having an acid value is preferable.
More preferably, the (meth) acrylic monomer having no carboxyl group used in (1) and (2) is methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and iso-butyl. An aliphatic chain (meth) acrylate such as (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and hexyl (meth) acrylate is preferable.
(1)2種以上のカルボキシル基を有さない(メタ)アクリレートモノマーと(メタ)アクリル酸等のカルボキシル基を有する(メタ)アクリレートモノマーとの共重合体である、酸価を有する(メタ)アクリルコポリマー
(2)2種以上のカルボキシル基を有さない(メタ)アクリレートモノマーとスチレン系モノマーと(メタ)アクリル酸等のカルボキシル基を有する(メタ)アクリレートモノマーとの共重合体である、酸価を有するスチレン(メタ)アクリルコポリマー
が好ましい。
(1)や(2)で使用されるカルボキシル基を有さない(メタ)アクリルモノマーとしてより好ましくは、メチル(メタ)アクリレート、エチル(メタ)アクリレート、n-ブチル(メタ)アクリレート、iso-ブチル(メタ)アクリレート、tert-ブチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、ヘキシル(メタ)アクリレート等の脂肪族鎖状の(メタ)アクリレートが好ましい。 Among them, as the copolymer (A), a copolymer of two or more kinds of (meth) acrylate monomers or a copolymer of one or more kinds of (meth) acrylate monomers and a vinyl-based monomer is preferable. For example, (1) a copolymer of (meth) acrylate monomer having two or more kinds of carboxyl groups and (meth) acrylate monomer having a carboxyl group such as (meth) acrylic acid, having an acid value (meth). ) Acrylic copolymer (2) A copolymer of a (meth) acrylate monomer having two or more kinds of carboxyl groups, a styrene-based monomer, and a (meth) acrylate monomer having a carboxyl group such as (meth) acrylic acid. A styrene (meth) acrylic copolymer having an acid value is preferable.
More preferably, the (meth) acrylic monomer having no carboxyl group used in (1) and (2) is methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and iso-butyl. An aliphatic chain (meth) acrylate such as (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and hexyl (meth) acrylate is preferable.
前記コポリマー(A)は、例えば、重合開始剤の存在下、50℃~180℃の温度領域で各種モノマーを重合させることにより製造することができ、80℃~150℃の温度領域であればより好ましい。重合の方法は、例えば、塊状重合法、溶液重合法、懸濁重合法、乳化重合法等が挙げられる。また、重合様式は、例えば、ランダム共重合体、ブロック共重合体、グラフト共重合体等が挙げられる。
The copolymer (A) can be produced, for example, by polymerizing various monomers in a temperature range of 50 ° C. to 180 ° C. in the presence of a polymerization initiator, and more if it is in a temperature range of 80 ° C. to 150 ° C. preferable. Examples of the polymerization method include a massive polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method. In addition, examples of the polymerization mode include random copolymers, block copolymers, graft copolymers, and the like.
本発明で使用するコポリマー(A)はコアシェル型を形成するエマルジョンであってもよい。本発明においてコアシェル型エマルジョンは、重合体(a2)が重合体(a1)によって水性媒体中に分散された状態を指し、通常、重合体(a1)が樹脂粒子の最外部に存在することでシェル部を形成し、重合体(a2)の一部または全部がコア部を形成したものであることが多い。以後本発明において、シェル部を形成する樹脂を重合体(a1)とし、コア部を形成する樹脂を重合体(a2)と称す。
The copolymer (A) used in the present invention may be an emulsion forming a core-shell type. In the present invention, the core-shell type emulsion refers to a state in which the polymer (a2) is dispersed in an aqueous medium by the polymer (a1), and usually, the polymer (a1) is present on the outermost side of the resin particles to form a shell. In many cases, a portion is formed and a part or all of the polymer (a2) forms a core portion. Hereinafter, in the present invention, the resin forming the shell portion will be referred to as a polymer (a1), and the resin forming the core portion will be referred to as a polymer (a2).
〔シェル部を構成する重合体(a1)〕
本発明で使用するコアシェル型エマルジョンは、シェル部を構成する重合体(a1)について、カルボキシル基及びそれを中和して形成されるカルボキシレート基からなる群より選ばれる1種以上の親水性基を有するアクリルコポリマーを含むものによって構成されていることが好ましい。その際、シェル部の酸価は40mgKOH/g以上250mgKOH/g以下の範囲であることが好ましく、120mgKOH/g以下がなお好ましい。 [Polymer constituting the shell portion (a1)]
The core-shell emulsion used in the present invention is one or more hydrophilic groups selected from the group consisting of a carboxyl group and a carboxylate group formed by neutralizing the carboxyl group (a1) constituting the shell portion. It is preferably composed of one containing an acrylic copolymer having. At that time, the acid value of the shell portion is preferably in the range of 40 mgKOH / g or more and 250 mgKOH / g or less, and more preferably 120 mgKOH / g or less.
本発明で使用するコアシェル型エマルジョンは、シェル部を構成する重合体(a1)について、カルボキシル基及びそれを中和して形成されるカルボキシレート基からなる群より選ばれる1種以上の親水性基を有するアクリルコポリマーを含むものによって構成されていることが好ましい。その際、シェル部の酸価は40mgKOH/g以上250mgKOH/g以下の範囲であることが好ましく、120mgKOH/g以下がなお好ましい。 [Polymer constituting the shell portion (a1)]
The core-shell emulsion used in the present invention is one or more hydrophilic groups selected from the group consisting of a carboxyl group and a carboxylate group formed by neutralizing the carboxyl group (a1) constituting the shell portion. It is preferably composed of one containing an acrylic copolymer having. At that time, the acid value of the shell portion is preferably in the range of 40 mgKOH / g or more and 250 mgKOH / g or less, and more preferably 120 mgKOH / g or less.
前記、シェル部を構成する重合体(a1)のカルボキシル基は、塩基性化合物によって中和されカルボキシレート基を形成することが好ましい。
It is preferable that the carboxyl group of the polymer (a1) constituting the shell portion is neutralized with a basic compound to form a carboxylate group.
前記中和に使用可能な塩基性化合物としては、例えばアンモニア、トリエチルアミン、モルホリン、モノエタノールアミン、ジエチルエタノールアミン等を使用することができ、アンモニア、トリエチルアミンを使用することが、塗膜の耐温水性、耐食性及び耐薬品性をより一層向上するうえで好ましい。
As the basic compound that can be used for the neutralization, for example, ammonia, triethylamine, morpholine, monoethanolamine, diethylethanolamine and the like can be used, and it is possible to use ammonia and triethylamine for the temperature resistance of the coating film. , It is preferable to further improve the corrosion resistance and the chemical resistance.
前記塩基性化合物の使用量は、得られるコアシェル型エマルジョンの水分散安定性をより一層向上するうえで、前記重合体(a1)が有するカルボキシル基の全量に対して[塩基性化合物/カルボキシル基]=0.2~2(モル比)となる範囲で使用することが好ましい。
The amount of the basic compound used is [basic compound / carboxyl group] with respect to the total amount of the carboxyl group of the polymer (a1) in order to further improve the water dispersion stability of the obtained core-shell emulsion. It is preferably used in the range of = 0.2 to 2 (molar ratio).
前記重合性不飽和二重結合を有するモノマーのうち、カルボキシル基を有する(メタ)アクリルモノマーを含む(メタ)アクリルモノマーを重合して得られるものを使用することが好ましい。特に、前記重合体(a1)としては、前記重合体(a1)のガラス転移温度(Tg1)を20℃~100℃の範囲に調整するうえで、メチル(メタ)アクリレート、ブチル(メタ)アクリレート、(メタ)アクリル酸等を組み合わせ重合して得られるものを使用することが、造膜性に優れ、かつ、耐温水性、耐食性及び耐薬品性に優れた塗膜を形成するうえでより好ましい。
Among the monomers having a polymerizable unsaturated double bond, it is preferable to use a monomer obtained by polymerizing a (meth) acrylic monomer containing a (meth) acrylic monomer having a carboxyl group. In particular, as the polymer (a1), methyl (meth) acrylate, butyl (meth) acrylate, in order to adjust the glass transition temperature (Tg1) of the polymer (a1) in the range of 20 ° C. to 100 ° C. It is more preferable to use a polymer obtained by combining and polymerizing (meth) acrylic acid or the like in order to form a coating film having excellent film-forming property and excellent temperature water resistance, corrosion resistance and chemical resistance.
〔コア部を構成する重合体(a2)〕
前記コア部を構成する重合体(a2)は、前述のアクリル樹脂と同様のアクリルモノマー等の共重合体を使用することができる。
この際、コア部の重量平均分子量は200,000~3,000,000の範囲であることが好ましく、800,000以上がなお好ましい。Tgは-30℃~30℃の範囲であることが好ましい。 [Polymer constituting the core portion (a2)]
As the polymer (a2) constituting the core portion, a copolymer such as an acrylic monomer similar to the above-mentioned acrylic resin can be used.
At this time, the weight average molecular weight of the core portion is preferably in the range of 200,000 to 3,000,000, and more preferably 800,000 or more. Tg is preferably in the range of −30 ° C. to 30 ° C.
前記コア部を構成する重合体(a2)は、前述のアクリル樹脂と同様のアクリルモノマー等の共重合体を使用することができる。
この際、コア部の重量平均分子量は200,000~3,000,000の範囲であることが好ましく、800,000以上がなお好ましい。Tgは-30℃~30℃の範囲であることが好ましい。 [Polymer constituting the core portion (a2)]
As the polymer (a2) constituting the core portion, a copolymer such as an acrylic monomer similar to the above-mentioned acrylic resin can be used.
At this time, the weight average molecular weight of the core portion is preferably in the range of 200,000 to 3,000,000, and more preferably 800,000 or more. Tg is preferably in the range of −30 ° C. to 30 ° C.
前記コア部を構成する重合体(a2)は、前述のアクリル樹脂と同様のアクリルモノマー等の共重合体を使用することができるが、中でも、水性媒体で製造することが好ましい。具体的には、前記、モノマーと重合開始剤等とを、水性媒体を含有する反応容器に一括供給または逐次供給し重合することによって製造することができる。その際、予め前記モノマーと水性媒体と必要に応じて反応性界面活性剤等とを混合することでプレエマルジョンを製造し、それと重合開始剤等とを、水性媒体を含有する反応容器に供給し重合してもよい。
As the polymer (a2) constituting the core portion, a copolymer such as an acrylic monomer similar to the above-mentioned acrylic resin can be used, but among them, it is preferably produced in an aqueous medium. Specifically, it can be produced by collectively supplying or sequentially supplying the monomer and the polymerization initiator or the like to a reaction vessel containing an aqueous medium for polymerization. At that time, a pre-emulsion is produced by mixing the monomer, an aqueous medium, and a reactive surfactant or the like in advance, and the polymerization initiator or the like is supplied to a reaction vessel containing the aqueous medium. It may be polymerized.
前記重合体(a2)を製造する際に使用可能な重合開始剤としては、例えば過硫酸塩、有機過酸化物、過酸化水素等のラジカル重合開始剤、4,4’-アゾビス(4-シアノ吉草酸)、2,2’-アゾビス(2-アミジノプロパン)二塩酸塩等のアゾ開始剤を使用することができる。また、前記ラジカル重合開始剤は、後述する還元剤と併用しレドックス重合開始剤として使用しても良い。
Examples of the polymerization initiator that can be used in producing the polymer (a2) include radical polymerization initiators such as persulfate, organic peroxide, and hydrogen peroxide, and 4,4'-azobis (4-cyano). Azo initiators such as valerate) and 2,2'-azobis (2-amidinopropane) dihydrochloride can be used. In addition, the radical polymerization initiator may be used as a redox polymerization initiator in combination with a reducing agent described later.
前記過硫酸塩としては、例えば過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム等を使用することができる。前記、有機過酸化物としては、例えば、過酸化ベンゾイル、ラウロイルパーオキサイド、デカノイルパーオキサイド、t-ブチルクミルパーオキサイド、ジクミルパーオキサイド、t-ブチルパーオキシラウレート、t-ブチルパーオキシベンゾエート、クメンハイドロパーオキサイド、パラメンタンハイドロパーオキサイド、t-ブチルハイドロパーオキサイド等を使用することができる。
As the persulfate, for example, potassium persulfate, sodium persulfate, ammonium persulfate and the like can be used. Examples of the organic peroxide include benzoyl peroxide, lauroyl peroxide, decanoyyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, t-butyl peroxylaurate, and t-butyl peroxybenzoate. , Kumen hydroperoxide, paramentan hydroperoxide, t-butyl hydroperoxide and the like can be used.
また、前記還元剤としては、例えば、アスコルビン酸及びその塩、エリソルビン酸及びその塩(ナトリウム塩等)、酒石酸及びその塩、クエン酸及びその塩、ホルムアルデヒドスルホキシラートの金属塩、チオ硫酸ナトリウム、重亜硫酸ナトリウム、塩化第二鉄等を使用することができる。
Examples of the reducing agent include ascorbic acid and its salt, erythorbic acid and its salt (sodium salt, etc.), tartrate acid and its salt, citric acid and its salt, formaldehyde sulfoxylate metal salt, sodium thiosulfate, and the like. Sodium bicarbonate, ferric chloride, etc. can be used.
重合開始剤の使用量は、重合が円滑に進行する量を使用すれば良いが、得られる塗膜の優れた耐食性を維持する観点から、少ない方が好ましく、ビニル重合体(a2)の製造に使用するモノマーの全量に対して、0.01質量%~0.5質量%とすることが好ましい。また、前記重合開始剤を前記還元剤と併用する場合には、それらの合計量の使用量も前記した範囲内であることが好ましい。
The amount of the polymerization initiator used may be an amount that allows the polymerization to proceed smoothly, but it is preferable that the amount used is as small as possible from the viewpoint of maintaining the excellent corrosion resistance of the obtained coating film, and is used for producing the vinyl polymer (a2). It is preferably 0.01% by mass to 0.5% by mass with respect to the total amount of the monomers used. When the polymerization initiator is used in combination with the reducing agent, the total amount of the polymerization initiator used is preferably within the above range.
また、前記プレエマルジョンを製造する際には、反応性界面活性剤、陰イオン性界面活性剤、非イオン性界面活性剤、陽イオン性界面活性剤、両性イオン性界面活性剤等を使用してもよい。
In addition, when producing the pre-emulsion, a reactive surfactant, an anionic surfactant, a nonionic surfactant, a cationic surfactant, a zwitterionic surfactant and the like are used. May be good.
前記コポリマー(A)の酸価は、酸価20mgKOH/g以上、120mgKOH/g以下が好ましく、より好ましくは酸価25mgKOH以上である。酸価が20mgKOH/g以上であれば、硬化剤添加時、積層体の耐摩擦性、耐水摩擦性、及び耐スクラッチ性を向上する事が出来る。
尚、ここで言う酸価とは、樹脂1g中に含まれる酸性成分を中和するのに要する水酸化カリウムのミリグラム数を示す。 The acid value of the copolymer (A) is preferably 20 mgKOH / g or more, 120 mgKOH / g or less, and more preferably 25 mgKOH or more. When the acid value is 20 mgKOH / g or more, the friction resistance, water friction resistance, and scratch resistance of the laminate can be improved when the curing agent is added.
The acid value referred to here indicates the number of milligrams of potassium hydroxide required to neutralize the acidic component contained in 1 g of the resin.
尚、ここで言う酸価とは、樹脂1g中に含まれる酸性成分を中和するのに要する水酸化カリウムのミリグラム数を示す。 The acid value of the copolymer (A) is preferably 20 mgKOH / g or more, 120 mgKOH / g or less, and more preferably 25 mgKOH or more. When the acid value is 20 mgKOH / g or more, the friction resistance, water friction resistance, and scratch resistance of the laminate can be improved when the curing agent is added.
The acid value referred to here indicates the number of milligrams of potassium hydroxide required to neutralize the acidic component contained in 1 g of the resin.
前記コポリマー(A)の重量平均分子量は、5,000~100,000の範囲のものが好ましい。重量平均分子量5,000以上であれば、樹脂皮膜の耐熱性が低下することなく、積層体の耐摩擦性、及び耐水摩擦性を保持できる傾向にある。100,000以下であれば、積層体の基材密着性、耐スクラッチ性が兼備できる傾向にある。
The weight average molecular weight of the copolymer (A) is preferably in the range of 5,000 to 100,000. When the weight average molecular weight is 5,000 or more, the heat resistance of the resin film does not decrease, and the friction resistance and the water friction resistance of the laminate tend to be maintained. If it is 100,000 or less, the laminate tends to have both substrate adhesion and scratch resistance.
前記コポリマー(A)のガラス転移温度(Tgと称する場合がある)は、0℃~55℃の範囲である事が好ましい。前記コポリマー(A)のTgが0℃以上であれば、皮膜強度が保たれ、積層体の耐水摩擦性が低下することなく、また55℃以下であれば、他の印刷層との相溶性が低下する事なく、積層体の耐摩擦性、耐水摩擦性、耐スクラッチ性が良好に保たれる傾向にある。
尚、前記ガラス転移温度(Tg)は、いわゆる計算ガラス転移温度を指し、下記の方法で算出された値を指す。
(式1) 1/Tg(K)=(W1/T1)+(W2/T2)+・・・(Wn/Tn)
(式2) Tg(℃)=Tg(K)-273
式1中のW1、W2、・・・Wnは、重合体の製造に使用したモノマーの合計質量に対する各モノマーの質量%を表し、T1、T2、・・・Tnは、各モノマーのホモポリマーのガラス転移温度(K)を表す。なお、T1、T2、・・Tnの値は、Polymer Handbook(Fourth Edition,J.Brandrup,E.H.Immergut,E.A.Grulke 編)に記載された値を用いる。
また、各モノマーのホモポリマーのガラス転移温度が前記Polymer Hand Bookに記載されていないもののガラス転移温度は、示差走査熱量計「DSC Q-100」(TA Instrument社製)を用い、JIS K7121に準拠した方法で測定した。具体的には、真空吸引して完全に溶剤を除去した重合体を、20℃/分の昇温速度で-100℃~+200℃の範囲で熱量変化を測定し、各ベースラインの延長した直線から縦軸方向に等距離にある直線と、ガラス転移の階段状変化部分の曲線とが交わる点をガラス転移温度とした。 The glass transition temperature (sometimes referred to as Tg) of the copolymer (A) is preferably in the range of 0 ° C. to 55 ° C. When the Tg of the copolymer (A) is 0 ° C. or higher, the film strength is maintained, the water friction resistance of the laminate is not lowered, and when the Tg is 55 ° C. or lower, the compatibility with other printing layers is good. The friction resistance, water friction resistance, and scratch resistance of the laminate tend to be kept good without deterioration.
The glass transition temperature (Tg) refers to a so-called calculated glass transition temperature, and refers to a value calculated by the following method.
(Equation 1) 1 / Tg (K) = (W1 / T1) + (W2 / T2) + ... (Wn / Tn)
(Equation 2) Tg (° C.) = Tg (K) -273
W1, W2, ... Wn in the formula 1 represent the mass% of each monomer with respect to the total mass of the monomers used for producing the polymer, and T1, T2, ... Tn are the homopolymers of each monomer. Represents the glass transition temperature (K). As the values of T1, T2, ... Tn, the values described in Polymer Handbook (Fourth Edition, J. Brandrup, E.H. Immunogut, EA Grulke) are used.
Although the glass transition temperature of the homopolymer of each monomer is not described in the Polymer Hand Book, the glass transition temperature is based on JIS K7121 using a differential scanning calorimeter "DSC Q-100" (manufactured by TA Instrument). It was measured by the method described above. Specifically, the polymer from which the solvent has been completely removed by vacuum suction is measured for a change in calorific value in the range of -100 ° C to + 200 ° C at a heating rate of 20 ° C./min, and a straight line extending each baseline. The point where the straight line equidistant from the vertical axis direction and the curve of the stepwise change portion of the glass transition intersect was defined as the glass transition temperature.
尚、前記ガラス転移温度(Tg)は、いわゆる計算ガラス転移温度を指し、下記の方法で算出された値を指す。
(式1) 1/Tg(K)=(W1/T1)+(W2/T2)+・・・(Wn/Tn)
(式2) Tg(℃)=Tg(K)-273
式1中のW1、W2、・・・Wnは、重合体の製造に使用したモノマーの合計質量に対する各モノマーの質量%を表し、T1、T2、・・・Tnは、各モノマーのホモポリマーのガラス転移温度(K)を表す。なお、T1、T2、・・Tnの値は、Polymer Handbook(Fourth Edition,J.Brandrup,E.H.Immergut,E.A.Grulke 編)に記載された値を用いる。
また、各モノマーのホモポリマーのガラス転移温度が前記Polymer Hand Bookに記載されていないもののガラス転移温度は、示差走査熱量計「DSC Q-100」(TA Instrument社製)を用い、JIS K7121に準拠した方法で測定した。具体的には、真空吸引して完全に溶剤を除去した重合体を、20℃/分の昇温速度で-100℃~+200℃の範囲で熱量変化を測定し、各ベースラインの延長した直線から縦軸方向に等距離にある直線と、ガラス転移の階段状変化部分の曲線とが交わる点をガラス転移温度とした。 The glass transition temperature (sometimes referred to as Tg) of the copolymer (A) is preferably in the range of 0 ° C. to 55 ° C. When the Tg of the copolymer (A) is 0 ° C. or higher, the film strength is maintained, the water friction resistance of the laminate is not lowered, and when the Tg is 55 ° C. or lower, the compatibility with other printing layers is good. The friction resistance, water friction resistance, and scratch resistance of the laminate tend to be kept good without deterioration.
The glass transition temperature (Tg) refers to a so-called calculated glass transition temperature, and refers to a value calculated by the following method.
(Equation 1) 1 / Tg (K) = (W1 / T1) + (W2 / T2) + ... (Wn / Tn)
(Equation 2) Tg (° C.) = Tg (K) -273
W1, W2, ... Wn in the formula 1 represent the mass% of each monomer with respect to the total mass of the monomers used for producing the polymer, and T1, T2, ... Tn are the homopolymers of each monomer. Represents the glass transition temperature (K). As the values of T1, T2, ... Tn, the values described in Polymer Handbook (Fourth Edition, J. Brandrup, E.H. Immunogut, EA Grulke) are used.
Although the glass transition temperature of the homopolymer of each monomer is not described in the Polymer Hand Book, the glass transition temperature is based on JIS K7121 using a differential scanning calorimeter "DSC Q-100" (manufactured by TA Instrument). It was measured by the method described above. Specifically, the polymer from which the solvent has been completely removed by vacuum suction is measured for a change in calorific value in the range of -100 ° C to + 200 ° C at a heating rate of 20 ° C./min, and a straight line extending each baseline. The point where the straight line equidistant from the vertical axis direction and the curve of the stepwise change portion of the glass transition intersect was defined as the glass transition temperature.
前記コポリマー(A)は、本発明の水性リキッドインキに固形分換算で5~50質量%含有することが好ましい。前記コポリマー(A)の含有量が5質量%以上であれば、インキ塗膜強度が低下することもなく、基材密着性、耐水摩擦性等も良好に保たれる。反対に50質量%を以下であれば、着色力が低下する事が抑制でき、また高粘度となる事が避けられ、作業性が低下することもない。
The copolymer (A) is preferably contained in the aqueous liquid ink of the present invention in an amount of 5 to 50% by mass in terms of solid content. When the content of the copolymer (A) is 5% by mass or more, the strength of the ink coating film does not decrease, and the substrate adhesion, water friction resistance, and the like are kept good. On the other hand, if it is 50% by mass or less, the decrease in coloring power can be suppressed, the high viscosity can be avoided, and the workability does not decrease.
(界面活性剤)
本発明で使用する界面活性剤としては、アセチレン系界面活性剤及び/又はアルコールアルコキシレート系界面活性剤が好ましい。
本発明で使用するアセチレン系界面活性剤として具体的には、2,5-ジメチル-3-ヘキシン-2,5-ジオール、3,6-ジメチル-4-オクチン-3,6-ジオール、2,4,7,9-テトラメチル-5-デシン-4,7-ジオール、3,5-ジメチル-1-ヘキシン-3-オール、3-メチル-1-ブチン-3-オール、3-メチル-1-ペンチン-3-オール、3-ヘキシン-2,5-ジオール、2-ブチン-1,4-ジオール等が挙げられる。又、市販品としては、サーフィノール61、82、104(いずれも、エアープロダクツ社製)等 のアルキレンオキサイド非変性アセチレングリコール系界面活性剤や、 (Surfactant)
As the surfactant used in the present invention, an acetylene-based surfactant and / or an alcohol alkoxylate-based surfactant is preferable.
Specifically, as the acetylene-based surfactant used in the present invention, 2,5-dimethyl-3-hexyne-2,5-diol, 3,6-dimethyl-4-octyne-3,6-diol, 2, 4,7,9-Tetramethyl-5-decine-4,7-diol, 3,5-dimethyl-1-hexyne-3-ol, 3-methyl-1-butyne-3-ol, 3-methyl-1 -Pentyne-3-ol, 3-hexyne-2,5-diol, 2-butyne-1,4-diol and the like can be mentioned. Commercially available products include alkylene oxide-non-modified acetylene glycol-based surfactants such as Surfinol 61, 82, and 104 (all manufactured by Air Products & Chemicals).
本発明で使用する界面活性剤としては、アセチレン系界面活性剤及び/又はアルコールアルコキシレート系界面活性剤が好ましい。
本発明で使用するアセチレン系界面活性剤として具体的には、2,5-ジメチル-3-ヘキシン-2,5-ジオール、3,6-ジメチル-4-オクチン-3,6-ジオール、2,4,7,9-テトラメチル-5-デシン-4,7-ジオール、3,5-ジメチル-1-ヘキシン-3-オール、3-メチル-1-ブチン-3-オール、3-メチル-1-ペンチン-3-オール、3-ヘキシン-2,5-ジオール、2-ブチン-1,4-ジオール等が挙げられる。又、市販品としては、サーフィノール61、82、104(いずれも、エアープロダクツ社製)等 のアルキレンオキサイド非変性アセチレングリコール系界面活性剤や、 (Surfactant)
As the surfactant used in the present invention, an acetylene-based surfactant and / or an alcohol alkoxylate-based surfactant is preferable.
Specifically, as the acetylene-based surfactant used in the present invention, 2,5-dimethyl-3-hexyne-2,5-diol, 3,6-dimethyl-4-octyne-3,6-diol, 2, 4,7,9-Tetramethyl-5-decine-4,7-diol, 3,5-dimethyl-1-hexyne-3-ol, 3-methyl-1-butyne-3-ol, 3-methyl-1 -Pentyne-3-ol, 3-hexyne-2,5-diol, 2-butyne-1,4-diol and the like can be mentioned. Commercially available products include alkylene oxide-non-modified acetylene glycol-based surfactants such as Surfinol 61, 82, and 104 (all manufactured by Air Products & Chemicals).
サーフィノール420、440、465、485、TG、2502、ダイノール604、607(いずれも、エアープロダクツ社製)、サーフィノールSE、MD-20、オルフィンE1004、E1010、PD-004、EXP4300、PD-501、PD-502、SPC(いずれも、日信化学工業(株)製)、アセチレノールEH、E40、E60、E81、E100、E200(いずれも、川研ファインケミカル(株)製)等のアルキレンオキサイド変性アセチレングリコール系界面活性剤等が挙げられる。中でもアルキレンオキサイド変性アセチレングリコール系界面活性剤が好ましい。
また、本発明で使用するアルコールアルコキシレート系界面活性剤として具体的には、アルコールエトキシレート、アルコールポリエトキシレート等が挙げられ、市販品としてはDYNWET800(ビックケミー・ジャパン社製)が挙げられる。
これらアセチレン系界面活性剤、アルコールアルコキシレート系界面活性剤は各々単独で使用してもよいし、2つ以上組み合わせて使用してもよい。 Surfinol 420, 440, 465, 485, TG, 2502, Dynol 604, 607 (all manufactured by Air Products & Chemicals), Surfinol SE, MD-20, Orfin E1004, E1010, PD-004, EXP4300, PD-501 , PD-502, SPC (all manufactured by Nisshin Kagaku Kogyo Co., Ltd.), acetylenol EH, E40, E60, E81, E100, E200 (all manufactured by Kawaken Fine Chemicals Co., Ltd.) and other alkylene oxide-modified acetylenes. Glycol-based surfactants and the like can be mentioned. Of these, an alkylene oxide-modified acetylene glycol-based surfactant is preferable.
Specific examples of the alcohol alkoxylate-based surfactant used in the present invention include alcohol ethoxylate and alcohol polyethoxylate, and commercially available products include DYNWET800 (manufactured by Big Chemie Japan).
These acetylene-based surfactants and alcohol alkoxylate-based surfactants may be used alone or in combination of two or more.
また、本発明で使用するアルコールアルコキシレート系界面活性剤として具体的には、アルコールエトキシレート、アルコールポリエトキシレート等が挙げられ、市販品としてはDYNWET800(ビックケミー・ジャパン社製)が挙げられる。
これらアセチレン系界面活性剤、アルコールアルコキシレート系界面活性剤は各々単独で使用してもよいし、2つ以上組み合わせて使用してもよい。 Surfinol 420, 440, 465, 485, TG, 2502, Dynol 604, 607 (all manufactured by Air Products & Chemicals), Surfinol SE, MD-20, Orfin E1004, E1010, PD-004, EXP4300, PD-501 , PD-502, SPC (all manufactured by Nisshin Kagaku Kogyo Co., Ltd.), acetylenol EH, E40, E60, E81, E100, E200 (all manufactured by Kawaken Fine Chemicals Co., Ltd.) and other alkylene oxide-modified acetylenes. Glycol-based surfactants and the like can be mentioned. Of these, an alkylene oxide-modified acetylene glycol-based surfactant is preferable.
Specific examples of the alcohol alkoxylate-based surfactant used in the present invention include alcohol ethoxylate and alcohol polyethoxylate, and commercially available products include DYNWET800 (manufactured by Big Chemie Japan).
These acetylene-based surfactants and alcohol alkoxylate-based surfactants may be used alone or in combination of two or more.
前記アセチレン系界面活性剤及び/又はアルコールアルコキシレート系界面活性剤の添加量の総量は、インキ全量の0.1~1質量%である事が好ましい。これらのアセチレン系界面活性剤は、単独で使用してもよいし、2つ以上組み合わせて使用しても良く、アセチレン系界面活性剤及び/又はアルコールアルコキシレート系界面活性剤の添加量の総量がインキ全量の0.1質量%以上であれば、基材との塗れ性が向上し基材との密着性を保持する事ができる。アセチレン系界面活性剤及び/又はアルコールアルコキシレート系界面活性剤の添加量の総量がインキ全量の1質量%以下であれば、耐摩耗性、耐水性摩耗性、及び耐スクラッチ性が低下する事もない。
更に必要に応じ、その他アクリルポリマー系界面活性剤(例えばポリフローWS-314共栄社化学(株)社製)や、変性シリコーン系界面活性剤(例えばポリフローKL-401共栄社化学(株)社製)を使用してもよい。
使用する界面活性剤の総量は前記理由からインキ全量の0.1~1質量%である事が好ましい。 The total amount of the acetylene-based surfactant and / or the alcohol alkoxylate-based surfactant added is preferably 0.1 to 1% by mass of the total amount of the ink. These acetylene-based surfactants may be used alone or in combination of two or more, and the total amount of the acetylene-based surfactant and / or the alcohol alkoxylate-based surfactant added is When it is 0.1% by mass or more of the total amount of ink, the coatability with the base material is improved and the adhesion with the base material can be maintained. If the total amount of the acetylene-based surfactant and / or the alcohol alkoxylate-based surfactant added is 1% by mass or less of the total amount of the ink, the abrasion resistance, the water abrasion resistance, and the scratch resistance may decrease. Absent.
Further, if necessary, other acrylic polymer-based surfactants (for example, Polyflow WS-314 Kyoeisha Chemical Co., Ltd.) and modified silicone-based surfactants (for example, Polyflow KL-401 Kyoeisha Chemical Co., Ltd.) are used. You may.
For the above reasons, the total amount of the surfactant used is preferably 0.1 to 1% by mass of the total amount of the ink.
更に必要に応じ、その他アクリルポリマー系界面活性剤(例えばポリフローWS-314共栄社化学(株)社製)や、変性シリコーン系界面活性剤(例えばポリフローKL-401共栄社化学(株)社製)を使用してもよい。
使用する界面活性剤の総量は前記理由からインキ全量の0.1~1質量%である事が好ましい。 The total amount of the acetylene-based surfactant and / or the alcohol alkoxylate-based surfactant added is preferably 0.1 to 1% by mass of the total amount of the ink. These acetylene-based surfactants may be used alone or in combination of two or more, and the total amount of the acetylene-based surfactant and / or the alcohol alkoxylate-based surfactant added is When it is 0.1% by mass or more of the total amount of ink, the coatability with the base material is improved and the adhesion with the base material can be maintained. If the total amount of the acetylene-based surfactant and / or the alcohol alkoxylate-based surfactant added is 1% by mass or less of the total amount of the ink, the abrasion resistance, the water abrasion resistance, and the scratch resistance may decrease. Absent.
Further, if necessary, other acrylic polymer-based surfactants (for example, Polyflow WS-314 Kyoeisha Chemical Co., Ltd.) and modified silicone-based surfactants (for example, Polyflow KL-401 Kyoeisha Chemical Co., Ltd.) are used. You may.
For the above reasons, the total amount of the surfactant used is preferably 0.1 to 1% by mass of the total amount of the ink.
(ワックス)
本発明で使用するワックスとしては、炭化水素系ワックスが好ましい。具体的には流動パラフィン、天然パラフィン、合成パラフィン、マイクロクリスタリンワックス、ポリエチレンワックス、フルオロカーボンワックス、エチレン-プロピレン共重合体ワックス、4フッ化エチレン樹脂ワックス、フィッシャー・トロプシュワックス等が挙げられる。中でもポリエチレンワックスが好ましい。
これらのワックスは、単独で使用してもよいし、2つ以上組み合わせて使用しても良く、これらワックスの添加量の総量がインキ全量の0.5~5質量%である事が好ましい。ワックスの添加量の総量がインキ全量の0.5質量%以上であれば、耐摩耗性、耐水性摩耗性、及び耐スクラッチ性を保持する事ができる。ワックスの添加量の総量がインキ全量の5質量%以下であれば、基材との密着性、耐摩耗性、耐水性摩耗性、及び耐スクラッチ性を保持する事ができる。 (wax)
As the wax used in the present invention, a hydrocarbon wax is preferable. Specific examples thereof include liquid paraffin, natural paraffin, synthetic paraffin, microcrystalline wax, polyethylene wax, fluorocarbon wax, ethylene-propylene copolymer wax, tetrafluoride ethylene resin wax, Fisher Tropsch wax and the like. Of these, polyethylene wax is preferable.
These waxes may be used alone or in combination of two or more, and the total amount of these waxes added is preferably 0.5 to 5% by mass of the total amount of the ink. When the total amount of wax added is 0.5% by mass or more of the total amount of ink, abrasion resistance, water abrasion resistance, and scratch resistance can be maintained. When the total amount of wax added is 5% by mass or less of the total amount of ink, adhesion to the substrate, abrasion resistance, water abrasion resistance, and scratch resistance can be maintained.
本発明で使用するワックスとしては、炭化水素系ワックスが好ましい。具体的には流動パラフィン、天然パラフィン、合成パラフィン、マイクロクリスタリンワックス、ポリエチレンワックス、フルオロカーボンワックス、エチレン-プロピレン共重合体ワックス、4フッ化エチレン樹脂ワックス、フィッシャー・トロプシュワックス等が挙げられる。中でもポリエチレンワックスが好ましい。
これらのワックスは、単独で使用してもよいし、2つ以上組み合わせて使用しても良く、これらワックスの添加量の総量がインキ全量の0.5~5質量%である事が好ましい。ワックスの添加量の総量がインキ全量の0.5質量%以上であれば、耐摩耗性、耐水性摩耗性、及び耐スクラッチ性を保持する事ができる。ワックスの添加量の総量がインキ全量の5質量%以下であれば、基材との密着性、耐摩耗性、耐水性摩耗性、及び耐スクラッチ性を保持する事ができる。 (wax)
As the wax used in the present invention, a hydrocarbon wax is preferable. Specific examples thereof include liquid paraffin, natural paraffin, synthetic paraffin, microcrystalline wax, polyethylene wax, fluorocarbon wax, ethylene-propylene copolymer wax, tetrafluoride ethylene resin wax, Fisher Tropsch wax and the like. Of these, polyethylene wax is preferable.
These waxes may be used alone or in combination of two or more, and the total amount of these waxes added is preferably 0.5 to 5% by mass of the total amount of the ink. When the total amount of wax added is 0.5% by mass or more of the total amount of ink, abrasion resistance, water abrasion resistance, and scratch resistance can be maintained. When the total amount of wax added is 5% by mass or less of the total amount of ink, adhesion to the substrate, abrasion resistance, water abrasion resistance, and scratch resistance can be maintained.
(硬化剤)
本発明では、酸と反応しうる硬化剤を併用してもよい。酸と反応しうる硬化剤としては、特に限定されることはなく水性媒体中で使用可能な公知の硬化剤を使用することができる。例えば、エポキシ系硬化剤、カルボジイミド系硬化剤、オキサゾリン系硬化剤などが挙げられる。 (Hardener)
In the present invention, a curing agent capable of reacting with an acid may be used in combination. The curing agent capable of reacting with the acid is not particularly limited, and a known curing agent that can be used in an aqueous medium can be used. For example, an epoxy-based curing agent, a carbodiimide-based curing agent, an oxazoline-based curing agent, and the like can be mentioned.
本発明では、酸と反応しうる硬化剤を併用してもよい。酸と反応しうる硬化剤としては、特に限定されることはなく水性媒体中で使用可能な公知の硬化剤を使用することができる。例えば、エポキシ系硬化剤、カルボジイミド系硬化剤、オキサゾリン系硬化剤などが挙げられる。 (Hardener)
In the present invention, a curing agent capable of reacting with an acid may be used in combination. The curing agent capable of reacting with the acid is not particularly limited, and a known curing agent that can be used in an aqueous medium can be used. For example, an epoxy-based curing agent, a carbodiimide-based curing agent, an oxazoline-based curing agent, and the like can be mentioned.
前記エポキシ系硬化剤は、少なくとも1つのエポキシ基を有する化合物であれば、特に限定されない。エポキシ系硬化剤としては、例えば、ビスフェノールAジグリシジルエーテル、変性ビスフェノールAジグリシジルエーテル、ノボラックグリシジルエーテル、グリセリンポリグリシジルエーテル、ポリグリセリンポリグリシジルエーテルなどのエポキシ樹脂が挙げられる。
The epoxy-based curing agent is not particularly limited as long as it is a compound having at least one epoxy group. Examples of the epoxy-based curing agent include epoxy resins such as bisphenol A diglycidyl ether, modified bisphenol A diglycidyl ether, novolak glycidyl ether, glycerin polyglycidyl ether, and polyglycerin polyglycidyl ether.
前記カルボジイミド系硬化剤は、カルボジイミド基(-N=C=N-)を少なくとも1つ有する化合物であれば、特に限定されない。カルボジイミド系硬化剤としては、カルボジイミド基を少なくとも2つ以上有するポリカルボジイミド化合物が好ましい。
The carbodiimide-based curing agent is not particularly limited as long as it is a compound having at least one carbodiimide group (-N = C = N-). As the carbodiimide-based curing agent, a polycarbodiimide compound having at least two or more carbodiimide groups is preferable.
前記オキサゾリン系硬化剤は、オキサゾリン骨格を有する化合物であれば、特に限定されない。オキサゾリン系硬化剤としては、具体的には、日本触媒社製のエポクロスシリーズなどが挙げられる。
前記エポキシ化合物としてはビスフェノールAのジグリシジルエーテルおよびそのオリゴマー、水素化ビスフェノールAのジグリシジルエーテルおよびそのオリゴマー、オルソフタル酸ジグリシジルエステル、イソフタル酸ジグリシジルエステル、テレフタル酸ジグリシジルエステル、p-オキシ安息香酸ジグリシジルエステル、テトラハイドロフタル酸ジグリシジルエステル、ヘキサハイドロフタル酸ジグリシジルエステル、コハク酸ジグリシジルエステル、アジピン酸ジグリシジルエステル、セバシン酸ジグリシジルエステル、エチレングリコールジグリシジルエエーテル、プロピレングリコールジグリシジルエーテル、1,4-ブタンジオールジグリシジルエーテル、1,6-ヘキサンジオールジグリシジルエーテルおよびポリアルキレングリコールジグリシジルエーテル類、トリメリット酸トリグリシジルエステル、トリグリシジルイソシアヌレート、1,4-ジグリシジルオキシベンゼン、ジグリシジルプロピレン尿素、グリセロールトリグリシジルエーテル、トリメチロールエタントリグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ペンタエリスリトールテトラグリシジルエーテル、グリセロールアルキレンオキサイド付加物のトリグリシジルエーテルなどを挙げることができる。 The oxazoline-based curing agent is not particularly limited as long as it is a compound having an oxazoline skeleton. Specific examples of the oxazoline-based curing agent include the Epocross series manufactured by Nippon Shokubai Co., Ltd.
Examples of the epoxy compound include bisphenol A diglycidyl ether and its oligomer, hydride bisphenol A diglycidyl ether and its oligomer, orthophthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, and p-oxybenzoic acid. Diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, succinic acid diglycidyl ester, adipate diglycidyl ester, sebacic acid diglycidyl ester, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether , 1,4-Butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether and polyalkylene glycol diglycidyl ethers, trimeric acid triglycidyl ester, triglycidyl isocyanurate, 1,4-diglycidyloxybenzene, Examples thereof include diglycidyl propylene urea, glycerol triglycidyl ether, trimethylol ethane triglycidyl ether, trimethylol propane triglycidyl ether, pentaerythritol tetraglycidyl ether, and triglycidyl ether as a glycerol alkylene oxide adduct.
前記エポキシ化合物としてはビスフェノールAのジグリシジルエーテルおよびそのオリゴマー、水素化ビスフェノールAのジグリシジルエーテルおよびそのオリゴマー、オルソフタル酸ジグリシジルエステル、イソフタル酸ジグリシジルエステル、テレフタル酸ジグリシジルエステル、p-オキシ安息香酸ジグリシジルエステル、テトラハイドロフタル酸ジグリシジルエステル、ヘキサハイドロフタル酸ジグリシジルエステル、コハク酸ジグリシジルエステル、アジピン酸ジグリシジルエステル、セバシン酸ジグリシジルエステル、エチレングリコールジグリシジルエエーテル、プロピレングリコールジグリシジルエーテル、1,4-ブタンジオールジグリシジルエーテル、1,6-ヘキサンジオールジグリシジルエーテルおよびポリアルキレングリコールジグリシジルエーテル類、トリメリット酸トリグリシジルエステル、トリグリシジルイソシアヌレート、1,4-ジグリシジルオキシベンゼン、ジグリシジルプロピレン尿素、グリセロールトリグリシジルエーテル、トリメチロールエタントリグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ペンタエリスリトールテトラグリシジルエーテル、グリセロールアルキレンオキサイド付加物のトリグリシジルエーテルなどを挙げることができる。 The oxazoline-based curing agent is not particularly limited as long as it is a compound having an oxazoline skeleton. Specific examples of the oxazoline-based curing agent include the Epocross series manufactured by Nippon Shokubai Co., Ltd.
Examples of the epoxy compound include bisphenol A diglycidyl ether and its oligomer, hydride bisphenol A diglycidyl ether and its oligomer, orthophthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, and p-oxybenzoic acid. Diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, succinic acid diglycidyl ester, adipate diglycidyl ester, sebacic acid diglycidyl ester, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether , 1,4-Butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether and polyalkylene glycol diglycidyl ethers, trimeric acid triglycidyl ester, triglycidyl isocyanurate, 1,4-diglycidyloxybenzene, Examples thereof include diglycidyl propylene urea, glycerol triglycidyl ether, trimethylol ethane triglycidyl ether, trimethylol propane triglycidyl ether, pentaerythritol tetraglycidyl ether, and triglycidyl ether as a glycerol alkylene oxide adduct.
本発明で使用する硬化剤の添加量は、インキ全量の固形分換算で0.1~10.0質量%が好ましく、より好ましくは0.5~9.0質量%の範囲である。
添加量が0.1質量%以上であれば硬化剤としての効果が得られる一方、10.0質量%以下であれば、基材密着性、耐摩擦性、耐水摩擦性が保持される傾向となる。 The amount of the curing agent added in the present invention is preferably 0.1 to 10.0% by mass, more preferably 0.5 to 9.0% by mass in terms of solid content of the total amount of ink.
If the amount added is 0.1% by mass or more, the effect as a curing agent can be obtained, while if it is 10.0% by mass or less, the substrate adhesion, abrasion resistance, and water friction resistance tend to be maintained. Become.
添加量が0.1質量%以上であれば硬化剤としての効果が得られる一方、10.0質量%以下であれば、基材密着性、耐摩擦性、耐水摩擦性が保持される傾向となる。 The amount of the curing agent added in the present invention is preferably 0.1 to 10.0% by mass, more preferably 0.5 to 9.0% by mass in terms of solid content of the total amount of ink.
If the amount added is 0.1% by mass or more, the effect as a curing agent can be obtained, while if it is 10.0% by mass or less, the substrate adhesion, abrasion resistance, and water friction resistance tend to be maintained. Become.
(溶剤)
本発明の水性リキッドインキに含まれる溶剤としては、水単独または水と混和する有機溶剤を使用することができる。有機溶剤としては、例えばメチルアルコール、エチルアルコール、イソプロピルアルコール、n-プロピルアルコール等のアルコール類やプロピレングリコール、グリセリン等の多価アルコール類、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノn-プロピルエーテル、エチルカルビトール等のエーテル類等が挙げられる。 (solvent)
As the solvent contained in the aqueous liquid ink of the present invention, water alone or an organic solvent miscible with water can be used. Examples of the organic solvent include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol and n-propyl alcohol, polyhydric alcohols such as propylene glycol and glycerin, propylene glycol monomethyl ether, propylene glycol monoethyl ether and propylene glycol mono n. -Ethers such as propyl ether and ethyl carbitol can be mentioned.
本発明の水性リキッドインキに含まれる溶剤としては、水単独または水と混和する有機溶剤を使用することができる。有機溶剤としては、例えばメチルアルコール、エチルアルコール、イソプロピルアルコール、n-プロピルアルコール等のアルコール類やプロピレングリコール、グリセリン等の多価アルコール類、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノn-プロピルエーテル、エチルカルビトール等のエーテル類等が挙げられる。 (solvent)
As the solvent contained in the aqueous liquid ink of the present invention, water alone or an organic solvent miscible with water can be used. Examples of the organic solvent include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol and n-propyl alcohol, polyhydric alcohols such as propylene glycol and glycerin, propylene glycol monomethyl ether, propylene glycol monoethyl ether and propylene glycol mono n. -Ethers such as propyl ether and ethyl carbitol can be mentioned.
(顔料)
本発明の水性リキッドインキは、色材を含まなければ印刷後透明皮膜となり無色透明インキ(本技術分野においては、カラー印刷層の最表層にベタ印刷しカラー印刷層を保護する目的で使用することから、通称オーバーコートニス、OPニスとも称される。本発明においては以後OPニスと称する場合がある)として使用することができる。また勿論、色材を含有しいわゆる白、黒、カラー印刷用のインキとしても使用する。
色材として具体的には一般のインキ、塗料、及び記録剤などに使用されている無機顔料、有機顔料を挙げることができる。有機顔料としては、溶性アゾ系、不溶性アゾ系、アゾ系、フタロシアニン系、ハロゲン化フタロシアニン系、アントラキノン系、アンサンスロン系、ジアンスラキノニル系、アンスラピリミジン系、ペリレン系、ペリノン系、キナクリドン系、チオインジゴ系、ジオキサジン系、イソインドリノン系、キノフタロン系、アゾメチンアゾ系、フラバンスロン系、ジケトピロロピロール系、イソインドリン系、インダンスロン系、カーボンブラック系などの顔料が挙げられる。また、例えば、カーミン6B、レーキレッドC、パーマネントレッド2B、ジスアゾイエロー、ピラゾロンオレンジ、カーミンFB、クロモフタルイエロー、クロモフタルレッド、フタロシアニンブルー、フタロシアニングリーン、ジオキサジンバイオレット、キナクリドンマゼンタ、キナクリドンレッド、インダンスロンブルー、ピリミジンイエロー、チオインジゴボルドー、チオインジゴマゼンタ、ペリレンレッド、ペリノンオレンジ、イソインドリノンイエロー、アニリンブラック、ジケトピロロピロールレッド、昼光蛍光顔料等が挙げられる。また未酸性処理顔料、酸性処理顔料のいずれも使用することができる。以下に有機顔料として好ましいものの具体的な例を挙げる。 (Pigment)
The water-based liquid ink of the present invention becomes a transparent film after printing if it does not contain a coloring material, and is a colorless transparent ink (in the present technical field, it is used for the purpose of solid printing on the outermost layer of a color printing layer to protect the color printing layer. Therefore, it is also commonly referred to as overcoat varnish or OP varnish. In the present invention, it may be referred to as OP varnish). Of course, it also contains a coloring material and is used as an ink for so-called white, black, and color printing.
Specific examples of the coloring material include inorganic pigments and organic pigments used in general inks, paints, recording agents and the like. Organic pigments include soluble azo-based, insoluble azo-based, azo-based, phthalocyanine-based, halogenated phthalocyanine-based, anthraquinone-based, anthraslon-based, dianthraquinone-based, anthrapyrimidine-based, perylene-based, perinone-based, quinacridone-based, Pigments such as thioindigo-based, dioxazine-based, isoindolinone-based, quinophthalone-based, azomethine-azo-based, flavanthlon-based, diketopyrrolopyrrole-based, isoindoline-based, indanslon-based, and carbon black-based pigments can be mentioned. Also, for example, Carmin 6B, Lake Red C, Permanent Red 2B, Disazo Yellow, Pyrazolone Orange, Carmin FB, Chromophtal Yellow, Chromophtal Red, Phthalocyanine Blue, Phthalocyanine Green, Dioxazine Violet, Quinacridone Magenta, Quinacridone Red, Indance. Examples thereof include lonblue, pyrimidine yellow, thioindigo bordeaux, thioindigo magenta, perylene red, perinone orange, isoindolinone yellow, aniline black, diketopyrrolopyrrole red, and daylight fluorescent pigment. Further, both unacidified treated pigments and acidic treated pigments can be used. Specific examples of preferable organic pigments are given below.
本発明の水性リキッドインキは、色材を含まなければ印刷後透明皮膜となり無色透明インキ(本技術分野においては、カラー印刷層の最表層にベタ印刷しカラー印刷層を保護する目的で使用することから、通称オーバーコートニス、OPニスとも称される。本発明においては以後OPニスと称する場合がある)として使用することができる。また勿論、色材を含有しいわゆる白、黒、カラー印刷用のインキとしても使用する。
色材として具体的には一般のインキ、塗料、及び記録剤などに使用されている無機顔料、有機顔料を挙げることができる。有機顔料としては、溶性アゾ系、不溶性アゾ系、アゾ系、フタロシアニン系、ハロゲン化フタロシアニン系、アントラキノン系、アンサンスロン系、ジアンスラキノニル系、アンスラピリミジン系、ペリレン系、ペリノン系、キナクリドン系、チオインジゴ系、ジオキサジン系、イソインドリノン系、キノフタロン系、アゾメチンアゾ系、フラバンスロン系、ジケトピロロピロール系、イソインドリン系、インダンスロン系、カーボンブラック系などの顔料が挙げられる。また、例えば、カーミン6B、レーキレッドC、パーマネントレッド2B、ジスアゾイエロー、ピラゾロンオレンジ、カーミンFB、クロモフタルイエロー、クロモフタルレッド、フタロシアニンブルー、フタロシアニングリーン、ジオキサジンバイオレット、キナクリドンマゼンタ、キナクリドンレッド、インダンスロンブルー、ピリミジンイエロー、チオインジゴボルドー、チオインジゴマゼンタ、ペリレンレッド、ペリノンオレンジ、イソインドリノンイエロー、アニリンブラック、ジケトピロロピロールレッド、昼光蛍光顔料等が挙げられる。また未酸性処理顔料、酸性処理顔料のいずれも使用することができる。以下に有機顔料として好ましいものの具体的な例を挙げる。 (Pigment)
The water-based liquid ink of the present invention becomes a transparent film after printing if it does not contain a coloring material, and is a colorless transparent ink (in the present technical field, it is used for the purpose of solid printing on the outermost layer of a color printing layer to protect the color printing layer. Therefore, it is also commonly referred to as overcoat varnish or OP varnish. In the present invention, it may be referred to as OP varnish). Of course, it also contains a coloring material and is used as an ink for so-called white, black, and color printing.
Specific examples of the coloring material include inorganic pigments and organic pigments used in general inks, paints, recording agents and the like. Organic pigments include soluble azo-based, insoluble azo-based, azo-based, phthalocyanine-based, halogenated phthalocyanine-based, anthraquinone-based, anthraslon-based, dianthraquinone-based, anthrapyrimidine-based, perylene-based, perinone-based, quinacridone-based, Pigments such as thioindigo-based, dioxazine-based, isoindolinone-based, quinophthalone-based, azomethine-azo-based, flavanthlon-based, diketopyrrolopyrrole-based, isoindoline-based, indanslon-based, and carbon black-based pigments can be mentioned. Also, for example, Carmin 6B, Lake Red C, Permanent Red 2B, Disazo Yellow, Pyrazolone Orange, Carmin FB, Chromophtal Yellow, Chromophtal Red, Phthalocyanine Blue, Phthalocyanine Green, Dioxazine Violet, Quinacridone Magenta, Quinacridone Red, Indance. Examples thereof include lonblue, pyrimidine yellow, thioindigo bordeaux, thioindigo magenta, perylene red, perinone orange, isoindolinone yellow, aniline black, diketopyrrolopyrrole red, and daylight fluorescent pigment. Further, both unacidified treated pigments and acidic treated pigments can be used. Specific examples of preferable organic pigments are given below.
黒色顔料としては、例えばC.I.ピグメントブラック1、C.I.ピグメントブラック6、C.I.ピグメントブラック7、C.I.ピグメントブラック9、C.I.ピグメントブラック20等が挙げられる。
Examples of the black pigment include C.I. I. Pigment Black 1, C.I. I. Pigment Black 6, C.I. I. Pigment Black 7, C.I. I. Pigment Black 9, C.I. I. Pigment Black 20 and the like.
藍色顔料としては、例えばC.I.ピグメントブルー15、C.I.ピグメントブルー15:1、C.I.ピグメントブルー15:2、C.I.ピグメントブルー15:3、C.I.ピグメントブルー15:4、C.I.ピグメントブルー15:5、C.I.ピグメントブルー15:6、C.I.ピグメントブルー16、C.I.ピグメントブルー17:1、C.I.ピグメントブルー22、C.I.ピグメントブルー24:1、C.I.ピグメントブルー25、C.I.ピグメントブルー26、C.I.ピグメントブルー60、C.I.ピグメントブルー61、C.I.ピグメントブルー62、C.I.ピグメントブルー63、C.I.ピグメントブルー64、C.I.ピグメントブルー75、C.I.ピグメントブルー79、C.I.ピグメントブルー80などが挙げられる。
Examples of the indigo pigment include C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 1, C.I. I. Pigment Blue 15: 2, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 15: 5, C.I. I. Pigment Blue 15: 6, C.I. I. Pigment Blue 16, C.I. I. Pigment Blue 17: 1, C.I. I. Pigment Blue 22, C.I. I. Pigment Blue 24: 1, C.I. I. Pigment Blue 25, C.I. I. Pigment Blue 26, C.I. I. Pigment Blue 60, C.I. I. Pigment Blue 61, C.I. I. Pigment Blue 62, C.I. I. Pigment Blue 63, C.I. I. Pigment Blue 64, C.I. I. Pigment Blue 75, C.I. I. Pigment Blue 79, C.I. I. Pigment Blue 80 and the like.
緑色顔料としては、例えばC.I.ピグメントグリーン1、C.I.ピグメントグリーン4、C.I.ピグメントグリーン7、C.I.ピグメントグリーン8、C.I.ピグメントグリーン10、C.I.ピグメントグリーン36などが挙げられる。
Examples of green pigments include C.I. I. Pigment Green 1, C.I. I. Pigment Green 4, C.I. I. Pigment Green 7, C.I. I. Pigment Green 8, C.I. I. Pigment Green 10, C.I. I. Pigment Green 36 and the like.
赤色顔料としては、例えばC.I.ピグメントレッド1、C.I.ピグメントレッド2、C.I.ピグメントレッド3、C.I.ピグメントレッド4、C.I.ピグメントレッド5、C.I.ピグメントレッド6、C.I.ピグメントレッド7、C.I.ピグメントレッド8、C.I.ピグメントレッド9、C.I.ピグメントレッド10、C.I.ピグメントレッド11、C.I.ピグメントレッド12、C.I.ピグメントレッド15、C.I.ピグメントレッド16、C.I.ピグメントレッド17、C.I.ピグメントレッド18、C.I.ピグメントレッド19、C.I.ピグメントレッド20、C.I.ピグメントレッド21、C.I.ピグメントレッド22、C.I.ピグメントレッド23、C.I.ピグメントレッド31、C.I.ピグメントレッド32、C.I.ピグメントレッド38、C.I.ピグメントレッド41、C.I.ピグメントレッド43、C.I.ピグメントレッド46、C.I.ピグメントレッド48、C.I.ピグメントレッド48:1、C.I.ピグメントレッド48:2、C.I.ピグメントレッド48:3、C.I.ピグメントレッド48:4、C.I.ピグメントレッド48:5、C.I.ピグメントレッド48:6、C.I.ピグメントレッド49、C.I.ピグメントレッド49:1、C.I.ピグメントレッド49:2、C.I.ピグメントレッド49:3、C.I.ピグメントレッド52、C.I.ピグメントレッド52:1、C.I.ピグメントレッド52:2、C.I.ピグメントレッド53、C.I.ピグメントレッド53:1、C.I.ピグメントレッド53:2、C.I.ピグメントレッド53:3、C.I.ピグメントレッド54、C.I.ピグメントレッド57、C.I.ピグメントレッド57:1、C.I.ピグメントレッド58、C.I.ピグメントレッド58:1、C.I.ピグメントレッド58:2、C.I.ピグメントレッド58:3、C.I.ピグメントレッド58:4、C.I.ピグメントレッド60:1、C.I.ピグメントレッド63、C.I.ピグメントレッド63:1、C.I.ピグメントレッド63:2、C.I.ピグメントレッド63:3、C.I.ピグメントレッド64:1、C.I.ピグメントレッド68、C.I.ピグメントレッド68、C.I.ピグメントレッド81:1、C.I.ピグメントレッド83、C.I.ピグメントレッド88、C.I.ピグメントレッド89、C.I.ピグメントレッド95、C.I.ピグメントレッド112、C.I.ピグメントレッド114、C.I.ピグメントレッド119、C.I.ピグメントレッド122、C.I.ピグメントレッド123、C.I.ピグメントレッド136、C.I.ピグメントレッド144、C.I.ピグメントレッド146、C.I.ピグメントレッド147、C.I.ピグメントレッド149、C.I.ピグメントレッド150、C.I.ピグメントレッド164、C.I.ピグメントレッド166、C.I.ピグメントレッド168、C.I.ピグメントレッド169、C.I.ピグメントレッド170、C.I.ピグメントレッド171、C.I.ピグメントレッド172、C.I.ピグメントレッド175、C.I.ピグメントレッド176、C.I.ピグメントレッド177、C.I.ピグメントレッド178、C.I.ピグメントレッド179、C.I.ピグメントレッド180、C.I.ピグメントレッド181、C.I.ピグメントレッド182、C.I.ピグメントレッド183、C.I.ピグメントレッド184、C.I.ピグメントレッド185、C.I.ピグメントレッド187、C.I.ピグメントレッド188、C.I.ピグメントレッド190、C.I.ピグメントレッド192、C.I.ピグメントレッド193、C.I.ピグメントレッド194、C.I.ピグメントレッド200、C.I.ピグメントレッド202、C.I.ピグメントレッド206、C.I.ピグメントレッド207、C.I.ピグメントレッド208、C.I.ピグメントレッド209、C.I.ピグメントレッド210、C.I.ピグメントレッド211、C.I.ピグメントレッド213、C.I.ピグメントレッド214、C.I.ピグメントレッド216、C.I.ピグメントレッド215、C.I.ピグメントレッド216、C.I.ピグメントレッド220、C.I.ピグメントレッド221、C.I.ピグメントレッド223、C.I.ピグメントレッド224、C.I.ピグメントレッド226、C.I.ピグメントレッド237、C.I.ピグメントレッド238、C.I.ピグメントレッド239、C.I.ピグメントレッド240、C.I.ピグメントレッド242、C.I.ピグメントレッド245、C.I.ピグメントレッド247、C.I.ピグメントレッド248、C.I.ピグメントレッド251、C.I.ピグメントレッド253、C.I.ピグメントレッド254、C.I.ピグメントレッド255、C.I.ピグメントレッド256、C.I.ピグメントレッド257、C.I.ピグメントレッド258、C.I.ピグメントレッド260、C.I.ピグメントレッド262、C.I.ピグメントレッド263、C.I.ピグメントレッド264、C.I.ピグメントレッド266、C.I.ピグメントレッド268、C.I.ピグメントレッド269、C.I.ピグメントレッド270、C.I.ピグメントレッド271、C.I.ピグメントレッド272、C.I.ピグメントレッド279、などが挙げられる。
Examples of the red pigment include C.I. I. Pigment Red 1, C.I. I. Pigment Red 2, C.I. I. Pigment Red 3, C.I. I. Pigment Red 4, C.I. I. Pigment Red 5, C.I. I. Pigment Red 6, C.I. I. Pigment Red 7, C.I. I. Pigment Red 8, C.I. I. Pigment Red 9, C.I. I. Pigment Red 10, C.I. I. Pigment Red 11, C.I. I. Pigment Red 12, C.I. I. Pigment Red 15, C.I. I. Pigment Red 16, C.I. I. Pigment Red 17, C.I. I. Pigment Red 18, C.I. I. Pigment Red 19, C.I. I. Pigment Red 20, C.I. I. Pigment Red 21, C.I. I. Pigment Red 22, C.I. I. Pigment Red 23, C.I. I. Pigment Red 31, C.I. I. Pigment Red 32, C.I. I. Pigment Red 38, C.I. I. Pigment Red 41, C.I. I. Pigment Red 43, C.I. I. Pigment Red 46, C.I. I. Pigment Red 48, C.I. I. Pigment Red 48: 1, C.I. I. Pigment Red 48: 2, C.I. I. Pigment Red 48: 3, C.I. I. Pigment Red 48: 4, C.I. I. Pigment Red 48: 5, C.I. I. Pigment Red 48: 6, C.I. I. Pigment Red 49, C.I. I. Pigment Red 49: 1, C.I. I. Pigment Red 49: 2, C.I. I. Pigment Red 49: 3, C.I. I. Pigment Red 52, C.I. I. Pigment Red 52: 1, C.I. I. Pigment Red 52: 2, C.I. I. Pigment Red 53, C.I. I. Pigment Red 53: 1, C.I. I. Pigment Red 53: 2, C.I. I. Pigment Red 53: 3, C.I. I. Pigment Red 54, C.I. I. Pigment Red 57, C.I. I. Pigment Red 57: 1, C.I. I. Pigment Red 58, C.I. I. Pigment Red 58: 1, C.I. I. Pigment Red 58: 2, C.I. I. Pigment Red 58: 3, C.I. I. Pigment Red 58: 4, C.I. I. Pigment Red 60: 1, C.I. I. Pigment Red 63, C.I. I. Pigment Red 63: 1, C.I. I. Pigment Red 63: 2, C.I. I. Pigment Red 63: 3, C.I. I. Pigment Red 64: 1, C.I. I. Pigment Red 68, C.I. I. Pigment Red 68, C.I. I. Pigment Red 81: 1, C.I. I. Pigment Red 83, C.I. I. Pigment Red 88, C.I. I. Pigment Red 89, C.I. I. Pigment Red 95, C.I. I. Pigment Red 112, C.I. I. Pigment Red 114, C.I. I. Pigment Red 119, C.I. I. Pigment Red 122, C.I. I. Pigment Red 123, C.I. I. Pigment Red 136, C.I. I. Pigment Red 144, C.I. I. Pigment Red 146, C.I. I. Pigment Red 147, C.I. I. Pigment Red 149, C.I. I. Pigment Red 150, C.I. I. Pigment Red 164, C.I. I. Pigment Red 166, C.I. I. Pigment Red 168, C.I. I. Pigment Red 169, C.I. I. Pigment Red 170, C.I. I. Pigment Red 171 and C.I. I. Pigment Red 172, C.I. I. Pigment Red 175, C.I. I. Pigment Red 176, C.I. I. Pigment Red 177, C.I. I. Pigment Red 178, C.I. I. Pigment Red 179, C.I. I. Pigment Red 180, C.I. I. Pigment Red 181 and C.I. I. Pigment Red 182, C.I. I. Pigment Red 183, C.I. I. Pigment Red 184, C.I. I. Pigment Red 185, C.I. I. Pigment Red 187, C.I. I. Pigment Red 188, C.I. I. Pigment Red 190, C.I. I. Pigment Red 192, C.I. I. Pigment Red 193, C.I. I. Pigment Red 194, C.I. I. Pigment Red 200, C.I. I. Pigment Red 202, C.I. I. Pigment Red 206, C.I. I. Pigment Red 207, C.I. I. Pigment Red 208, C.I. I. Pigment Red 209, C.I. I. Pigment Red 210, C.I. I. Pigment Red 211, C.I. I. Pigment Red 213, C.I. I. Pigment Red 214, C.I. I. Pigment Red 216, C.I. I. Pigment Red 215, C.I. I. Pigment Red 216, C.I. I. Pigment Red 220, C.I. I. Pigment Red 221 and C.I. I. Pigment Red 223, C.I. I. Pigment Red 224, C.I. I. Pigment Red 226, C.I. I. Pigment Red 237, C.I. I. Pigment Red 238, C.I. I. Pigment Red 239, C.I. I. Pigment Red 240, C.I. I. Pigment Red 242, C.I. I. Pigment Red 245, C.I. I. Pigment Red 247, C.I. I. Pigment Red 248, C.I. I. Pigment Red 251 and C.I. I. Pigment Red 253, C.I. I. Pigment Red 254, C.I. I. Pigment Red 255, C.I. I. Pigment Red 256, C.I. I. Pigment Red 257, C.I. I. Pigment Red 258, C.I. I. Pigment Red 260, C.I. I. Pigment Red 262, C.I. I. Pigment Red 263, C.I. I. Pigment Red 264, C.I. I. Pigment Red 266, C.I. I. Pigment Red 268, C.I. I. Pigment Red 269, C.I. I. Pigment Red 270, C.I. I. Pigment Red 271, C.I. I. Pigment Red 272, C.I. I. Pigment Red 279, etc.
紫色顔料としては、例えばC.I.ピグメントバイオレット1、C.I.ピグメントバイオレット2、C.I.ピグメントバイオレット3、C.I.ピグメントバイオレット3:1、C.I.ピグメントバイオレット3:3、C.I.ピグメントバイオレット5:1、C.I.ピグメントバイオレット13、C.I.ピグメントバイオレット19(γ型、β型)、C.I.ピグメントバイオレット23、C.I.ピグメントバイオレット25、C.I.ピグメントバイオレット27、C.I.ピグメントバイオレット29、C.I.ピグメントバイオレット31、C.I.ピグメントバイオレット32、C.I.ピグメントバイオレット36、C.I.ピグメントバイオレット37、C.I.ピグメントバイオレット38、C.I.ピグメントバイオレット42、C.I.ピグメントバイオレット50、などが挙げられる。
Examples of purple pigments include C.I. I. Pigment Violet 1, C.I. I. Pigment Violet 2, C.I. I. Pigment Violet 3, C.I. I. Pigment Violet 3: 1, C.I. I. Pigment Violet 3: 3, C.I. I. Pigment Violet 5: 1, C.I. I. Pigment Violet 13, C.I. I. Pigment Violet 19 (γ type, β type), C.I. I. Pigment Violet 23, C.I. I. Pigment Violet 25, C.I. I. Pigment Violet 27, C.I. I. Pigment Violet 29, C.I. I. Pigment Violet 31, C.I. I. Pigment Violet 32, C.I. I. Pigment Violet 36, C.I. I. Pigment Violet 37, C.I. I. Pigment Violet 38, C.I. I. Pigment Violet 42, C.I. I. Pigment Violet 50 and the like.
黄色顔料としては、例えばC.I.ピグメントイエロー1、C.I.ピグメントイエロー3、C.I.ピグメントイエロー12、C.I.ピグメントイエロー13、C.I.ピグメントイエロー14、ピグメントイエロー17、C.I.ピグメントイエロー24、C.I.ピグメントイエロー42、C.I.ピグメントイエロー55、C.I.ピグメントイエロー62、C.I.ピグメントイエロー65、C.I.ピグメントイエロー74、C.I.ピグメントイエロー83、C.I.ピグメントイエロー86、C.I.ピグメントイエロー93、C.I.ピグメントイエロー94、C.I.ピグメントイエロー95、C.I.ピグメントイエロー109、C.I.ピグメントイエロー110、C.I.ピグメントイエロー117、C.I.ピグメントイエロー120、ピグメントイエロー125、C.I.ピグメントイエロー128、C.I.ピグメントイエロー129、C.I.ピグメントイエロー137、C.I.ピグメント、イエロー138、C.I.ピグメントイエロー139、C.I.ピグメントイエロー147、C.I.ピグメントイエロー148、C.I.ピグメントイエロー150、C.I.ピグメントイエロー151、C.I.ピグメントイエロー153、C.I.ピグメントイエロー154、C.I.ピグメントイエロー155、C.I.ピグメントイエロー166、C.I.ピグメントイエロー168、C.I.ピグメントイエロー174、C.I.ピグメントイエロー180、C.I.ピグメントイエロー185およびC.I.ピグメントイエロー213等が挙げられる。
Examples of the yellow pigment include C.I. I. Pigment Yellow 1, C.I. I. Pigment Yellow 3, C.I. I. Pigment Yellow 12, C.I. I. Pigment Yellow 13, C.I. I. Pigment Yellow 14, Pigment Yellow 17, C.I. I. Pigment Yellow 24, C.I. I. Pigment Yellow 42, C.I. I. Pigment Yellow 55, C.I. I. Pigment Yellow 62, C.I. I. Pigment Yellow 65, C.I. I. Pigment Yellow 74, C.I. I. Pigment Yellow 83, C.I. I. Pigment Yellow 86, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 94, C.I. I. Pigment Yellow 95, C.I. I. Pigment Yellow 109, C.I. I. Pigment Yellow 110, C.I. I. Pigment Yellow 117, C.I. I. Pigment Yellow 120, Pigment Yellow 125, C.I. I. Pigment Yellow 128, C.I. I. Pigment Yellow 129, C.I. I. Pigment Yellow 137, C.I. I. Pigment, Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 147, C.I. I. Pigment Yellow 148, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 151, C.I. I. Pigment Yellow 153, C.I. I. Pigment Yellow 154, C.I. I. Pigment Yellow 155, C.I. I. Pigment Yellow 166, C.I. I. Pigment Yellow 168, C.I. I. Pigment Yellow 174, C.I. I. Pigment Yellow 180, C.I. I. Pigment Yellow 185 and C.I. I. Pigment Yellow 213 and the like.
橙色顔料としては、例えばC.I.ピグメントオレンジ5、C.I.ピグメントオレンジ13、C.I.ピグメントオレンジ16、C.I.ピグメントオレンジ34、C.I.ピグメントオレンジ36、C.I.ピグメントオレンジ37、C.I.ピグメントオオレンジ38、C.I.ピグメントオレンジ43、C.I.ピグメントオレンジ51、C.I.ピグメントレンジ55、C.I.ピグメントオレンジ59、C.I.ピグメントオレンジ61、C.I.ピグメントオレンジ64、C.I.ピグメントオレンジ71、又はC.I.ピグメントオレンジ74などが挙げられる。
Examples of the orange pigment include C.I. I. Pigment Orange 5, C.I. I. Pigment Orange 13, C.I. I. Pigment Orange 16, C.I. I. Pigment Orange 34, C.I. I. Pigment Orange 36, C.I. I. Pigment Orange 37, C.I. I. Pigment O Orange 38, C.I. I. Pigment Orange 43, C.I. I. Pigment Orange 51, C.I. I. Pigment range 55, C.I. I. Pigment Orange 59, C.I. I. Pigment Orange 61, C.I. I. Pigment Orange 64, C.I. I. Pigment Orange 71, or C.I. I. Pigment Orange 74 and the like.
茶色顔料としては、例えばC.I.ピグメントブラウン23、C.I.ピグメントブラウン25、又はC.I.ピグメントブラウン26などが挙げられる。
Examples of brown pigments include C.I. I. Pigment Brown 23, C.I. I. Pigment Brown 25, or C.I. I. Pigment Brown 26 and the like.
中でも、好ましい顔料として、黒色顔料としてC.I.ピグメントブラック7、
藍色顔料としてC.I.ピグメントブルー15、C.I.ピグメントブルー15:1、C.I.ピグメントブルー15:2、C.I.ピグメントブルー15:3、C.I.ピグメントブルー15:4、C.I.ピグメントブルー15:6、
緑色顔料としてC.I.ピグメントグリーン7、
赤色顔料としてC.I.ピグメントレッド57:1、C.I.ピグメントレッド48:1、C.I.ピグメントレッド48:2、C.I.ピグメントレッド48:3、C.I.ピグメントレッド146、C.I.ピグメントレッド242、C.I.ピグメントレッド185、C.I.ピグメントレッド122、C.I.ピグメントレッド178、C.I.ピグメントレッド149、C.I.ピグメントレッド144、C.I.ピグメントレッド166、
紫色顔料としてC.I.ピグメントバイオレット23、C.I.ピグメントバイオレット37、
黄色顔料としてC.I.ピグメントイエロー83、C.I.ピグメントイエロー14、C.I.ピグメントイエロー180、C.I.ピグメントイエロー139、
橙色顔料としてC.I.ピグメントオレンジ38、C.I.ピグメントオレンジ13、C.I.ピグメントオレンジ34、C.I.ピグメントオレンジ64、
等が挙げられ、これらの群から選ばれる少なくとも一種または二種以上を使用することが好ましい。 Among them, as a preferable pigment, as a black pigment, C.I. I. Pigment Black 7,
As an indigo pigment, C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 1, C.I. I. Pigment Blue 15: 2, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 15: 6,
As a green pigment, C.I. I. Pigment Green 7,
As a red pigment, C.I. I. Pigment Red 57: 1, C.I. I. Pigment Red 48: 1, C.I. I. Pigment Red 48: 2, C.I. I. Pigment Red 48: 3, C.I. I. Pigment Red 146, C.I. I. Pigment Red 242, C.I. I. Pigment Red 185, C.I. I. Pigment Red 122, C.I. I. Pigment Red 178, C.I. I. Pigment Red 149, C.I. I. Pigment Red 144, C.I. I. Pigment Red 166,
As a purple pigment, C.I. I. Pigment Violet 23, C.I. I. Pigment Violet 37,
As a yellow pigment, C.I. I. Pigment Yellow 83, C.I. I. Pigment Yellow 14, C.I. I. Pigment Yellow 180, C.I. I. Pigment Yellow 139,
As an orange pigment, C.I. I. Pigment Orange 38, C.I. I. Pigment Orange 13, C.I. I. Pigment Orange 34, C.I. I. Pigment Orange 64,
Etc., and it is preferable to use at least one or two or more selected from these groups.
藍色顔料としてC.I.ピグメントブルー15、C.I.ピグメントブルー15:1、C.I.ピグメントブルー15:2、C.I.ピグメントブルー15:3、C.I.ピグメントブルー15:4、C.I.ピグメントブルー15:6、
緑色顔料としてC.I.ピグメントグリーン7、
赤色顔料としてC.I.ピグメントレッド57:1、C.I.ピグメントレッド48:1、C.I.ピグメントレッド48:2、C.I.ピグメントレッド48:3、C.I.ピグメントレッド146、C.I.ピグメントレッド242、C.I.ピグメントレッド185、C.I.ピグメントレッド122、C.I.ピグメントレッド178、C.I.ピグメントレッド149、C.I.ピグメントレッド144、C.I.ピグメントレッド166、
紫色顔料としてC.I.ピグメントバイオレット23、C.I.ピグメントバイオレット37、
黄色顔料としてC.I.ピグメントイエロー83、C.I.ピグメントイエロー14、C.I.ピグメントイエロー180、C.I.ピグメントイエロー139、
橙色顔料としてC.I.ピグメントオレンジ38、C.I.ピグメントオレンジ13、C.I.ピグメントオレンジ34、C.I.ピグメントオレンジ64、
等が挙げられ、これらの群から選ばれる少なくとも一種または二種以上を使用することが好ましい。 Among them, as a preferable pigment, as a black pigment, C.I. I. Pigment Black 7,
As an indigo pigment, C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 1, C.I. I. Pigment Blue 15: 2, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 15: 6,
As a green pigment, C.I. I. Pigment Green 7,
As a red pigment, C.I. I. Pigment Red 57: 1, C.I. I. Pigment Red 48: 1, C.I. I. Pigment Red 48: 2, C.I. I. Pigment Red 48: 3, C.I. I. Pigment Red 146, C.I. I. Pigment Red 242, C.I. I. Pigment Red 185, C.I. I. Pigment Red 122, C.I. I. Pigment Red 178, C.I. I. Pigment Red 149, C.I. I. Pigment Red 144, C.I. I. Pigment Red 166,
As a purple pigment, C.I. I. Pigment Violet 23, C.I. I. Pigment Violet 37,
As a yellow pigment, C.I. I. Pigment Yellow 83, C.I. I. Pigment Yellow 14, C.I. I. Pigment Yellow 180, C.I. I. Pigment Yellow 139,
As an orange pigment, C.I. I. Pigment Orange 38, C.I. I. Pigment Orange 13, C.I. I. Pigment Orange 34, C.I. I. Pigment Orange 64,
Etc., and it is preferable to use at least one or two or more selected from these groups.
無機顔料としては、酸化チタン、酸化亜鉛、硫化亜鉛、硫酸バリウム、炭酸カルシウム、酸化クロム、シリカ、リトボン、アンチモンホワイト、石膏などの白色無機顔料が挙げられる。無機顔料の中では酸化チタンの使用が特に好ましい。酸化チタンは白色を呈し、着色力、隠ぺい力、耐薬品性、耐候性の点から好ましく、印刷性能の観点から該酸化チタンはシリカおよび/またはアルミナ処理を施されているものが好ましい。
Examples of inorganic pigments include white inorganic pigments such as titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silica, lithobon, antimony white, and gypsum. Among the inorganic pigments, the use of titanium oxide is particularly preferable. Titanium oxide has a white color and is preferable from the viewpoints of coloring power, hiding power, chemical resistance and weather resistance, and from the viewpoint of printing performance, the titanium oxide is preferably treated with silica and / or alumina.
白色以外の無機顔料としては、例えば、アルミニウム粒子、マイカ(雲母)、ブロンズ粉、クロムバーミリオン、黄鉛、カドミウムイエロー、カドミウムレッド、群青、紺青、ベンガラ、黄色酸化鉄、鉄黒、ジルコンが挙げられ、アルミニウムは粉末またはペースト状であるが、取扱い性および安全性の面からペースト状で使用するのが好ましく、リーフィングまたはノンリーフィングを使用するかは輝度感および濃度の点から適宜選択される。
Examples of non-white inorganic pigments include aluminum particles, mica (mica), bronze powder, chrome vermilion, chrome yellow, cadmium yellow, cadmium red, ultramarine, dark blue, red iron oxide, yellow iron oxide, iron black, and zircon. Although aluminum is in the form of powder or paste, it is preferably used in the form of paste from the viewpoint of handleability and safety, and whether chrome yellow or non-leafing is used is appropriately selected from the viewpoint of brightness and density.
前記顔料の平均粒子径は、1~300nmの範囲にあるものが好ましく、より好ましくは50~150nm程度のものである。
前記顔料は、水性リキッド印刷インキの濃度・着色力を確保するのに充分な量、すなわちインキ組成物の総重量に対して1~60重量%、インキ組成物中の固形分重量比では10~90重量%の割合で含まれることが好ましい。また、これらの顔料は単独で、または2種以上を併用して用いることができる。 The average particle size of the pigment is preferably in the range of 1 to 300 nm, more preferably about 50 to 150 nm.
The amount of the pigment is sufficient to secure the concentration and coloring power of the water-based liquid printing ink, that is, 1 to 60% by weight based on the total weight of the ink composition, and 10 to 10 to 60% by weight of the solid content in the ink composition. It is preferably contained in a proportion of 90% by weight. In addition, these pigments can be used alone or in combination of two or more.
前記顔料は、水性リキッド印刷インキの濃度・着色力を確保するのに充分な量、すなわちインキ組成物の総重量に対して1~60重量%、インキ組成物中の固形分重量比では10~90重量%の割合で含まれることが好ましい。また、これらの顔料は単独で、または2種以上を併用して用いることができる。 The average particle size of the pigment is preferably in the range of 1 to 300 nm, more preferably about 50 to 150 nm.
The amount of the pigment is sufficient to secure the concentration and coloring power of the water-based liquid printing ink, that is, 1 to 60% by weight based on the total weight of the ink composition, and 10 to 10 to 60% by weight of the solid content in the ink composition. It is preferably contained in a proportion of 90% by weight. In addition, these pigments can be used alone or in combination of two or more.
(その他の成分)
本発明の水性リキッドインキは、その他必要に応じて、前記コポリマー(A)以外の汎用の樹脂、体質顔料、顔料分散剤、レベリング剤、消泡剤、可塑剤、赤外線吸収剤、紫外線吸収剤、芳香剤、難燃剤などを含有することができる。中でも、耐摩擦性、滑り性等を付与するためのオレイン酸アミド、ステアリン酸アミド、エルカ酸アミド等の脂肪酸アミド類、印刷時の発泡を抑制するためのシリコン系や非シリコン系消泡剤、顔料の濡れを向上させる各種顔料分散剤等を含有することが多い。 (Other ingredients)
The water-based liquid ink of the present invention may be used as a general-purpose resin other than the copolymer (A), a extender pigment, a pigment dispersant, a leveling agent, a defoaming agent, a plasticizer, an infrared absorber, an ultraviolet absorber, as required. It can contain a fragrance, a flame retardant, and the like. Among them, fatty acid amides such as oleic acid amide, stearic acid amide, and erucic acid amide for imparting abrasion resistance and slipperiness, and silicon-based and non-silicon-based defoamers for suppressing foaming during printing. It often contains various pigment dispersants and the like that improve the wetting of pigments.
本発明の水性リキッドインキは、その他必要に応じて、前記コポリマー(A)以外の汎用の樹脂、体質顔料、顔料分散剤、レベリング剤、消泡剤、可塑剤、赤外線吸収剤、紫外線吸収剤、芳香剤、難燃剤などを含有することができる。中でも、耐摩擦性、滑り性等を付与するためのオレイン酸アミド、ステアリン酸アミド、エルカ酸アミド等の脂肪酸アミド類、印刷時の発泡を抑制するためのシリコン系や非シリコン系消泡剤、顔料の濡れを向上させる各種顔料分散剤等を含有することが多い。 (Other ingredients)
The water-based liquid ink of the present invention may be used as a general-purpose resin other than the copolymer (A), a extender pigment, a pigment dispersant, a leveling agent, a defoaming agent, a plasticizer, an infrared absorber, an ultraviolet absorber, as required. It can contain a fragrance, a flame retardant, and the like. Among them, fatty acid amides such as oleic acid amide, stearic acid amide, and erucic acid amide for imparting abrasion resistance and slipperiness, and silicon-based and non-silicon-based defoamers for suppressing foaming during printing. It often contains various pigment dispersants and the like that improve the wetting of pigments.
(製造方法)
本発明の水性リキッドインキは、顔料、水単独、あるいは水と水と混和する有機溶剤、顔料分散剤、消泡剤等を添加した混合物を分散機で分散し、顔料分散体を得る。得られた顔料分散体に樹脂、水、又は水と混和する有機溶剤、必要に応じてレベリング剤等の添加剤を加え、撹拌混合することで、本発明の水性リキッドインキが得られる。分散機としてはグラビア、フレキソ印刷インキの製造に一般的に使用されているビーズミル、アイガーミル、サンドミル、ガンマミル、アトライター等を用いて製造される。 (Production method)
In the water-based liquid ink of the present invention, a pigment, water alone, or a mixture containing water and an organic solvent mixed with water, a pigment dispersant, a defoaming agent, etc. is dispersed by a disperser to obtain a pigment dispersion. The aqueous liquid ink of the present invention can be obtained by adding an additive such as a resin, water, or an organic solvent miscible with water, and if necessary, a leveling agent, to the obtained pigment dispersion, and stirring and mixing. As the disperser, a bead mill, an Eiger mill, a sand mill, a gamma mill, an attritor, or the like, which are generally used for manufacturing gravure and flexographic printing inks, are used.
本発明の水性リキッドインキは、顔料、水単独、あるいは水と水と混和する有機溶剤、顔料分散剤、消泡剤等を添加した混合物を分散機で分散し、顔料分散体を得る。得られた顔料分散体に樹脂、水、又は水と混和する有機溶剤、必要に応じてレベリング剤等の添加剤を加え、撹拌混合することで、本発明の水性リキッドインキが得られる。分散機としてはグラビア、フレキソ印刷インキの製造に一般的に使用されているビーズミル、アイガーミル、サンドミル、ガンマミル、アトライター等を用いて製造される。 (Production method)
In the water-based liquid ink of the present invention, a pigment, water alone, or a mixture containing water and an organic solvent mixed with water, a pigment dispersant, a defoaming agent, etc. is dispersed by a disperser to obtain a pigment dispersion. The aqueous liquid ink of the present invention can be obtained by adding an additive such as a resin, water, or an organic solvent miscible with water, and if necessary, a leveling agent, to the obtained pigment dispersion, and stirring and mixing. As the disperser, a bead mill, an Eiger mill, a sand mill, a gamma mill, an attritor, or the like, which are generally used for manufacturing gravure and flexographic printing inks, are used.
本発明の水性リキッドインキをフレキソインキとして使用する場合、その粘度が離合社製ザーンカップ#4を使用し25℃にて7~25秒であればよく、より好ましくは10~20秒である。また、得られたフレキソインキの25℃における表面張力は、25~50mN/mが好ましく、33~43mN/mであればより好ましい。インキの表面張力が低いほどフィルム等の基材へのインキの濡れ性は向上するが、表面張力が25mN/mを下回るとインキの濡れ広がりにより、中間調の網点部分で隣り合う網点どうしが繋がり易い傾向にあり、ドットブリッジと呼ばれる印刷面の汚れの原因と成りやすい。一方、表面張力が50mN/mを上回るとフィルム等の基材へのインキの濡れ性が低下し、ハジキの原因と成り易い。
When the water-based liquid ink of the present invention is used as a flexo ink, its viscosity may be 7 to 25 seconds at 25 ° C., more preferably 10 to 20 seconds, using Zahn Cup # 4 manufactured by Rigosha. The surface tension of the obtained flexographic ink at 25 ° C. is preferably 25 to 50 mN / m, more preferably 33 to 43 mN / m. The lower the surface tension of the ink, the better the wettability of the ink to the substrate such as a film. However, when the surface tension is less than 25 mN / m, the ink spreads and the halftone dots are adjacent to each other. Tend to be easily connected, which tends to cause stains on the printed surface called dot bridge. On the other hand, when the surface tension exceeds 50 mN / m, the wettability of the ink to a base material such as a film is lowered, which tends to cause repelling.
一方で本発明の水性リキッドインキをグラビアインキとして使用する場合、その粘度が離合社製ザーンカップ#3を使用し25℃にて7~25秒であればよく、より好ましくは10~20秒である。また、得られたグラビアインキの25℃における表面張力は、フレキソインキと同様に25~50mN/mが好ましく、33~43mN/mであればより好ましい。インキの表面張力が低いほどフィルム等の基材へのインキの濡れ性は向上するが、表面張力が25mN/mを下回るとインキの濡れ広がりにより、中間調の網点部分で隣り合う網点どうしが繋がり易い傾向にあり、ドットブリッジと呼ばれる印刷面の汚れの原因と成りやすい。一方、表面張力が50mN/mを上回るとフィルム等の基材へのインキの濡れ性が低下し、ハジキの原因と成り易い。
On the other hand, when the water-based liquid ink of the present invention is used as a gravure ink, its viscosity may be 7 to 25 seconds at 25 ° C. using Zahn Cup # 3 manufactured by Rigosha, more preferably 10 to 20 seconds. is there. The surface tension of the obtained gravure ink at 25 ° C. is preferably 25 to 50 mN / m, more preferably 33 to 43 mN / m, as with flexographic ink. The lower the surface tension of the ink, the better the wettability of the ink to the substrate such as a film. However, when the surface tension is less than 25 mN / m, the ink spreads and the halftone dots are adjacent to each other. Tend to be easily connected, which tends to cause stains on the printed surface called dot bridge. On the other hand, when the surface tension exceeds 50 mN / m, the wettability of the ink to a base material such as a film is lowered, which tends to cause repelling.
(印刷物)
本発明においては、本発明の水性リキッドインキを基材上に印刷し印刷層を設けることで印刷物を得る。通常は、グラビア方式やフレキソ方式の印刷方式を用いてインキを基材に塗布し、オーブンによる乾燥によって乾燥させて定着することで印刷層が得られる。乾燥温度は通常40~60℃程度である。 (Printed matter)
In the present invention, a printed matter is obtained by printing the water-based liquid ink of the present invention on a substrate and providing a printed layer. Usually, a printing layer is obtained by applying an ink to a base material using a gravure method or a flexographic printing method, drying the ink by drying in an oven, and fixing the ink. The drying temperature is usually about 40 to 60 ° C.
本発明においては、本発明の水性リキッドインキを基材上に印刷し印刷層を設けることで印刷物を得る。通常は、グラビア方式やフレキソ方式の印刷方式を用いてインキを基材に塗布し、オーブンによる乾燥によって乾燥させて定着することで印刷層が得られる。乾燥温度は通常40~60℃程度である。 (Printed matter)
In the present invention, a printed matter is obtained by printing the water-based liquid ink of the present invention on a substrate and providing a printed layer. Usually, a printing layer is obtained by applying an ink to a base material using a gravure method or a flexographic printing method, drying the ink by drying in an oven, and fixing the ink. The drying temperature is usually about 40 to 60 ° C.
本発明においては、リキッド印刷インキをフレキソ印刷方式を用いて印刷することが高速印刷適性、印刷再現性等の面から好ましい。
フレキソ印刷は、凸版印刷の一種であり、主にゴム版を印刷版(凸版)として用い、当該刷版にインキを供給する部分にアニロックスロールと呼ばれる細かいメッシュの彫刻ロールを使用する。アニロックスロールは、チャンバ型ドクタからインキを受け取って、刷版上にインキ付けを行う役割を担っており、アニロックスロールを介することでインキを刷版に均一に転移できる利点がある。 In the present invention, it is preferable to print the liquid printing ink by using the flexographic printing method from the viewpoints of high-speed printing suitability, print reproducibility, and the like.
Flexographic printing is a type of letterpress printing, in which a rubber plate is mainly used as a printing plate (letter plate), and a fine mesh engraving roll called anilox roll is used for a portion that supplies ink to the printing plate. Anilox roll receives ink from a chamber type doctor and applies ink on the printing plate, and has an advantage that the ink can be uniformly transferred to the printing plate via the anilox roll.
フレキソ印刷は、凸版印刷の一種であり、主にゴム版を印刷版(凸版)として用い、当該刷版にインキを供給する部分にアニロックスロールと呼ばれる細かいメッシュの彫刻ロールを使用する。アニロックスロールは、チャンバ型ドクタからインキを受け取って、刷版上にインキ付けを行う役割を担っており、アニロックスロールを介することでインキを刷版に均一に転移できる利点がある。 In the present invention, it is preferable to print the liquid printing ink by using the flexographic printing method from the viewpoints of high-speed printing suitability, print reproducibility, and the like.
Flexographic printing is a type of letterpress printing, in which a rubber plate is mainly used as a printing plate (letter plate), and a fine mesh engraving roll called anilox roll is used for a portion that supplies ink to the printing plate. Anilox roll receives ink from a chamber type doctor and applies ink on the printing plate, and has an advantage that the ink can be uniformly transferred to the printing plate via the anilox roll.
具体的には、隔壁及び隔壁で囲まれた開口部を多数有するアニロックスロールの表面にインキを塗布し、アニロックスロールの表面にドクタを押し付けて、アニロックスロールの隔壁天面に存在するインクを掻き落とし、開口部である凹部にインクを充填する。続いて、アニロックスロールにフレキソ版を押し付けて、アニロックスロールの凹部に存在するインクを印刷版の凸部(パターン部)に転移させ、次に版を基材に接触させて版のパターン部に存在するインクを基材に転移させて、印刷物を得る。
Specifically, ink is applied to the bulkhead and the surface of the anilox roll having many openings surrounded by the bulkhead, and the doctor is pressed against the surface of the anilox roll to scrape off the ink existing on the top surface of the bulkhead of the anilox roll. , Fill the recesses, which are the openings, with ink. Subsequently, the flexographic plate is pressed against the anilox roll to transfer the ink existing in the concave portion of the anilox roll to the convex portion (pattern portion) of the printing plate, and then the plate is brought into contact with the substrate and exists in the pattern portion of the plate. The ink to be used is transferred to a substrate to obtain a printed matter.
また、輪転印刷方式を組み合わせてもよい。例えば、熱可塑性樹脂フィルム輪転印刷物の製造方法は、巻取り熱可塑性樹脂フィルムの表面に、水性リキッドインキを用いて輪転印刷を行う。印刷後は、ラミネート、スリット(幅部分の不要部をカット)、製袋(切り取ってヒートシールして袋にする)等の工程を行うことができる。リキッド印刷インキを巻き取り熱可塑性樹脂フィルムへ輪転印刷することにより、高速印刷が可能であり、生産性に優れる。
輪転印刷にはグラビア輪転印刷やフレキソ輪転印刷があり、どちらの方式でも構わないが、本願においては前述の通り水性リキッド印刷インキをフレキソ印刷方式を用いて印刷することが好ましいことから、ここではフレキソ輪転印刷について詳細に説明する。なお、本明細書において輪転印刷とは、グラビア輪転印刷及びフレキソ輪転印刷を意味するものであり、その他の印刷方式であるインキジェット印刷及びシルクスクリーン印刷方式を含まない。 Further, a rotary printing method may be combined. For example, in the method for producing a rotary printed matter of a thermoplastic resin film, rotary printing is performed on the surface of a wound thermoplastic resin film using a water-based liquid ink. After printing, processes such as laminating, slitting (cutting unnecessary parts in the width portion), and bag making (cutting and heat-sealing to make a bag) can be performed. High-speed printing is possible and productivity is excellent by winding the liquid printing ink and rotating it on a thermoplastic resin film.
There are gravure rotation printing and flexo rotation printing in the rotation printing, and either method may be used. However, in the present application, it is preferable to print the water-based liquid printing ink by using the flexo printing method as described above. Rotational printing will be described in detail. In the present specification, the rotary printing means gravure rotary printing and flexographic rotary printing, and does not include ink jet printing and silk screen printing, which are other printing methods.
輪転印刷にはグラビア輪転印刷やフレキソ輪転印刷があり、どちらの方式でも構わないが、本願においては前述の通り水性リキッド印刷インキをフレキソ印刷方式を用いて印刷することが好ましいことから、ここではフレキソ輪転印刷について詳細に説明する。なお、本明細書において輪転印刷とは、グラビア輪転印刷及びフレキソ輪転印刷を意味するものであり、その他の印刷方式であるインキジェット印刷及びシルクスクリーン印刷方式を含まない。 Further, a rotary printing method may be combined. For example, in the method for producing a rotary printed matter of a thermoplastic resin film, rotary printing is performed on the surface of a wound thermoplastic resin film using a water-based liquid ink. After printing, processes such as laminating, slitting (cutting unnecessary parts in the width portion), and bag making (cutting and heat-sealing to make a bag) can be performed. High-speed printing is possible and productivity is excellent by winding the liquid printing ink and rotating it on a thermoplastic resin film.
There are gravure rotation printing and flexo rotation printing in the rotation printing, and either method may be used. However, in the present application, it is preferable to print the water-based liquid printing ink by using the flexo printing method as described above. Rotational printing will be described in detail. In the present specification, the rotary printing means gravure rotary printing and flexographic rotary printing, and does not include ink jet printing and silk screen printing, which are other printing methods.
フレキソ輪転印刷では、リキッド印刷インキを溜める容器からインキを直接、又はインキ供給用ポンプ等を介して、表面に凹凸形状を有するアニロックスローラに供給し、このアニロックスローラに供給されたインキが、版面の凸部との接触により版面に転移し、さらに版面と熱可塑性樹脂フィルムとの接触により最終的に熱可塑性樹脂フィルムに転移して、絵柄及び/又は文字が形成される。
In flexographic rotary printing, ink is supplied directly from a container for storing liquid printing ink or via an ink supply pump or the like to an Anirox roller having an uneven shape on the surface, and the ink supplied to the Anirox roller is used on the plate surface. The contact with the convex portion transfers to the plate surface, and the contact between the plate surface and the thermoplastic resin film finally transfers to the thermoplastic resin film to form a pattern and / or characters.
水性フレキソ印刷インキを使用する場合、インキ乾燥性が溶剤型のフレキソ印刷インキよりも若干劣ることから、インキの膜厚はできるだけ薄いことが好ましい。この観点から、アロニックスローラに供給されるインキ量はできるだけ少ないことが好ましい。一方で印字濃度は膜厚が薄くなると薄くなる傾向にあるので、適宜使用する水性フレキソ印刷インキの顔料濃度をコントロールすればよい。具体的には水性フレキソ印刷インキの顔料濃度は、溶剤型のフレキソ印刷インキの濃度よりも、1~5重量%増量した濃度であると適性な印字濃度が得られる。
When a water-based flexographic printing ink is used, the ink drying property is slightly inferior to that of the solvent-based flexographic printing ink, so that the ink film thickness is preferably as thin as possible. From this point of view, it is preferable that the amount of ink supplied to the Aronix roller is as small as possible. On the other hand, the print density tends to decrease as the film thickness decreases, so the pigment concentration of the water-based flexographic printing ink used may be appropriately controlled. Specifically, when the pigment concentration of the water-based flexographic printing ink is 1 to 5% by weight higher than the concentration of the solvent-type flexographic printing ink, an appropriate printing density can be obtained.
巻取り熱可塑性樹脂フィルムとは、規定の幅に揃えられたロール状の熱可塑性樹脂フィルムのことであり、1枚1枚が予め切り離されている枚葉紙とは異なる、輪転印刷用のフィルムである。フィルムの幅は、使用する輪転印刷機の版幅、及びグラビア版の画像(絵柄)部分の幅を基準として適宜選択される。
なお、複数の色の輪転印刷インキを用いて色を重ねる場合、それらの印刷の順番は特に限定されない。 The take-up thermoplastic resin film is a roll-shaped thermoplastic resin film having a specified width, which is different from the sheet paper in which each sheet is separated in advance, and is a film for rotary printing. Is. The width of the film is appropriately selected based on the plate width of the rotary printing press to be used and the width of the image (picture) portion of the gravure plate.
When the colors are superimposed using the rotary printing inks of a plurality of colors, the printing order thereof is not particularly limited.
なお、複数の色の輪転印刷インキを用いて色を重ねる場合、それらの印刷の順番は特に限定されない。 The take-up thermoplastic resin film is a roll-shaped thermoplastic resin film having a specified width, which is different from the sheet paper in which each sheet is separated in advance, and is a film for rotary printing. Is. The width of the film is appropriately selected based on the plate width of the rotary printing press to be used and the width of the image (picture) portion of the gravure plate.
When the colors are superimposed using the rotary printing inks of a plurality of colors, the printing order thereof is not particularly limited.
表刷り印刷を行うときは、必要に応じて先に白インキを印刷し、その後色インキを印刷するのが一般的である。色インキが複数の場合、例えばイエロー、マゼンタ、シアン、及びブラックの順に印刷することができるが、特に制限されるものではない。表刷り印刷構成の場合、必要に応じて輪転印刷物の印刷面にオーバーコート剤を塗布することにより、耐摩耗性、及び耐水性等を向上させることができる。
基材が白色系の場合、すなわち、例えば紙基材、及び白色系顔料を練り込んだ熱可塑性樹脂フィルムの場合、必要に応じて色インキのみでの印刷も可能である。 When performing front printing, it is common to print white ink first, and then color ink, if necessary. When there are a plurality of color inks, for example, yellow, magenta, cyan, and black can be printed in this order, but the printing is not particularly limited. In the case of a front print configuration, abrasion resistance, water resistance, and the like can be improved by applying an overcoat agent to the printed surface of the rotary printed matter as needed.
When the base material is white, that is, for example, a paper base material and a thermoplastic resin film kneaded with a white pigment, printing with only color ink is possible if necessary.
基材が白色系の場合、すなわち、例えば紙基材、及び白色系顔料を練り込んだ熱可塑性樹脂フィルムの場合、必要に応じて色インキのみでの印刷も可能である。 When performing front printing, it is common to print white ink first, and then color ink, if necessary. When there are a plurality of color inks, for example, yellow, magenta, cyan, and black can be printed in this order, but the printing is not particularly limited. In the case of a front print configuration, abrasion resistance, water resistance, and the like can be improved by applying an overcoat agent to the printed surface of the rotary printed matter as needed.
When the base material is white, that is, for example, a paper base material and a thermoplastic resin film kneaded with a white pigment, printing with only color ink is possible if necessary.
また裏刷り印刷を行う場合、巻取り熱可塑性樹脂フィルムに、先に色インキを印刷し、次に白インキを印刷するのが一般的である。色インキが複数色の場合、例えばブラック、シアン、マゼンタ、及びイエローの順に印刷することができるが、特に制限されるものではない。なお、大型印刷機では更に、前記基本色に加えて特色等を用いることができる。すなわち、大型印刷機には5~10色に対応する複数の印刷ユニットがあり、1印刷ユニットには1色のインキが備えられ、5~10色の重ね印刷を一度に行うことができる。
裏刷り印刷で得た印刷物は、そのままで使用することもあるし、前記方法で得られた輪転印刷物の印刷面にアンカーコート剤及び接着剤等を塗布し、必要に応じて乾燥後に、フィルム等と貼り合せてラミネート体とすることもできる。 Further, in the case of back printing, it is common to print the color ink on the take-up thermoplastic resin film first, and then print the white ink. When the color ink has a plurality of colors, for example, black, cyan, magenta, and yellow can be printed in this order, but the printing is not particularly limited. In the large printing machine, special colors and the like can be used in addition to the basic colors. That is, the large-sized printing machine has a plurality of printing units corresponding to 5 to 10 colors, one printing unit is provided with one color of ink, and 5 to 10 colors can be overprinted at one time.
The printed matter obtained by back printing may be used as it is, or an anchor coating agent, an adhesive or the like may be applied to the printed surface of the rotary printed matter obtained by the above method, and if necessary, after drying, a film or the like may be used. It can also be laminated with.
裏刷り印刷で得た印刷物は、そのままで使用することもあるし、前記方法で得られた輪転印刷物の印刷面にアンカーコート剤及び接着剤等を塗布し、必要に応じて乾燥後に、フィルム等と貼り合せてラミネート体とすることもできる。 Further, in the case of back printing, it is common to print the color ink on the take-up thermoplastic resin film first, and then print the white ink. When the color ink has a plurality of colors, for example, black, cyan, magenta, and yellow can be printed in this order, but the printing is not particularly limited. In the large printing machine, special colors and the like can be used in addition to the basic colors. That is, the large-sized printing machine has a plurality of printing units corresponding to 5 to 10 colors, one printing unit is provided with one color of ink, and 5 to 10 colors can be overprinted at one time.
The printed matter obtained by back printing may be used as it is, or an anchor coating agent, an adhesive or the like may be applied to the printed surface of the rotary printed matter obtained by the above method, and if necessary, after drying, a film or the like may be used. It can also be laminated with.
本発明の水性リキッドインキ(A)の印刷物は、塗膜強度、特に耐摩擦性や耐スクラッチ性に優れるので、印刷層が最表層となる形態に適している。前記表刷り印刷物や、前記裏刷り印刷物において、流通時に最表層となる面に本発明に水性リキッドインキ(A)の印刷層がある印刷物が本発明の効果を最大限に発揮でき好ましい。
The printed matter of the water-based liquid ink (A) of the present invention is excellent in coating film strength, particularly abrasion resistance and scratch resistance, and is therefore suitable for a form in which the printed layer is the outermost layer. In the front-printed matter and the back-printed matter, a printed matter having a printed layer of the water-based liquid ink (A) in the present invention on the surface that becomes the outermost layer at the time of distribution is preferable because the effect of the present invention can be maximized.
(積層体)
本発明の積層体は、基材上に版による印刷方法で本発明の水性リキッドインキによる印刷層を有する印刷物を積層構造に含む積層体であればよい。 (Laminated body)
The laminate of the present invention may be a laminate that includes a printed matter having a printed layer of the water-based liquid ink of the present invention on a substrate by a printing method using a plate.
本発明の積層体は、基材上に版による印刷方法で本発明の水性リキッドインキによる印刷層を有する印刷物を積層構造に含む積層体であればよい。 (Laminated body)
The laminate of the present invention may be a laminate that includes a printed matter having a printed layer of the water-based liquid ink of the present invention on a substrate by a printing method using a plate.
基材としては、例えば、紙、合成紙、熱可塑性樹脂フィルム、鋼板、アルミ箔、木材、織布、編布、不織布、石膏ボード、木質ボード等が挙げられる。中でも紙、合成紙、熱可塑性樹脂フィルム等が好ましい。またこれらの基材を複数種組み合わせた基材、例えば紙と熱可塑性樹脂フィルムとが積層された基材、熱可塑性樹脂フィルムとアルミ箔とが積層された基材であってもよい。積層方法も特に限定はなく、汎用の1液型接着剤、2液型接着剤等を使用して接着させてもよいし、複数の熱可塑性樹脂フィルムであれば押出成形によって貼り合せた積層体であってもよい。
Examples of the base material include paper, synthetic paper, thermoplastic resin film, steel plate, aluminum foil, wood, woven cloth, knitted cloth, non-woven fabric, gypsum board, wood board and the like. Of these, paper, synthetic paper, thermoplastic resin film and the like are preferable. Further, a base material obtained by combining a plurality of types of these base materials may be used, for example, a base material in which paper and a thermoplastic resin film are laminated, or a base material in which a thermoplastic resin film and an aluminum foil are laminated. The laminating method is not particularly limited, and a general-purpose one-component adhesive, a two-component adhesive, or the like may be used for bonding, or if there are a plurality of thermoplastic resin films, the laminated body is bonded by extrusion molding. It may be.
熱可塑性樹脂フィルムとしては、特に限定は無く、例えば、ナイロン6、ナイロン66、ナイロン46等のポリアミド樹脂、ポリエチレンフタレート(PET)、ポリエチレンナフタレート、ポリトリメチレンテレフタレート、ポリトリメチレンナフタレート、ポリブチレンテレフタレート、ポリブチレンナフタレート等のポリエステル系樹脂、ポリ乳酸等のポリヒドロキシカルボン酸、ポリ(エチレンサクシネート)、ポリ(ブチレンサクシネート)等の脂肪族ポリエステル系樹脂に代表される生分解性樹脂、ポリプロピレン(PP)、ポリエチレン等のポリオレフィン樹脂、ポリイミド樹脂、ポリアリレート樹脂またはそれらの混合物等の熱可塑性樹脂よりなるフィルムやこれらの積層体が挙げられるが、中でも、ポリエステル、ポリアミド、ポリエチレン、ポリプロピレンからなるフィルムが好適に使用できる。
これらのフィルムは、未延伸フィルムでも延伸フィルムでも良く、その製法も限定されるものではない。また、基材フィルムの厚さも特に限定されるものではないが、通常は1~500μmの範囲であればよい。
また、フィルムの印刷面には、コロナ放電処理がされていれば更に基材密着性を向上させる事ができ好ましい。また、シリカ、アルミナ等が蒸着されていてもよく、酸素ガスバリア層等のガスバリアコート層が積層されていてもよい。
い。 The thermoplastic resin film is not particularly limited, and for example, polyamide resins such as nylon 6, nylon 66, and nylon 46, polyethylene phthalate (PET), polyethylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, and polybutylene. Biodegradable resins typified by polyester resins such as terephthalate and polybutylene naphthalate, polyhydroxycarboxylic acids such as polylactic acid, and aliphatic polyester resins such as poly (ethylene succinate) and poly (butylene succinate). Examples thereof include films made of polyolefin resins such as polypropylene (PP) and polyethylene, polyimide resins, polyarylate resins or thermoplastic resins such as mixtures thereof, and laminates thereof. Among them, polyester, polyamide, polyethylene and polypropylene are used. A film can be preferably used.
These films may be unstretched films or stretched films, and the production method thereof is not limited. Further, the thickness of the base film is not particularly limited, but usually it may be in the range of 1 to 500 μm.
Further, if the printed surface of the film is subjected to a corona discharge treatment, the adhesion to the base material can be further improved, which is preferable. Further, silica, alumina or the like may be vapor-deposited, or a gas barrier coat layer such as an oxygen gas barrier layer may be laminated.
I.
これらのフィルムは、未延伸フィルムでも延伸フィルムでも良く、その製法も限定されるものではない。また、基材フィルムの厚さも特に限定されるものではないが、通常は1~500μmの範囲であればよい。
また、フィルムの印刷面には、コロナ放電処理がされていれば更に基材密着性を向上させる事ができ好ましい。また、シリカ、アルミナ等が蒸着されていてもよく、酸素ガスバリア層等のガスバリアコート層が積層されていてもよい。
い。 The thermoplastic resin film is not particularly limited, and for example, polyamide resins such as nylon 6, nylon 66, and nylon 46, polyethylene phthalate (PET), polyethylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, and polybutylene. Biodegradable resins typified by polyester resins such as terephthalate and polybutylene naphthalate, polyhydroxycarboxylic acids such as polylactic acid, and aliphatic polyester resins such as poly (ethylene succinate) and poly (butylene succinate). Examples thereof include films made of polyolefin resins such as polypropylene (PP) and polyethylene, polyimide resins, polyarylate resins or thermoplastic resins such as mixtures thereof, and laminates thereof. Among them, polyester, polyamide, polyethylene and polypropylene are used. A film can be preferably used.
These films may be unstretched films or stretched films, and the production method thereof is not limited. Further, the thickness of the base film is not particularly limited, but usually it may be in the range of 1 to 500 μm.
Further, if the printed surface of the film is subjected to a corona discharge treatment, the adhesion to the base material can be further improved, which is preferable. Further, silica, alumina or the like may be vapor-deposited, or a gas barrier coat layer such as an oxygen gas barrier layer may be laminated.
I.
基材として紙を用いる場合、基材紙としては、クラフト紙、ライナー紙、アート紙、コート紙、カートン紙等を挙げることができる。また合成紙を用いてもよい。合成紙の構造は特に限定されず単層構造であっても多層構造であってもよい。多層構造としては、例えば基材層と表面層の2層構造、基材層と表裏面に表面層が存在する3層構造、基材層と表面層の間に他の樹脂フィルム層が存在する多層構造を例示することができる。また、各層は無機や有機のフィラーを含有していてもよいし、含有していなくてもよい。また、微細なボイドを多数有する微多孔性合成紙も使用することができる。
When paper is used as the base material, examples of the base paper include kraft paper, liner paper, art paper, coated paper, and carton paper. Moreover, you may use synthetic paper. The structure of the synthetic paper is not particularly limited and may be a single-layer structure or a multi-layer structure. As the multilayer structure, for example, there are a two-layer structure of a base material layer and a surface layer, a three-layer structure in which the base material layer and the front and back surfaces are present, and another resin film layer between the base material layer and the surface layer. A multi-layer structure can be exemplified. Further, each layer may or may not contain an inorganic or organic filler. Further, a microporous synthetic paper having a large number of fine voids can also be used.
前記基材に、本発明の水性リキッドインキによる印刷層を設けるが、印刷層は1層であっても複数層であってもよい。通常印刷時には、白、プロセスカラー(墨(ブラックとも表現する、黒系の色である)、紅(マゼンタとも表現する、赤系の色である)、藍(シアンとも表現する、青系の色である)、黄(イエローとも表現する、黄色系の色である)、及びこれらの基本色以外の特色インキを適宜組み合わせて印刷する。本発明においてはこれらの各色のインキに本発明の水性リキッドインキを使用し、または、本発明の水性リキッドインキと本発明の水性リキッドインキ以外の汎用の水性または油性のリキッドインキや、オーバーコートニスを併用することができる。使用するオーバーコートニスとしては、市販のオーバーコートニスを使用することもできるが、前述の通り本発明の水性リキッドインキにおいて色材を含まない形態のオーバーコートニスとして使用することもできる。
A printing layer using the water-based liquid ink of the present invention is provided on the base material, and the printing layer may be one layer or a plurality of layers. During normal printing, white, process color (black (also referred to as black, blackish color), red (also referred to as magenta, reddish color), indigo (also referred to as cyan, bluish color) ), Yellow (also referred to as yellow, which is a yellowish color), and special color inks other than these basic colors are appropriately combined for printing. In the present invention, the water-based liquid of the present invention is applied to each of these color inks. An ink can be used, or a general-purpose water-based or oil-based liquid ink other than the water-based liquid ink of the present invention and the water-based liquid ink of the present invention, or an overcoat varnish can be used in combination. A commercially available overcoat varnish can be used, but as described above, it can also be used as an overcoat varnish in a form that does not contain a coloring material in the water-based liquid ink of the present invention.
これらの印刷層のより具体的な構成を次に挙げる。もちろん本発明においては本構成に限定されることはなく所望の意匠に応じた複数の印刷層で表現された印刷物及び積層体を得ることができる。
なお略語として、
本発明の水性リキッドインキによる印刷層を「本印刷層(色)」
汎用の水性リキッドインキによる印刷層を「汎用印刷層(色)」
本発明の水性リキッドインキオーバーコートニスを「本OP」
汎用の水性リキッドインキオーバーコートニスを「汎用OP」
と表現する。なお「/」は、隣接する、という意味であり、例えば「基材/本印刷層(白以外)/本OP」であれば、基材に隣接して本発明の水性リキッドインキによる印刷層(白以外)が設けられ、該印刷層(白以外)に隣接して、本発明の水性リキッドインキオーバーコートニスが設けられている。という意味となる。 More specific configurations of these print layers are listed below. Of course, the present invention is not limited to this configuration, and a printed matter and a laminate represented by a plurality of printing layers according to a desired design can be obtained.
As an abbreviation,
The printing layer using the water-based liquid ink of the present invention is referred to as "the present printing layer (color)".
"General-purpose printing layer (color)" is the printing layer using general-purpose water-based liquid ink.
The water-based liquid ink overcoat varnish of the present invention is referred to as "this OP".
"General-purpose OP" for general-purpose water-based liquid ink overcoat varnish
It is expressed as. Note that "/" means that they are adjacent to each other. For example, in the case of "base material / main printing layer (other than white) / main OP", the printing layer using the water-based liquid ink of the present invention is adjacent to the base material ( (Other than white) is provided, and the water-based liquid ink overcoat varnish of the present invention is provided adjacent to the print layer (other than white). It means that.
なお略語として、
本発明の水性リキッドインキによる印刷層を「本印刷層(色)」
汎用の水性リキッドインキによる印刷層を「汎用印刷層(色)」
本発明の水性リキッドインキオーバーコートニスを「本OP」
汎用の水性リキッドインキオーバーコートニスを「汎用OP」
と表現する。なお「/」は、隣接する、という意味であり、例えば「基材/本印刷層(白以外)/本OP」であれば、基材に隣接して本発明の水性リキッドインキによる印刷層(白以外)が設けられ、該印刷層(白以外)に隣接して、本発明の水性リキッドインキオーバーコートニスが設けられている。という意味となる。 More specific configurations of these print layers are listed below. Of course, the present invention is not limited to this configuration, and a printed matter and a laminate represented by a plurality of printing layers according to a desired design can be obtained.
As an abbreviation,
The printing layer using the water-based liquid ink of the present invention is referred to as "the present printing layer (color)".
"General-purpose printing layer (color)" is the printing layer using general-purpose water-based liquid ink.
The water-based liquid ink overcoat varnish of the present invention is referred to as "this OP".
"General-purpose OP" for general-purpose water-based liquid ink overcoat varnish
It is expressed as. Note that "/" means that they are adjacent to each other. For example, in the case of "base material / main printing layer (other than white) / main OP", the printing layer using the water-based liquid ink of the present invention is adjacent to the base material ( (Other than white) is provided, and the water-based liquid ink overcoat varnish of the present invention is provided adjacent to the print layer (other than white). It means that.
基材/本OP
基材/本印刷層(白)/本OP
基材/本印刷層(白)/本印刷層(白)
基材/本印刷層(白)/本印刷層(白)/本OP
基材/本印刷層(白以外)/本OP
基材/本印刷層(白以外)/本印刷層(白)
基材/本印刷層(白以外)/本印刷層(白)/本印刷層(白)
基材/本印刷層(白以外)/本印刷層(白)/本印刷層(白)
基材/本印刷層(白以外)/本印刷層(白)/本印刷層(白)/本OP
基材/本印刷層(白以外)/本印刷層(白)
基材/本印刷層(白以外)/本印刷層(白)/本印刷層(色)
基材/本印刷層(白以外)/本印刷層(白)/本印刷層(色)/本OP
基材/本印刷層(白以外)/本印刷層(白)/本印刷層(白)/本印刷層(色)
基材/本印刷層(白以外)/本印刷層(白)/本印刷層(白)/本印刷層(色)/本OP
基材/汎用印刷層(白以外)/本OP
基材/汎用印刷層(白以外)/本印刷層(白)
基材/汎用印刷層(白以外)/本印刷層(白)/本印刷層(白)
基材/汎用印刷層(白以外)/本印刷層(白)/本印刷層(白)
基材/汎用印刷層(白以外)/本印刷層(白)/本印刷層(白)/本OP
基材/本印刷層(白以外)/汎用OP
基材/本印刷層(白以外)/汎用印刷層(白)
基材/本印刷層(白以外)/汎用印刷層(白)/本印刷層(白)
基材/本印刷層(白以外)/汎用印刷層(白)/本印刷層(白)
基材/本印刷層(白以外)/汎用印刷層(白)/本印刷層(白)/本OP
基材/本印刷層(白以外)/本印刷層(白)/汎用印刷層(白)
基材/本印刷層(白以外)/汎用印刷層(白)/汎用印刷層(白)
基材/本印刷層(白以外)/汎用印刷層(白)/汎用印刷層(白)/本OP Base material / book OP
Base material / main printing layer (white) / main OP
Base material / main printing layer (white) / main printing layer (white)
Base material / main printing layer (white) / main printing layer (white) / main OP
Base material / main printing layer (other than white) / main OP
Base material / main printing layer (other than white) / main printing layer (white)
Base material / Main printing layer (other than white) / Main printing layer (white) / Main printing layer (white)
Base material / Main printing layer (other than white) / Main printing layer (white) / Main printing layer (white)
Substrate / Main printing layer (other than white) / Main printing layer (white) / Main printing layer (white) / Main OP
Base material / main printing layer (other than white) / main printing layer (white)
Base material / Main printing layer (other than white) / Main printing layer (white) / Main printing layer (color)
Base material / Main printing layer (other than white) / Main printing layer (white) / Main printing layer (color) / Main OP
Base material / Main printing layer (other than white) / Main printing layer (white) / Main printing layer (white) / Main printing layer (color)
Substrate / Main print layer (other than white) / Main print layer (white) / Main print layer (white) / Main print layer (color) / Main OP
Base material / general-purpose printing layer (other than white) / book OP
Base material / General-purpose printing layer (other than white) / Main printing layer (white)
Base material / General-purpose printing layer (other than white) / Main printing layer (white) / Main printing layer (white)
Base material / General-purpose printing layer (other than white) / Main printing layer (white) / Main printing layer (white)
Base material / General-purpose printing layer (other than white) / Main printing layer (white) / Main printing layer (white) / Main OP
Base material / main printing layer (other than white) / general-purpose OP
Base material / Main printing layer (other than white) / General-purpose printing layer (white)
Base material / Main printing layer (other than white) / General-purpose printing layer (white) / Main printing layer (white)
Base material / Main printing layer (other than white) / General-purpose printing layer (white) / Main printing layer (white)
Base material / Main printing layer (other than white) / General-purpose printing layer (white) / Main printing layer (white) / Main OP
Base material / Main printing layer (other than white) / Main printing layer (white) / General-purpose printing layer (white)
Base material / Main printing layer (other than white) / General-purpose printing layer (white) / General-purpose printing layer (white)
Base material / Main printing layer (other than white) / General-purpose printing layer (white) / General-purpose printing layer (white) / Main OP
基材/本印刷層(白)/本OP
基材/本印刷層(白)/本印刷層(白)
基材/本印刷層(白)/本印刷層(白)/本OP
基材/本印刷層(白以外)/本OP
基材/本印刷層(白以外)/本印刷層(白)
基材/本印刷層(白以外)/本印刷層(白)/本印刷層(白)
基材/本印刷層(白以外)/本印刷層(白)/本印刷層(白)
基材/本印刷層(白以外)/本印刷層(白)/本印刷層(白)/本OP
基材/本印刷層(白以外)/本印刷層(白)
基材/本印刷層(白以外)/本印刷層(白)/本印刷層(色)
基材/本印刷層(白以外)/本印刷層(白)/本印刷層(色)/本OP
基材/本印刷層(白以外)/本印刷層(白)/本印刷層(白)/本印刷層(色)
基材/本印刷層(白以外)/本印刷層(白)/本印刷層(白)/本印刷層(色)/本OP
基材/汎用印刷層(白以外)/本OP
基材/汎用印刷層(白以外)/本印刷層(白)
基材/汎用印刷層(白以外)/本印刷層(白)/本印刷層(白)
基材/汎用印刷層(白以外)/本印刷層(白)/本印刷層(白)
基材/汎用印刷層(白以外)/本印刷層(白)/本印刷層(白)/本OP
基材/本印刷層(白以外)/汎用OP
基材/本印刷層(白以外)/汎用印刷層(白)
基材/本印刷層(白以外)/汎用印刷層(白)/本印刷層(白)
基材/本印刷層(白以外)/汎用印刷層(白)/本印刷層(白)
基材/本印刷層(白以外)/汎用印刷層(白)/本印刷層(白)/本OP
基材/本印刷層(白以外)/本印刷層(白)/汎用印刷層(白)
基材/本印刷層(白以外)/汎用印刷層(白)/汎用印刷層(白)
基材/本印刷層(白以外)/汎用印刷層(白)/汎用印刷層(白)/本OP Base material / book OP
Base material / main printing layer (white) / main OP
Base material / main printing layer (white) / main printing layer (white)
Base material / main printing layer (white) / main printing layer (white) / main OP
Base material / main printing layer (other than white) / main OP
Base material / main printing layer (other than white) / main printing layer (white)
Base material / Main printing layer (other than white) / Main printing layer (white) / Main printing layer (white)
Base material / Main printing layer (other than white) / Main printing layer (white) / Main printing layer (white)
Substrate / Main printing layer (other than white) / Main printing layer (white) / Main printing layer (white) / Main OP
Base material / main printing layer (other than white) / main printing layer (white)
Base material / Main printing layer (other than white) / Main printing layer (white) / Main printing layer (color)
Base material / Main printing layer (other than white) / Main printing layer (white) / Main printing layer (color) / Main OP
Base material / Main printing layer (other than white) / Main printing layer (white) / Main printing layer (white) / Main printing layer (color)
Substrate / Main print layer (other than white) / Main print layer (white) / Main print layer (white) / Main print layer (color) / Main OP
Base material / general-purpose printing layer (other than white) / book OP
Base material / General-purpose printing layer (other than white) / Main printing layer (white)
Base material / General-purpose printing layer (other than white) / Main printing layer (white) / Main printing layer (white)
Base material / General-purpose printing layer (other than white) / Main printing layer (white) / Main printing layer (white)
Base material / General-purpose printing layer (other than white) / Main printing layer (white) / Main printing layer (white) / Main OP
Base material / main printing layer (other than white) / general-purpose OP
Base material / Main printing layer (other than white) / General-purpose printing layer (white)
Base material / Main printing layer (other than white) / General-purpose printing layer (white) / Main printing layer (white)
Base material / Main printing layer (other than white) / General-purpose printing layer (white) / Main printing layer (white)
Base material / Main printing layer (other than white) / General-purpose printing layer (white) / Main printing layer (white) / Main OP
Base material / Main printing layer (other than white) / Main printing layer (white) / General-purpose printing layer (white)
Base material / Main printing layer (other than white) / General-purpose printing layer (white) / General-purpose printing layer (white)
Base material / Main printing layer (other than white) / General-purpose printing layer (white) / General-purpose printing layer (white) / Main OP
前記構成において、基材として好ましくは熱可塑性樹脂フィルムである。熱可塑性フィルムに白以外の印刷層と白印刷層とを有する印刷物とを有することで、好ましい視認性が得られる。
In the above configuration, the base material is preferably a thermoplastic resin film. By having the thermoplastic film having a printed matter having a print layer other than white and a white print layer, preferable visibility can be obtained.
(印刷インキB)
汎用の水性リキッドインキとしてより好ましくは、ポリウレタン樹脂又はアクリルポリウレタン樹脂と顔料を含有する印刷インキである。(以後ポリウレタン樹脂又はアクリルポリウレタン樹脂と顔料を含有する印刷インキを印刷インキ(B)と称する場合がある。)
特に基材として熱可塑性樹脂フィルムを使用する場合では、ポリウレタン樹脂又はアクリルポリウレタン樹脂を含有する印刷インキを熱可塑性樹脂フィルムに接するインキに使用することで、アクリル樹脂と比較して塗膜に柔軟性があり、熱可塑性樹脂フィルムに対する密着性が高くフィルム基材の変形に伴う追従性も高いため好ましい。
また、ポリウレタン樹脂又はアクリルポリウレタン樹脂は顔料分散性、印刷時の再溶解性、顔料を分散した際の発色性の点でも、アクリル樹脂に劣らない同等以上の性能が得られ顔料との相性もよい。
特にアクリルポリウレタン樹脂を含有する印刷インキは、ポリウレタン樹脂を含有する印刷インキと比較して、発色や再溶解性が良好であり、印刷時の糸曳きが発生し難い特徴がありより好ましい。なお該インキにおいて、ポリウレタン樹脂とアクリルポリウレタン樹脂とは、双方混合して使用してもよいし、必要に応じてアクリル樹脂を適宜混合して使用してもよい。 (Printing ink B)
A general-purpose water-based liquid ink is more preferably a printing ink containing a polyurethane resin or an acrylic polyurethane resin and a pigment. (Hereinafter, a printing ink containing a polyurethane resin or an acrylic polyurethane resin and a pigment may be referred to as a printing ink (B).)
In particular, when a thermoplastic resin film is used as the base material, by using a printing ink containing a polyurethane resin or an acrylic polyurethane resin as the ink in contact with the thermoplastic resin film, the coating film is more flexible than the acrylic resin. This is preferable because it has high adhesion to the thermoplastic resin film and high followability due to deformation of the film base material.
In addition, the polyurethane resin or acrylic polyurethane resin has the same or better performance as the acrylic resin in terms of pigment dispersibility, resolubility during printing, and color development when the pigment is dispersed, and is compatible with the pigment. ..
In particular, a printing ink containing an acrylic polyurethane resin is more preferable than a printing ink containing a polyurethane resin because it has better color development and resolubility and is less likely to cause stringing during printing. In the ink, both the polyurethane resin and the acrylic polyurethane resin may be mixed and used, or if necessary, the acrylic resin may be appropriately mixed and used.
汎用の水性リキッドインキとしてより好ましくは、ポリウレタン樹脂又はアクリルポリウレタン樹脂と顔料を含有する印刷インキである。(以後ポリウレタン樹脂又はアクリルポリウレタン樹脂と顔料を含有する印刷インキを印刷インキ(B)と称する場合がある。)
特に基材として熱可塑性樹脂フィルムを使用する場合では、ポリウレタン樹脂又はアクリルポリウレタン樹脂を含有する印刷インキを熱可塑性樹脂フィルムに接するインキに使用することで、アクリル樹脂と比較して塗膜に柔軟性があり、熱可塑性樹脂フィルムに対する密着性が高くフィルム基材の変形に伴う追従性も高いため好ましい。
また、ポリウレタン樹脂又はアクリルポリウレタン樹脂は顔料分散性、印刷時の再溶解性、顔料を分散した際の発色性の点でも、アクリル樹脂に劣らない同等以上の性能が得られ顔料との相性もよい。
特にアクリルポリウレタン樹脂を含有する印刷インキは、ポリウレタン樹脂を含有する印刷インキと比較して、発色や再溶解性が良好であり、印刷時の糸曳きが発生し難い特徴がありより好ましい。なお該インキにおいて、ポリウレタン樹脂とアクリルポリウレタン樹脂とは、双方混合して使用してもよいし、必要に応じてアクリル樹脂を適宜混合して使用してもよい。 (Printing ink B)
A general-purpose water-based liquid ink is more preferably a printing ink containing a polyurethane resin or an acrylic polyurethane resin and a pigment. (Hereinafter, a printing ink containing a polyurethane resin or an acrylic polyurethane resin and a pigment may be referred to as a printing ink (B).)
In particular, when a thermoplastic resin film is used as the base material, by using a printing ink containing a polyurethane resin or an acrylic polyurethane resin as the ink in contact with the thermoplastic resin film, the coating film is more flexible than the acrylic resin. This is preferable because it has high adhesion to the thermoplastic resin film and high followability due to deformation of the film base material.
In addition, the polyurethane resin or acrylic polyurethane resin has the same or better performance as the acrylic resin in terms of pigment dispersibility, resolubility during printing, and color development when the pigment is dispersed, and is compatible with the pigment. ..
In particular, a printing ink containing an acrylic polyurethane resin is more preferable than a printing ink containing a polyurethane resin because it has better color development and resolubility and is less likely to cause stringing during printing. In the ink, both the polyurethane resin and the acrylic polyurethane resin may be mixed and used, or if necessary, the acrylic resin may be appropriately mixed and used.
前記印刷インキ(B)に使用するポリウレタン樹脂としては、重量平均分子量が20,000~2,000,000、酸価は10~50mgKOH/gが望ましく、より好ましくは、重量平均分子量が、30,000~1,500,000、20~50mgKOH/gである。重量平均分子量が20,000以上であれば、耐摩擦性、及び耐水摩擦性が低下することなく、重量平均分子量が2,000,000以下であれば、基材密着性が低下を抑制する事ができる。また酸価が10mgKOH/g以上であれば、印刷におけるインキ皮膜の水系溶剤への再溶解性が悪くなり、印刷物の調子再現性が低下することなく、リキッド印刷インキ積層体を形成した際の画像再現性が低下する事も抑制できる。一方酸価が50mgKOH/g以下であれば、樹脂の耐水性が低下することがなく、印刷層の基材密着性、耐水摩擦性の低下を抑制する事ができる。尚、ここで言う酸価とは、樹脂1g中に含まれる酸性成分を中和するのに要する水酸化カリウムのミリグラム数を示す。
The polyurethane resin used in the printing ink (B) preferably has a weight average molecular weight of 20,000 to 2,000,000 and an acid value of 10 to 50 mgKOH / g, more preferably a weight average molecular weight of 30, It is 000 to 1,500,000 and 20 to 50 mgKOH / g. If the weight average molecular weight is 20,000 or more, the friction resistance and the water friction resistance do not decrease, and if the weight average molecular weight is 2,000,000 or less, the decrease in substrate adhesion is suppressed. Can be done. Further, when the acid value is 10 mgKOH / g or more, the resolubility of the ink film in the aqueous solvent in printing is deteriorated, and the tone reproducibility of the printed matter is not deteriorated, and the image when the liquid printing ink laminate is formed. It is also possible to suppress a decrease in reproducibility. On the other hand, when the acid value is 50 mgKOH / g or less, the water resistance of the resin does not decrease, and the deterioration of the substrate adhesion and the water friction resistance of the printed layer can be suppressed. The acid value referred to here indicates the number of milligrams of potassium hydroxide required to neutralize the acidic component contained in 1 g of the resin.
前記印刷インキ(B)に使用するアクリルポリウレタン樹脂としては、重量平均分子量が20,000~2,000,000、酸価は10~60mgKOH/gが望ましく、より好ましくは、重量平均分子量が、30,000~1,500,000、20~50mgKOH/gである。重量平均分子量が20,000以上であれば、耐摩擦性、及び耐水摩擦性が低下することなく、重量平均分子量が2,000,000以下であれば、基材密着性が低下を抑制する事ができる。また、酸価が10mgKOH/g以上であれば、印刷物の調子再現性が低下することなく、リキッド印刷インキ積層体としての画像再現性も良好に保持できる。
一方で、酸価が60mgKOH/g以下であれば、樹脂の耐水性が低下することなく、積層体の基材密着性、耐水摩擦性を良好に保つ事ができる。 The acrylic polyurethane resin used in the printing ink (B) preferably has a weight average molecular weight of 20,000 to 2,000,000 and an acid value of 10 to 60 mgKOH / g, more preferably a weight average molecular weight of 30. It is 000 to 1,500,000 and 20 to 50 mgKOH / g. If the weight average molecular weight is 20,000 or more, the friction resistance and the water friction resistance do not decrease, and if the weight average molecular weight is 2,000,000 or less, the decrease in substrate adhesion is suppressed. Can be done. Further, when the acid value is 10 mgKOH / g or more, the image reproducibility as a liquid printing ink laminate can be well maintained without deteriorating the tone reproducibility of the printed matter.
On the other hand, when the acid value is 60 mgKOH / g or less, the water resistance of the resin does not decrease, and the substrate adhesion and water friction resistance of the laminate can be kept good.
一方で、酸価が60mgKOH/g以下であれば、樹脂の耐水性が低下することなく、積層体の基材密着性、耐水摩擦性を良好に保つ事ができる。 The acrylic polyurethane resin used in the printing ink (B) preferably has a weight average molecular weight of 20,000 to 2,000,000 and an acid value of 10 to 60 mgKOH / g, more preferably a weight average molecular weight of 30. It is 000 to 1,500,000 and 20 to 50 mgKOH / g. If the weight average molecular weight is 20,000 or more, the friction resistance and the water friction resistance do not decrease, and if the weight average molecular weight is 2,000,000 or less, the decrease in substrate adhesion is suppressed. Can be done. Further, when the acid value is 10 mgKOH / g or more, the image reproducibility as a liquid printing ink laminate can be well maintained without deteriorating the tone reproducibility of the printed matter.
On the other hand, when the acid value is 60 mgKOH / g or less, the water resistance of the resin does not decrease, and the substrate adhesion and water friction resistance of the laminate can be kept good.
一方、本発明の水性リキッドインキ(A)の印刷層は、塗膜強度、特に耐摩擦性や耐スクラッチ性に優れるので、積層体の最表層即ち基材である熱可塑性樹脂フィルムから最も遠い最上層に水性リキッドインキ(A)の印刷層が設けることで、積層体の強度はより十分なものとなり、基材密着性、耐摩擦性、耐水摩擦性、耐スクラッチ性と言った基本的な塗膜強度がより保持される傾向にある。この時の印刷層は所望される意匠によって適宜色材を含有する色インキとしてもよく色材を含まないオーバーコートニスとして適用してもよい。色材を含有する色インキとして最もよく適用されるのは白色顔料を含有する白インキである。また、水性リキッドインキ(A)を刷り重ねて印刷層を複数層積層させることでより強固な印刷層面が得られることから、同色(例えば白インキ上に再度白インキ)を複数層重ねた印刷層とすることもある。また、色インキ(例えば白インキ)上に色材を含まないオーバーコートニスを複数層重ねた印刷層とすることもある。
On the other hand, the printing layer of the water-based liquid ink (A) of the present invention is excellent in coating film strength, particularly abrasion resistance and scratch resistance, and is therefore the farthest from the outermost layer of the laminate, that is, the thermoplastic resin film which is the base material. By providing a printing layer of water-based liquid ink (A) on the upper layer, the strength of the laminated body becomes more sufficient, and basic coatings such as substrate adhesion, abrasion resistance, water friction resistance, and scratch resistance are applied. The film strength tends to be more retained. The printing layer at this time may be appropriately applied as a color ink containing a color material or as an overcoat varnish containing no color material depending on the desired design. The most commonly applied color ink containing a coloring material is a white ink containing a white pigment. Further, since a stronger print layer surface can be obtained by printing the water-based liquid ink (A) on top of each other and laminating a plurality of print layers, a print layer in which a plurality of layers of the same color (for example, white ink again on the white ink) are laminated. It may be. Further, a printing layer may be formed in which a plurality of layers of overcoat varnish containing no coloring material are laminated on a color ink (for example, white ink).
前記水性リキッドインキ(A)に、前記硬化剤を適量添加して印刷した印刷層を有する積層体では、硬化スピードが増す分、インキの粘度安定性はやや低下するものの、基材密着性、耐摩耗性、耐水摩擦性、耐スクラッチ性を兼備するより強靭な積層体を得る事ができる。
In a laminate having a printed layer printed by adding an appropriate amount of the curing agent to the water-based liquid ink (A), the viscosity stability of the ink is slightly lowered by the increase in the curing speed, but the substrate adhesion and resistance to the substrate. It is possible to obtain a tougher laminate having abrasion resistance, water friction resistance, and scratch resistance.
本発明の水性リキッドインキ(A)の印刷層を有する積層体は、該印刷層が、塗膜強度、特に耐摩擦性や耐スクラッチ性に優れるので、印刷層が最表層となる形態に適している。前記表刷り印刷物や、前記裏刷り印刷物において、流通時に最表層となる面に本発明に水性リキッドインキ(A)の印刷層がある印刷物が本発明の効果を最大限に発揮でき好ましい。飲料や食品用ボトルに適用するプラスチックラベル(シュリンクラベルや胴巻きラベルが該当する)や、集積包装体、外装用包装体等、様々な用途に展開可能である。
The laminate having the print layer of the water-based liquid ink (A) of the present invention is suitable for a form in which the print layer is the outermost layer because the print layer is excellent in coating film strength, particularly abrasion resistance and scratch resistance. There is. In the front-printed matter and the back-printed matter, a printed matter having a printed layer of the water-based liquid ink (A) in the present invention on the surface that becomes the outermost layer at the time of distribution is preferable because the effect of the present invention can be maximized. It can be applied to various applications such as plastic labels (corresponding to shrink labels and body-wrap labels) applied to beverage and food bottles, integrated packaging, and exterior packaging.
以下実施例により、本発明をより詳しく説明する。尚、実施例中の「部」は「質量部」を、「%」は「質量%」をそれぞれ表す。
The present invention will be described in more detail with reference to the following examples. In the examples, "part" represents "parts by mass" and "%" represents "% by mass".
尚、本発明におけるGPC(ゲルパーミエーションクロマトグラフィー)による重量平均分子量(ポリスチレン換算)の測定は東ソー(株)社製HLC8220システムを用い以下の条件で行った。
分離カラム:東ソー(株)製TSKgelGMHHR-Nを4本使用。カラム温度:40℃。移動層:和光純薬工業(株)製テトラヒドロフラン。流速:1.0ml/分。試料濃度:1.0質量%。試料注入量:100マイクロリットル。検出器:示差屈折計。
また、アクリル樹脂の酸価は、樹脂1g中に含まれる酸性成分を中和するのに要する水酸化カリウムのミリグラム数を示すものであり、各々乾燥させた水溶性樹脂を、JIS K2501に準じた水酸化カリウム・エタノール溶液による電位差滴定から算出した。
また、ガラス転移温度(Tg)は、いわゆる計算ガラス転移温度を指し、下記の方法で算出された値を指す。
(式1) 1/Tg(K)=(W1/T1)+(W2/T2)+・・・(Wn/Tn)
(式2) Tg(℃)=Tg(K)-273
式1中のW1、W2、・・・Wnは、重合体の製造に使用したモノマーの合計質量に対する各モノマーの質量%を表し、T1、T2、・・・Tnは、各モノマーのホモポリマーのガラス転移温度(K)を表す。なお、T1、T2、・・Tnの値は、Polymer Handbook(Fourth Edition,J.Brandrup,E.H.Immergut,E.A.Grulke 編)に記載された値を用いる。
また、各モノマーのホモポリマーのガラス転移温度が前記Polymer Hand Bookに記載されていないもののガラス転移温度は、示差走査熱量計「DSC Q-100」(TA Instrument社製)を用い、JIS K7121に準拠した方法で測定した。具体的には、真空吸引して完全に溶剤を除去した重合体を、20℃/分の昇温速度で-100℃~+200℃の範囲で熱量変化を測定し、各ベースラインの延長した直線から縦軸方向に等距離にある直線と、ガラス転移の階段状変化部分の曲線とが交わる点をガラス転移温度とした。 The weight average molecular weight (in terms of polystyrene) measured by GPC (gel permeation chromatography) in the present invention was measured using an HLC8220 system manufactured by Toso Co., Ltd. under the following conditions.
Separation column: Uses 4 TSKgelGMH HR- N manufactured by Tosoh Corporation. Column temperature: 40 ° C. Moving layer: Tetrahydrofuran manufactured by Wako Pure Chemical Industries, Ltd. Flow velocity: 1.0 ml / min. Sample concentration: 1.0% by mass. Sample injection volume: 100 microliters. Detector: Differential refractometer.
The acid value of the acrylic resin indicates the number of milligrams of potassium hydroxide required to neutralize the acidic component contained in 1 g of the resin, and each dried water-soluble resin was prepared according to JIS K2501. It was calculated from potentiometric titration with a potassium hydroxide / ethanol solution.
The glass transition temperature (Tg) refers to the so-called calculated glass transition temperature, and refers to a value calculated by the following method.
(Equation 1) 1 / Tg (K) = (W1 / T1) + (W2 / T2) + ... (Wn / Tn)
(Equation 2) Tg (° C.) = Tg (K) -273
W1, W2, ... Wn in the formula 1 represent the mass% of each monomer with respect to the total mass of the monomers used for producing the polymer, and T1, T2, ... Tn are the homopolymers of each monomer. Represents the glass transition temperature (K). As the values of T1, T2, ... Tn, the values described in Polymer Handbook (Fourth Edition, J. Brandrup, E.H. Immersut, EA Grulke) are used.
Although the glass transition temperature of the homopolymer of each monomer is not described in the Polymer Hand Book, the glass transition temperature is based on JIS K7121 using a differential scanning calorimeter "DSC Q-100" (manufactured by TA Instrument). It was measured by the method described above. Specifically, the polymer from which the solvent has been completely removed by vacuum suction is measured for a change in calorific value in the range of -100 ° C to + 200 ° C at a heating rate of 20 ° C./min, and an extended straight line of each baseline. The point where the straight line equidistant from the vertical axis direction and the curve of the stepwise change portion of the glass transition intersect was defined as the glass transition temperature.
分離カラム:東ソー(株)製TSKgelGMHHR-Nを4本使用。カラム温度:40℃。移動層:和光純薬工業(株)製テトラヒドロフラン。流速:1.0ml/分。試料濃度:1.0質量%。試料注入量:100マイクロリットル。検出器:示差屈折計。
また、アクリル樹脂の酸価は、樹脂1g中に含まれる酸性成分を中和するのに要する水酸化カリウムのミリグラム数を示すものであり、各々乾燥させた水溶性樹脂を、JIS K2501に準じた水酸化カリウム・エタノール溶液による電位差滴定から算出した。
また、ガラス転移温度(Tg)は、いわゆる計算ガラス転移温度を指し、下記の方法で算出された値を指す。
(式1) 1/Tg(K)=(W1/T1)+(W2/T2)+・・・(Wn/Tn)
(式2) Tg(℃)=Tg(K)-273
式1中のW1、W2、・・・Wnは、重合体の製造に使用したモノマーの合計質量に対する各モノマーの質量%を表し、T1、T2、・・・Tnは、各モノマーのホモポリマーのガラス転移温度(K)を表す。なお、T1、T2、・・Tnの値は、Polymer Handbook(Fourth Edition,J.Brandrup,E.H.Immergut,E.A.Grulke 編)に記載された値を用いる。
また、各モノマーのホモポリマーのガラス転移温度が前記Polymer Hand Bookに記載されていないもののガラス転移温度は、示差走査熱量計「DSC Q-100」(TA Instrument社製)を用い、JIS K7121に準拠した方法で測定した。具体的には、真空吸引して完全に溶剤を除去した重合体を、20℃/分の昇温速度で-100℃~+200℃の範囲で熱量変化を測定し、各ベースラインの延長した直線から縦軸方向に等距離にある直線と、ガラス転移の階段状変化部分の曲線とが交わる点をガラス転移温度とした。 The weight average molecular weight (in terms of polystyrene) measured by GPC (gel permeation chromatography) in the present invention was measured using an HLC8220 system manufactured by Toso Co., Ltd. under the following conditions.
Separation column: Uses 4 TSKgelGMH HR- N manufactured by Tosoh Corporation. Column temperature: 40 ° C. Moving layer: Tetrahydrofuran manufactured by Wako Pure Chemical Industries, Ltd. Flow velocity: 1.0 ml / min. Sample concentration: 1.0% by mass. Sample injection volume: 100 microliters. Detector: Differential refractometer.
The acid value of the acrylic resin indicates the number of milligrams of potassium hydroxide required to neutralize the acidic component contained in 1 g of the resin, and each dried water-soluble resin was prepared according to JIS K2501. It was calculated from potentiometric titration with a potassium hydroxide / ethanol solution.
The glass transition temperature (Tg) refers to the so-called calculated glass transition temperature, and refers to a value calculated by the following method.
(Equation 1) 1 / Tg (K) = (W1 / T1) + (W2 / T2) + ... (Wn / Tn)
(Equation 2) Tg (° C.) = Tg (K) -273
W1, W2, ... Wn in the formula 1 represent the mass% of each monomer with respect to the total mass of the monomers used for producing the polymer, and T1, T2, ... Tn are the homopolymers of each monomer. Represents the glass transition temperature (K). As the values of T1, T2, ... Tn, the values described in Polymer Handbook (Fourth Edition, J. Brandrup, E.H. Immersut, EA Grulke) are used.
Although the glass transition temperature of the homopolymer of each monomer is not described in the Polymer Hand Book, the glass transition temperature is based on JIS K7121 using a differential scanning calorimeter "DSC Q-100" (manufactured by TA Instrument). It was measured by the method described above. Specifically, the polymer from which the solvent has been completely removed by vacuum suction is measured for a change in calorific value in the range of -100 ° C to + 200 ° C at a heating rate of 20 ° C./min, and an extended straight line of each baseline. The point where the straight line equidistant from the vertical axis direction and the curve of the stepwise change portion of the glass transition intersect was defined as the glass transition temperature.
〔合成例1:シェル部アクリル樹脂(重合体a1)の作製〕
反応容器に攪拌器、温度計、滴下ロート、還流管を備え、酢酸n-プロピル60.0部を仕込む。窒素雰囲気下で攪拌しながら、温度90℃まで昇温した。一方でメチルメタクリレート36.0部、エチルメタクリレート10.0部、n-ブチルメタクリレート20.0部、イソブチルメタクリレート10.0部、2-エチルヘキシルアクリレート10.0部、アクリル酸14.0部、アゾビスイソブチロニトリル1.0部を酢酸n-プロピル40.0部に溶解し、滴下ロートを用いて4時間かけて滴下した。滴下終了後、更に6時間反応させた。反応終了後に冷却を行い、得られたアクリル樹脂溶液に30%アンモニア水を8.0部加えて中和した。更にイオン交換水を加えて加熱しながら溶剤置換を行い、固形分55%のアクリル樹脂の水溶液を得た。酸価は105 mgKOH/g、Tgは65℃、重量平均分子量は16,000であった。 [Synthesis Example 1: Preparation of Shell Acrylic Resin (Polymer a1)]
The reaction vessel is equipped with a stirrer, a thermometer, a dropping funnel, and a reflux tube, and 60.0 parts of n-propyl acetate is charged. The temperature was raised to 90 ° C. while stirring in a nitrogen atmosphere. On the other hand, 36.0 parts of methyl methacrylate, 10.0 parts of ethyl methacrylate, 20.0 parts of n-butyl methacrylate, 10.0 parts of isobutyl methacrylate, 10.0 parts of 2-ethylhexyl acrylate, 14.0 parts of acrylic acid, and azobis. 1.0 part of isobutyronitrile was dissolved in 40.0 parts of n-propyl acetate and added dropwise over 4 hours using a dropping funnel. After completion of the dropping, the reaction was carried out for another 6 hours. After completion of the reaction, the mixture was cooled and neutralized by adding 8.0 parts of 30% aqueous ammonia to the obtained acrylic resin solution. Further, ion-exchanged water was added and solvent substitution was carried out while heating to obtain an aqueous solution of an acrylic resin having a solid content of 55%. The acid value was 105 mgKOH / g, Tg was 65 ° C., and the weight average molecular weight was 16,000.
反応容器に攪拌器、温度計、滴下ロート、還流管を備え、酢酸n-プロピル60.0部を仕込む。窒素雰囲気下で攪拌しながら、温度90℃まで昇温した。一方でメチルメタクリレート36.0部、エチルメタクリレート10.0部、n-ブチルメタクリレート20.0部、イソブチルメタクリレート10.0部、2-エチルヘキシルアクリレート10.0部、アクリル酸14.0部、アゾビスイソブチロニトリル1.0部を酢酸n-プロピル40.0部に溶解し、滴下ロートを用いて4時間かけて滴下した。滴下終了後、更に6時間反応させた。反応終了後に冷却を行い、得られたアクリル樹脂溶液に30%アンモニア水を8.0部加えて中和した。更にイオン交換水を加えて加熱しながら溶剤置換を行い、固形分55%のアクリル樹脂の水溶液を得た。酸価は105 mgKOH/g、Tgは65℃、重量平均分子量は16,000であった。 [Synthesis Example 1: Preparation of Shell Acrylic Resin (Polymer a1)]
The reaction vessel is equipped with a stirrer, a thermometer, a dropping funnel, and a reflux tube, and 60.0 parts of n-propyl acetate is charged. The temperature was raised to 90 ° C. while stirring in a nitrogen atmosphere. On the other hand, 36.0 parts of methyl methacrylate, 10.0 parts of ethyl methacrylate, 20.0 parts of n-butyl methacrylate, 10.0 parts of isobutyl methacrylate, 10.0 parts of 2-ethylhexyl acrylate, 14.0 parts of acrylic acid, and azobis. 1.0 part of isobutyronitrile was dissolved in 40.0 parts of n-propyl acetate and added dropwise over 4 hours using a dropping funnel. After completion of the dropping, the reaction was carried out for another 6 hours. After completion of the reaction, the mixture was cooled and neutralized by adding 8.0 parts of 30% aqueous ammonia to the obtained acrylic resin solution. Further, ion-exchanged water was added and solvent substitution was carried out while heating to obtain an aqueous solution of an acrylic resin having a solid content of 55%. The acid value was 105 mgKOH / g, Tg was 65 ° C., and the weight average molecular weight was 16,000.
〔合成例2:コポリマーを有するコアシェル型アクリルエマルジョン(A1)の作製〕 酸価42
合成例1で調製したアクリル樹脂水溶液121.2部を仕込んだ反応容器に、攪拌器、温度計、滴下ロート、還流管を備え、イオン交換水195.5部を加える。窒素雰囲気下で攪拌を行いながら温度75℃まで昇温した。続いて滴下ロートを用いてメチルメタクリレート30.0部、エチルメタクリレート20.0部、n-ブチルアクリレート25.0部、2-エチルヘキシルアクリレート25.0部、30%過硫酸アンモニウム3.3部を4時間かけて滴下した。滴下完了後、更に6時間反応を行い、固形分40%のコアシェル型アクリルエマルジョン(A1)を得た。酸価は42mgKOH/g、Tgは10℃、重量平均分子量は1,200,000であった。 [Synthesis Example 2: Preparation of Core Shell Acrylic Emulsion (A1) Having Copolymer] Acid Value 42
A stirrer, a thermometer, a dropping funnel, and a reflux tube are provided in a reaction vessel containing 121.2 parts of the acrylic resin aqueous solution prepared in Synthesis Example 1, and 195.5 parts of ion-exchanged water is added. The temperature was raised to 75 ° C. while stirring in a nitrogen atmosphere. Subsequently, using a dropping funnel, 30.0 parts of methyl methacrylate, 20.0 parts of ethyl methacrylate, 25.0 parts of n-butyl acrylate, 25.0 parts of 2-ethylhexyl acrylate, and 3.3 parts of 30% ammonium persulfate were added for 4 hours. Dropped over. After the dropping was completed, the reaction was further carried out for 6 hours to obtain a core-shell acrylic emulsion (A1) having a solid content of 40%. The acid value was 42 mgKOH / g, Tg was 10 ° C., and the weight average molecular weight was 1,200,000.
合成例1で調製したアクリル樹脂水溶液121.2部を仕込んだ反応容器に、攪拌器、温度計、滴下ロート、還流管を備え、イオン交換水195.5部を加える。窒素雰囲気下で攪拌を行いながら温度75℃まで昇温した。続いて滴下ロートを用いてメチルメタクリレート30.0部、エチルメタクリレート20.0部、n-ブチルアクリレート25.0部、2-エチルヘキシルアクリレート25.0部、30%過硫酸アンモニウム3.3部を4時間かけて滴下した。滴下完了後、更に6時間反応を行い、固形分40%のコアシェル型アクリルエマルジョン(A1)を得た。酸価は42mgKOH/g、Tgは10℃、重量平均分子量は1,200,000であった。 [Synthesis Example 2: Preparation of Core Shell Acrylic Emulsion (A1) Having Copolymer] Acid Value 42
A stirrer, a thermometer, a dropping funnel, and a reflux tube are provided in a reaction vessel containing 121.2 parts of the acrylic resin aqueous solution prepared in Synthesis Example 1, and 195.5 parts of ion-exchanged water is added. The temperature was raised to 75 ° C. while stirring in a nitrogen atmosphere. Subsequently, using a dropping funnel, 30.0 parts of methyl methacrylate, 20.0 parts of ethyl methacrylate, 25.0 parts of n-butyl acrylate, 25.0 parts of 2-ethylhexyl acrylate, and 3.3 parts of 30% ammonium persulfate were added for 4 hours. Dropped over. After the dropping was completed, the reaction was further carried out for 6 hours to obtain a core-shell acrylic emulsion (A1) having a solid content of 40%. The acid value was 42 mgKOH / g, Tg was 10 ° C., and the weight average molecular weight was 1,200,000.
〔合成例3:コポリマーを有するコアシェル型アクリルエマルジョン(A2)の作製〕 酸価42
合成例1で調製したアクリル樹脂水溶液121.2部を仕込んだ反応容器に、攪拌器、温度計、滴下ロート、還流管を備え、イオン交換水195.5部を加える。窒素雰囲気下で攪拌を行いながら温度75℃まで昇温した。続いて滴下ロートを用いてメチルメタクリレート32.0部、ブチルアクリレート28.0部、エチルメタクリレート10.0部、イソブチルメタクリレート30.0部、30%過硫酸アンモニウム3.5部を4時間かけて滴下した。滴下完了後、更に6時間反応を行い、固形分40%のコアシェル型アクリルエマルジョン(A2)を得た。酸価は42mgKOH/g、Tgは45℃、重量平均分子量は1,200,000であった。 [Synthesis Example 3: Preparation of Core Shell Acrylic Emulsion (A2) Having Copolymer] Acid Value 42
A stirrer, a thermometer, a dropping funnel, and a reflux tube are provided in a reaction vessel containing 121.2 parts of the acrylic resin aqueous solution prepared in Synthesis Example 1, and 195.5 parts of ion-exchanged water is added. The temperature was raised to 75 ° C. while stirring in a nitrogen atmosphere. Subsequently, using a dropping funnel, 32.0 parts of methyl methacrylate, 28.0 parts of butyl acrylate, 10.0 parts of ethyl methacrylate, 30.0 parts of isobutyl methacrylate, and 3.5 parts of 30% ammonium persulfate were added dropwise over 4 hours. .. After the dropping was completed, the reaction was further carried out for 6 hours to obtain a core-shell acrylic emulsion (A2) having a solid content of 40%. The acid value was 42 mgKOH / g, Tg was 45 ° C., and the weight average molecular weight was 1,200,000.
合成例1で調製したアクリル樹脂水溶液121.2部を仕込んだ反応容器に、攪拌器、温度計、滴下ロート、還流管を備え、イオン交換水195.5部を加える。窒素雰囲気下で攪拌を行いながら温度75℃まで昇温した。続いて滴下ロートを用いてメチルメタクリレート32.0部、ブチルアクリレート28.0部、エチルメタクリレート10.0部、イソブチルメタクリレート30.0部、30%過硫酸アンモニウム3.5部を4時間かけて滴下した。滴下完了後、更に6時間反応を行い、固形分40%のコアシェル型アクリルエマルジョン(A2)を得た。酸価は42mgKOH/g、Tgは45℃、重量平均分子量は1,200,000であった。 [Synthesis Example 3: Preparation of Core Shell Acrylic Emulsion (A2) Having Copolymer] Acid Value 42
A stirrer, a thermometer, a dropping funnel, and a reflux tube are provided in a reaction vessel containing 121.2 parts of the acrylic resin aqueous solution prepared in Synthesis Example 1, and 195.5 parts of ion-exchanged water is added. The temperature was raised to 75 ° C. while stirring in a nitrogen atmosphere. Subsequently, using a dropping funnel, 32.0 parts of methyl methacrylate, 28.0 parts of butyl acrylate, 10.0 parts of ethyl methacrylate, 30.0 parts of isobutyl methacrylate, and 3.5 parts of 30% ammonium persulfate were added dropwise over 4 hours. .. After the dropping was completed, the reaction was further carried out for 6 hours to obtain a core-shell acrylic emulsion (A2) having a solid content of 40%. The acid value was 42 mgKOH / g, Tg was 45 ° C., and the weight average molecular weight was 1,200,000.
〔合成例4:シェル部スチレンアクリル樹脂の作製〕
反応容器に攪拌器、温度計、滴下ロート、還流管を備え、酢酸n-プロピル65.0部を仕込む。窒素雰囲気下で攪拌しながら、温度90℃まで昇温した。一方でスチレン36.0部、エチルメタクリレート12.0部、2-エチルヘキシルアクリレート20.0部、アクリル酸32.0部、アゾビスイソブチロニトリル1.6部を酢酸n-プロピル35.0部に溶解し、滴下ロートを用いて4時間かけて滴下した。滴下終了後、更に6時間反応させた。反応終了後に冷却を行い、得られたアクリル樹脂溶液に30%アンモニア水を20.0部加えて中和した。更にイオン交換水を加えて加熱しながら溶剤置換を行い、固形分30%のアクリル樹脂の水溶液を得た。酸価は250 mgKOH/g、Tgは61℃、重量平均分子量は10,200であった。 [Synthesis Example 4: Preparation of Shell Styrene Acrylic Resin]
The reaction vessel is equipped with a stirrer, a thermometer, a dropping funnel, and a reflux tube, and 65.0 parts of n-propyl acetate is charged. The temperature was raised to 90 ° C. while stirring in a nitrogen atmosphere. On the other hand, 36.0 parts of styrene, 12.0 parts of ethyl methacrylate, 20.0 parts of 2-ethylhexyl acrylate, 32.0 parts of acrylic acid, 1.6 parts of azobisisobutyronitrile and 35.0 parts of n-propyl acetate. It was dissolved in and dropped over 4 hours using a dropping funnel. After completion of the dropping, the reaction was carried out for another 6 hours. After completion of the reaction, the mixture was cooled and neutralized by adding 20.0 parts of 30% aqueous ammonia to the obtained acrylic resin solution. Further, ion-exchanged water was added and solvent substitution was carried out while heating to obtain an aqueous solution of an acrylic resin having a solid content of 30%. The acid value was 250 mgKOH / g, Tg was 61 ° C., and the weight average molecular weight was 10,200.
反応容器に攪拌器、温度計、滴下ロート、還流管を備え、酢酸n-プロピル65.0部を仕込む。窒素雰囲気下で攪拌しながら、温度90℃まで昇温した。一方でスチレン36.0部、エチルメタクリレート12.0部、2-エチルヘキシルアクリレート20.0部、アクリル酸32.0部、アゾビスイソブチロニトリル1.6部を酢酸n-プロピル35.0部に溶解し、滴下ロートを用いて4時間かけて滴下した。滴下終了後、更に6時間反応させた。反応終了後に冷却を行い、得られたアクリル樹脂溶液に30%アンモニア水を20.0部加えて中和した。更にイオン交換水を加えて加熱しながら溶剤置換を行い、固形分30%のアクリル樹脂の水溶液を得た。酸価は250 mgKOH/g、Tgは61℃、重量平均分子量は10,200であった。 [Synthesis Example 4: Preparation of Shell Styrene Acrylic Resin]
The reaction vessel is equipped with a stirrer, a thermometer, a dropping funnel, and a reflux tube, and 65.0 parts of n-propyl acetate is charged. The temperature was raised to 90 ° C. while stirring in a nitrogen atmosphere. On the other hand, 36.0 parts of styrene, 12.0 parts of ethyl methacrylate, 20.0 parts of 2-ethylhexyl acrylate, 32.0 parts of acrylic acid, 1.6 parts of azobisisobutyronitrile and 35.0 parts of n-propyl acetate. It was dissolved in and dropped over 4 hours using a dropping funnel. After completion of the dropping, the reaction was carried out for another 6 hours. After completion of the reaction, the mixture was cooled and neutralized by adding 20.0 parts of 30% aqueous ammonia to the obtained acrylic resin solution. Further, ion-exchanged water was added and solvent substitution was carried out while heating to obtain an aqueous solution of an acrylic resin having a solid content of 30%. The acid value was 250 mgKOH / g, Tg was 61 ° C., and the weight average molecular weight was 10,200.
〔合成例5:コポリマーを有するコアシェル型スチレンアクリルエマルジョン(A3)の作製〕 酸価100
合成例4で調製したスチレンアクリル樹脂水溶液222.2部を仕込んだ反応容器に、攪拌器、温度計、滴下ロート、還流管を備え、イオン交換水119.6部を加える。窒素雰囲気下で攪拌を行いながら温度75℃まで昇温した。続いて滴下ロートを用いてメチルメタクリレート32.0部、ブチルアクリレート46.0部、エチルメタクリレート10.0部、イソブチルメタクリレート18.0部、30%過硫酸アンモニウム3.5部を4時間かけて滴下した。滴下完了後、更に6時間反応を行い、固形分38.5%のコアシェル型スチレンアクリルエマルジョン(A3)を得た。酸価は100mgKOH/g、Tgは42℃、重量平均分子量は1,200,000であった。 [Synthesis Example 5: Preparation of Core-Shell Type Styrene Acrylic Emulsion (A3) Having Copolymer] Acid Value 100
A stirrer, a thermometer, a dropping funnel, and a reflux tube are provided in a reaction vessel containing 222.2 parts of the styrene acrylic resin aqueous solution prepared in Synthesis Example 4, and 119.6 parts of ion-exchanged water is added. The temperature was raised to 75 ° C. while stirring in a nitrogen atmosphere. Subsequently, using a dropping funnel, 32.0 parts of methyl methacrylate, 46.0 parts of butyl acrylate, 10.0 parts of ethyl methacrylate, 18.0 parts of isobutyl methacrylate, and 3.5 parts of 30% ammonium persulfate were added dropwise over 4 hours. .. After the dropping was completed, the reaction was further carried out for 6 hours to obtain a core-shell type styrene acrylic emulsion (A3) having a solid content of 38.5%. The acid value was 100 mgKOH / g, Tg was 42 ° C., and the weight average molecular weight was 1,200,000.
合成例4で調製したスチレンアクリル樹脂水溶液222.2部を仕込んだ反応容器に、攪拌器、温度計、滴下ロート、還流管を備え、イオン交換水119.6部を加える。窒素雰囲気下で攪拌を行いながら温度75℃まで昇温した。続いて滴下ロートを用いてメチルメタクリレート32.0部、ブチルアクリレート46.0部、エチルメタクリレート10.0部、イソブチルメタクリレート18.0部、30%過硫酸アンモニウム3.5部を4時間かけて滴下した。滴下完了後、更に6時間反応を行い、固形分38.5%のコアシェル型スチレンアクリルエマルジョン(A3)を得た。酸価は100mgKOH/g、Tgは42℃、重量平均分子量は1,200,000であった。 [Synthesis Example 5: Preparation of Core-Shell Type Styrene Acrylic Emulsion (A3) Having Copolymer] Acid Value 100
A stirrer, a thermometer, a dropping funnel, and a reflux tube are provided in a reaction vessel containing 222.2 parts of the styrene acrylic resin aqueous solution prepared in Synthesis Example 4, and 119.6 parts of ion-exchanged water is added. The temperature was raised to 75 ° C. while stirring in a nitrogen atmosphere. Subsequently, using a dropping funnel, 32.0 parts of methyl methacrylate, 46.0 parts of butyl acrylate, 10.0 parts of ethyl methacrylate, 18.0 parts of isobutyl methacrylate, and 3.5 parts of 30% ammonium persulfate were added dropwise over 4 hours. .. After the dropping was completed, the reaction was further carried out for 6 hours to obtain a core-shell type styrene acrylic emulsion (A3) having a solid content of 38.5%. The acid value was 100 mgKOH / g, Tg was 42 ° C., and the weight average molecular weight was 1,200,000.
〔合成例6:コポリマー(B)の作製〕 酸価220
反応容器に攪拌器、温度計、滴下ロート、還流管を備え、酢酸n-プロピル65.0部を仕込む。窒素雰囲気下で攪拌しながら、温度90℃まで昇温した。一方でスチレン45.0部、エチルメタクリレート10.0部、2-エチルヘキシルアクリレート20.0部、アクリル酸25.0部、アゾビスイソブチロニトリル1.6部を酢酸n-プロピル35.0部に溶解し、滴下ロートを用いて4時間かけて滴下した。滴下終了後、更に6時間反応させた。反応終了後に冷却を行い、得られたアクリル樹脂溶液に30%アンモニア水を20.0部加えて中和した。更にイオン交換水を加えて加熱しながら溶剤置換を行い、固形分30%のアクリル樹脂の水溶液であるコポリマー(B)を得た。酸価は220 mgKOH/g、Tgは60℃、重量平均分子量は10,000であった。 [Synthesis Example 6: Preparation of Copolymer (B)] Acid Value 220
The reaction vessel is equipped with a stirrer, a thermometer, a dropping funnel, and a reflux tube, and 65.0 parts of n-propyl acetate is charged. The temperature was raised to 90 ° C. while stirring in a nitrogen atmosphere. On the other hand, 45.0 parts of styrene, 10.0 parts of ethyl methacrylate, 20.0 parts of 2-ethylhexyl acrylate, 25.0 parts of acrylic acid, 1.6 parts of azobisisobutyronitrile and 35.0 parts of n-propyl acetate. It was dissolved in and dropped over 4 hours using a dropping funnel. After completion of the dropping, the reaction was carried out for another 6 hours. After completion of the reaction, the mixture was cooled and neutralized by adding 20.0 parts of 30% aqueous ammonia to the obtained acrylic resin solution. Further, ion-exchanged water was added and solvent substitution was carried out while heating to obtain a copolymer (B) which is an aqueous solution of an acrylic resin having a solid content of 30%. The acid value was 220 mgKOH / g, Tg was 60 ° C., and the weight average molecular weight was 10,000.
反応容器に攪拌器、温度計、滴下ロート、還流管を備え、酢酸n-プロピル65.0部を仕込む。窒素雰囲気下で攪拌しながら、温度90℃まで昇温した。一方でスチレン45.0部、エチルメタクリレート10.0部、2-エチルヘキシルアクリレート20.0部、アクリル酸25.0部、アゾビスイソブチロニトリル1.6部を酢酸n-プロピル35.0部に溶解し、滴下ロートを用いて4時間かけて滴下した。滴下終了後、更に6時間反応させた。反応終了後に冷却を行い、得られたアクリル樹脂溶液に30%アンモニア水を20.0部加えて中和した。更にイオン交換水を加えて加熱しながら溶剤置換を行い、固形分30%のアクリル樹脂の水溶液であるコポリマー(B)を得た。酸価は220 mgKOH/g、Tgは60℃、重量平均分子量は10,000であった。 [Synthesis Example 6: Preparation of Copolymer (B)] Acid Value 220
The reaction vessel is equipped with a stirrer, a thermometer, a dropping funnel, and a reflux tube, and 65.0 parts of n-propyl acetate is charged. The temperature was raised to 90 ° C. while stirring in a nitrogen atmosphere. On the other hand, 45.0 parts of styrene, 10.0 parts of ethyl methacrylate, 20.0 parts of 2-ethylhexyl acrylate, 25.0 parts of acrylic acid, 1.6 parts of azobisisobutyronitrile and 35.0 parts of n-propyl acetate. It was dissolved in and dropped over 4 hours using a dropping funnel. After completion of the dropping, the reaction was carried out for another 6 hours. After completion of the reaction, the mixture was cooled and neutralized by adding 20.0 parts of 30% aqueous ammonia to the obtained acrylic resin solution. Further, ion-exchanged water was added and solvent substitution was carried out while heating to obtain a copolymer (B) which is an aqueous solution of an acrylic resin having a solid content of 30%. The acid value was 220 mgKOH / g, Tg was 60 ° C., and the weight average molecular weight was 10,000.
〔合成例7:ポリウレタン樹脂(Pu)の作製〕
PLACCEL 212(ダイセル化学工業(株)製、ポリカプロラクトンジオール、水酸基価90 mgKOH/g)の186.9部およびイソホロジイソシアネート(IPDIと略す)の100.0部を仕込んだ。これを攪拌しながら、110℃に加熱した。1時間後、80℃まで冷却し、ジメチロールプロピオン酸(DMPAと略す)の20.1部、ジブチル錫ジラウレートの0.3部および酢酸エチルの76.8部を加え、80℃で2時間反応させた。ここに、バーノック DN-980S(DIC社製、ヘキサメチレンジイソシアネート系ポリイソシアネート、NCO含量20%)の18.1部とメチルエチルケトン(MEKと略す)の408部を加えた。この時のNCO基含有量は固形分換算で4.9%であった。
これを30℃以下まで冷却し、トリエチルアミンの15.2部を加え、次いでイオン交換水の1293部を加えて水中油滴(O/W)型のエマルジョンを得た。続いてジエチレントリアミン5%水溶液の234部を徐々に加え、加え終わった後60℃に昇温して30分攪拌を続けた。次いで減圧下において蒸留を行い、溶剤と水の一部を除去し、ポリウレタン樹脂(Pu)の水溶液を得た。
このものはやや乳白色を呈する半透明液体であり、少量を試験管に取ってテトラヒドロフラン(THFと略す)を加えると濁りを呈し、架橋して不溶解になっていることを示した。不揮発分39.6%で、粘度が160cpsで、pHが7.7で、平均粒子径が28.5nmであった。 [Synthesis Example 7: Preparation of Polyurethane Resin (Pu)]
186.9 parts of PLACCEL 212 (polycaprolactone diol manufactured by Daicel Chemical Industries, Ltd., hydroxyl value 90 mgKOH / g) and 100.0 parts of isophorone diisocyanate (abbreviated as IPDI) were charged. This was heated to 110 ° C. with stirring. After 1 hour, the mixture was cooled to 80 ° C., 20.1 parts of dimethylolpropionic acid (abbreviated as DMPA), 0.3 part of dibutyltin dilaurate and 76.8 parts of ethyl acetate were added, and the reaction was carried out at 80 ° C. for 2 hours. I let you. To this, 18.1 part of Bernock DN-980S (manufactured by DIC, hexamethylene diisocyanate polyisocyanate, NCO content 20%) and 408 parts of methyl ethyl ketone (abbreviated as MEK) were added. The NCO group content at this time was 4.9% in terms of solid content.
This was cooled to 30 ° C. or lower, 15.2 parts of triethylamine was added, and then 1293 parts of ion-exchanged water was added to obtain an oil droplet (O / W) type emulsion in water. Subsequently, 234 parts of a 5% aqueous solution of diethylenetriamine was gradually added, and after the addition was completed, the temperature was raised to 60 ° C. and stirring was continued for 30 minutes. Then, distillation was carried out under reduced pressure to remove a part of the solvent and water to obtain an aqueous solution of polyurethane resin (Pu).
This is a translucent liquid that is slightly milky white, and when a small amount is taken in a test tube and tetrahydrofuran (abbreviated as THF) is added, it becomes turbid and cross-linked to be insoluble. The non-volatile content was 39.6%, the viscosity was 160 cps, the pH was 7.7, and the average particle size was 28.5 nm.
PLACCEL 212(ダイセル化学工業(株)製、ポリカプロラクトンジオール、水酸基価90 mgKOH/g)の186.9部およびイソホロジイソシアネート(IPDIと略す)の100.0部を仕込んだ。これを攪拌しながら、110℃に加熱した。1時間後、80℃まで冷却し、ジメチロールプロピオン酸(DMPAと略す)の20.1部、ジブチル錫ジラウレートの0.3部および酢酸エチルの76.8部を加え、80℃で2時間反応させた。ここに、バーノック DN-980S(DIC社製、ヘキサメチレンジイソシアネート系ポリイソシアネート、NCO含量20%)の18.1部とメチルエチルケトン(MEKと略す)の408部を加えた。この時のNCO基含有量は固形分換算で4.9%であった。
これを30℃以下まで冷却し、トリエチルアミンの15.2部を加え、次いでイオン交換水の1293部を加えて水中油滴(O/W)型のエマルジョンを得た。続いてジエチレントリアミン5%水溶液の234部を徐々に加え、加え終わった後60℃に昇温して30分攪拌を続けた。次いで減圧下において蒸留を行い、溶剤と水の一部を除去し、ポリウレタン樹脂(Pu)の水溶液を得た。
このものはやや乳白色を呈する半透明液体であり、少量を試験管に取ってテトラヒドロフラン(THFと略す)を加えると濁りを呈し、架橋して不溶解になっていることを示した。不揮発分39.6%で、粘度が160cpsで、pHが7.7で、平均粒子径が28.5nmであった。 [Synthesis Example 7: Preparation of Polyurethane Resin (Pu)]
186.9 parts of PLACCEL 212 (polycaprolactone diol manufactured by Daicel Chemical Industries, Ltd., hydroxyl value 90 mgKOH / g) and 100.0 parts of isophorone diisocyanate (abbreviated as IPDI) were charged. This was heated to 110 ° C. with stirring. After 1 hour, the mixture was cooled to 80 ° C., 20.1 parts of dimethylolpropionic acid (abbreviated as DMPA), 0.3 part of dibutyltin dilaurate and 76.8 parts of ethyl acetate were added, and the reaction was carried out at 80 ° C. for 2 hours. I let you. To this, 18.1 part of Bernock DN-980S (manufactured by DIC, hexamethylene diisocyanate polyisocyanate, NCO content 20%) and 408 parts of methyl ethyl ketone (abbreviated as MEK) were added. The NCO group content at this time was 4.9% in terms of solid content.
This was cooled to 30 ° C. or lower, 15.2 parts of triethylamine was added, and then 1293 parts of ion-exchanged water was added to obtain an oil droplet (O / W) type emulsion in water. Subsequently, 234 parts of a 5% aqueous solution of diethylenetriamine was gradually added, and after the addition was completed, the temperature was raised to 60 ° C. and stirring was continued for 30 minutes. Then, distillation was carried out under reduced pressure to remove a part of the solvent and water to obtain an aqueous solution of polyurethane resin (Pu).
This is a translucent liquid that is slightly milky white, and when a small amount is taken in a test tube and tetrahydrofuran (abbreviated as THF) is added, it becomes turbid and cross-linked to be insoluble. The non-volatile content was 39.6%, the viscosity was 160 cps, the pH was 7.7, and the average particle size was 28.5 nm.
〔合成例8:アクリルウレタン樹脂(Au)の作製〕
反応容器に攪拌器、温度計、滴下ロート、還流管を備え、酢酸n-プロピル80.0部を仕込む。窒素雰囲気下で攪拌しながら、温度90℃まで昇温した。一方でスチレン32.0部、メタクリル酸2-ヒドロキシエチル20.0部、2-エチルヘキシルアクリレート40.0部、アクリル酸8.0部、アゾビスイソブチロニトリル3.0部を酢酸n-プロピル40.0部に溶解し、滴下ロートを用いて4時間かけて滴下した。滴下終了後、バーノック DN-980S(DIC社製、ヘキサメチレンジイソシアネート系ポリイソシアネート、NCO含量20%)1.6部を徐々に加え、更に6時間反応させた。反応終了後に冷却を行い、得られたアクリル樹脂溶液に30%アンモニア水を4.0部加えて中和した。更にイオン交換水を加えて加熱しながら溶剤置換を行い、固形分25%のアクリルウレタン樹脂(Au)の水溶液を得た。酸価は62 mgKOH/g、Tgは30℃、重量平均分子量は600,000であった。 [Synthesis Example 8: Preparation of Acrylic Urethane Resin (Au)]
The reaction vessel is equipped with a stirrer, a thermometer, a dropping funnel, and a reflux tube, and 80.0 parts of n-propyl acetate is charged. The temperature was raised to 90 ° C. while stirring in a nitrogen atmosphere. On the other hand, 32.0 parts of styrene, 20.0 parts of 2-hydroxyethyl methacrylate, 40.0 parts of 2-ethylhexyl acrylate, 8.0 parts of acrylic acid, and 3.0 parts of azobisisobutyronitrile were added to n-propyl acetate. It was dissolved in 40.0 parts and added dropwise over 4 hours using a dropping funnel. After completion of the dropping, 1.6 parts of Burnock DN-980S (manufactured by DIC, hexamethylene diisocyanate polyisocyanate, NCO content 20%) was gradually added, and the mixture was further reacted for 6 hours. After completion of the reaction, the mixture was cooled and neutralized by adding 4.0 parts of 30% aqueous ammonia to the obtained acrylic resin solution. Further, ion-exchanged water was added and solvent substitution was carried out while heating to obtain an aqueous solution of acrylic urethane resin (Au) having a solid content of 25%. The acid value was 62 mgKOH / g, the Tg was 30 ° C., and the weight average molecular weight was 600,000.
反応容器に攪拌器、温度計、滴下ロート、還流管を備え、酢酸n-プロピル80.0部を仕込む。窒素雰囲気下で攪拌しながら、温度90℃まで昇温した。一方でスチレン32.0部、メタクリル酸2-ヒドロキシエチル20.0部、2-エチルヘキシルアクリレート40.0部、アクリル酸8.0部、アゾビスイソブチロニトリル3.0部を酢酸n-プロピル40.0部に溶解し、滴下ロートを用いて4時間かけて滴下した。滴下終了後、バーノック DN-980S(DIC社製、ヘキサメチレンジイソシアネート系ポリイソシアネート、NCO含量20%)1.6部を徐々に加え、更に6時間反応させた。反応終了後に冷却を行い、得られたアクリル樹脂溶液に30%アンモニア水を4.0部加えて中和した。更にイオン交換水を加えて加熱しながら溶剤置換を行い、固形分25%のアクリルウレタン樹脂(Au)の水溶液を得た。酸価は62 mgKOH/g、Tgは30℃、重量平均分子量は600,000であった。 [Synthesis Example 8: Preparation of Acrylic Urethane Resin (Au)]
The reaction vessel is equipped with a stirrer, a thermometer, a dropping funnel, and a reflux tube, and 80.0 parts of n-propyl acetate is charged. The temperature was raised to 90 ° C. while stirring in a nitrogen atmosphere. On the other hand, 32.0 parts of styrene, 20.0 parts of 2-hydroxyethyl methacrylate, 40.0 parts of 2-ethylhexyl acrylate, 8.0 parts of acrylic acid, and 3.0 parts of azobisisobutyronitrile were added to n-propyl acetate. It was dissolved in 40.0 parts and added dropwise over 4 hours using a dropping funnel. After completion of the dropping, 1.6 parts of Burnock DN-980S (manufactured by DIC, hexamethylene diisocyanate polyisocyanate, NCO content 20%) was gradually added, and the mixture was further reacted for 6 hours. After completion of the reaction, the mixture was cooled and neutralized by adding 4.0 parts of 30% aqueous ammonia to the obtained acrylic resin solution. Further, ion-exchanged water was added and solvent substitution was carried out while heating to obtain an aqueous solution of acrylic urethane resin (Au) having a solid content of 25%. The acid value was 62 mgKOH / g, the Tg was 30 ° C., and the weight average molecular weight was 600,000.
〔実施例1:OPニスの製造〕
合成例2で作製したコポリマーを有するコアシェル型アクリルエマルジョン(A1)を固形分換算で35部、アセチレン系界面活性剤としてアルキレンオキサイド変性アセチレングリコール系界面活性剤であるサーフィノール420(Cas番号:9014-85-1 日信化学工業(株)社製)0.1部、ポリエチレンワックス5部、ノルマルプロパノール4部、消泡剤0.1部、アンモニア水1.2部、水54.6部を撹拌混合した後、ビーズミルで練肉しOPニスを作製した。得られた水性ニスの粘度がザーンカップ#4(離合社製)で16秒(25℃)である事を確認した。 [Example 1: Production of OP varnish]
35 parts of the core-shell type acrylic emulsion (A1) having the copolymer prepared in Synthesis Example 2 in terms of solid content, Surfinol 420 (Cas No .: 9014-), which is an alkylene oxide-modified acetylene glycol-based surfactant as an acetylene-based surfactant. 85-1 Nisshin Kagaku Kogyo Co., Ltd.) 0.1 parts, polyethylene wax 5 parts, normal propanol 4 parts, defoamer 0.1 parts, ammonia water 1.2 parts, water 54.6 parts are stirred. After mixing, the meat was kneaded with a bead mill to prepare an OP varnish. It was confirmed that the viscosity of the obtained aqueous varnish was 16 seconds (25 ° C.) with Zahn Cup # 4 (manufactured by Rigosha).
合成例2で作製したコポリマーを有するコアシェル型アクリルエマルジョン(A1)を固形分換算で35部、アセチレン系界面活性剤としてアルキレンオキサイド変性アセチレングリコール系界面活性剤であるサーフィノール420(Cas番号:9014-85-1 日信化学工業(株)社製)0.1部、ポリエチレンワックス5部、ノルマルプロパノール4部、消泡剤0.1部、アンモニア水1.2部、水54.6部を撹拌混合した後、ビーズミルで練肉しOPニスを作製した。得られた水性ニスの粘度がザーンカップ#4(離合社製)で16秒(25℃)である事を確認した。 [Example 1: Production of OP varnish]
35 parts of the core-shell type acrylic emulsion (A1) having the copolymer prepared in Synthesis Example 2 in terms of solid content, Surfinol 420 (Cas No .: 9014-), which is an alkylene oxide-modified acetylene glycol-based surfactant as an acetylene-based surfactant. 85-1 Nisshin Kagaku Kogyo Co., Ltd.) 0.1 parts, polyethylene wax 5 parts, normal propanol 4 parts, defoamer 0.1 parts, ammonia water 1.2 parts, water 54.6 parts are stirred. After mixing, the meat was kneaded with a bead mill to prepare an OP varnish. It was confirmed that the viscosity of the obtained aqueous varnish was 16 seconds (25 ° C.) with Zahn Cup # 4 (manufactured by Rigosha).
(実施例2~24、比較例1~13:OPニスの製造)
表1~3、表5,6の通りの配合で、OPニスを得た。 (Examples 2 to 24, Comparative Examples 1 to 13: Production of OP varnish)
OP varnishes were obtained with the formulations shown in Tables 1 to 3 and Tables 5 and 6.
表1~3、表5,6の通りの配合で、OPニスを得た。 (Examples 2 to 24, Comparative Examples 1 to 13: Production of OP varnish)
OP varnishes were obtained with the formulations shown in Tables 1 to 3 and Tables 5 and 6.
(実施例25:水性リキッドインキの製造〕
合成例2で作製したコポリマーを有するコアシェル型アクリルエマルジョン(A1)を固形分換算で20部、酸化チタン(テイカ社製 製品名:JR-800)40部、サーフィノール420を1部、ポリエチレンワックス5部、ノルマルプロパノール3部、消泡剤0.1部、アンモニア水0.6部、水31.3部の計100部を撹拌混合した後、ビーズミルで練肉し白色の水性リキッドインキを作製した。得られた水性リキッドインキの粘度がザーンカップ#4(離合社製)で16秒(25℃)である事を確認した。 (Example 25: Production of water-based liquid ink]
20 parts of core-shell type acrylic emulsion (A1) having the copolymer prepared in Synthesis Example 2, 40 parts of titanium oxide (product name: JR-800 manufactured by TAYCA Corporation), 1 part of Surfinol 420, polyethylene wax 5 A total of 100 parts, 3 parts of normal propanol, 0.1 part of defoaming agent, 0.6 part of ammonia water, and 31.3 parts of water, were stirred and mixed, and then kneaded with a bead mill to prepare a white aqueous liquid ink. .. It was confirmed that the viscosity of the obtained aqueous liquid ink was 16 seconds (25 ° C.) with Zahn Cup # 4 (manufactured by Rigosha).
合成例2で作製したコポリマーを有するコアシェル型アクリルエマルジョン(A1)を固形分換算で20部、酸化チタン(テイカ社製 製品名:JR-800)40部、サーフィノール420を1部、ポリエチレンワックス5部、ノルマルプロパノール3部、消泡剤0.1部、アンモニア水0.6部、水31.3部の計100部を撹拌混合した後、ビーズミルで練肉し白色の水性リキッドインキを作製した。得られた水性リキッドインキの粘度がザーンカップ#4(離合社製)で16秒(25℃)である事を確認した。 (Example 25: Production of water-based liquid ink]
20 parts of core-shell type acrylic emulsion (A1) having the copolymer prepared in Synthesis Example 2, 40 parts of titanium oxide (product name: JR-800 manufactured by TAYCA Corporation), 1 part of Surfinol 420, polyethylene wax 5 A total of 100 parts, 3 parts of normal propanol, 0.1 part of defoaming agent, 0.6 part of ammonia water, and 31.3 parts of water, were stirred and mixed, and then kneaded with a bead mill to prepare a white aqueous liquid ink. .. It was confirmed that the viscosity of the obtained aqueous liquid ink was 16 seconds (25 ° C.) with Zahn Cup # 4 (manufactured by Rigosha).
(実施例26~33:水性リキッドインキの製造)
表4の通りの配合で、水性リキッドインキを得た。 (Examples 26 to 33: Production of water-based liquid ink)
Aqueous liquid ink was obtained by the formulation shown in Table 4.
表4の通りの配合で、水性リキッドインキを得た。 (Examples 26 to 33: Production of water-based liquid ink)
Aqueous liquid ink was obtained by the formulation shown in Table 4.
表中の略語は次の通りである。
・コポリマー(A1):合成例2で作成したコポリマーを有するコアシェル型アクリルエマルジョン(A1)
・コポリマー(A2):合成例3で作成したコポリマーを有するコアシェル型アクリルエマルジョン(A2)
・コポリマー(A3):合成例5で作成したコポリマーを有するコアシェル型スチレンアクリルエマルジョン(A3)
・コポリマー(B):合成例6で作成したコポリマー(B)
・コポリマーを有するコアシェル型アクリルエマルジョン(C):エマポリーDG-197(ガラス転移温度マイナス30℃、酸価38mgKOH/g、(株)岐阜セラック製造所製)
・アセチレン系界面活性剤:サーフィノール420(アルキレンオキサイド変性アセチレングリコール系界面活性剤 Cas番号:9014-85-1 日信化学工業(株)社製)
・アルコールアルコキシレート系界面活性剤:DYNWET800アルコールアルコキシレート系界面活性剤 ビックケミー・ジャパン社製)
・水
・ノルマルプロパノール
・ポリエチレンワックス
・消泡剤
・アンモニア水
・エポキシ硬化剤:デナコールEX-612(ソルビトールポリグリシジルエーテル ナガセケムテックス(株)社製)
・ポリウレタン(Pu):合成例7で作成したポリウレタン樹脂(Pu)
・アクリルウレタン(Au):合成例8で作成したアクリルウレタン樹脂(Au)
・顔料分散樹脂:スチレン・マレイン酸系顔料分散樹脂
・酸化チタン(IV):JR-800(テイカ社製)
・藍顔料:FASTPGEN BLUE LA5380(DIC社製)
The abbreviations in the table are as follows.
-Copolymer (A1): A core-shell acrylic emulsion (A1) having the copolymer prepared in Synthesis Example 2.
-Copolymer (A2): A core-shell acrylic emulsion (A2) having the copolymer prepared in Synthesis Example 3.
-Copolymer (A3): Core-shell type styrene acrylic emulsion (A3) having the copolymer prepared in Synthesis Example 5.
-Copolymer (B): The copolymer (B) prepared in Synthesis Example 6
-Core-shell acrylic emulsion (C) with copolymer: Emmapoly DG-197 (glass transition temperature -30 ° C, acid value 38 mgKOH / g, manufactured by Gifu Shellac Manufacturing Co., Ltd.)
-Acetylene-based surfactant: Surfinol 420 (alkylene oxide-modified acetylene glycol-based surfactant Cas No .: 9014-85-1 manufactured by Nisshin Chemical Industry Co., Ltd.)
-Alcohol alkoxylate-based surfactant: DYNWET800 Alcohol alkoxylate-based surfactant manufactured by Big Chemie Japan Co., Ltd.)
・ Water ・ Normal propanol ・ Polyethylene wax ・ Defoamer ・ Ammonia water ・ Epoxy curing agent: Denacol EX-612 (sorbitol polyglycidyl ether Nagase ChemteX Co., Ltd.)
-Polyurethane (Pu): Polyurethane resin (Pu) prepared in Synthesis Example 7.
-Acrylic urethane (Au): Acrylic urethane resin (Au) prepared in Synthesis Example 8
-Pigment dispersion resin: Styrene-maleic acid-based pigment dispersion resin-Titanium oxide (IV): JR-800 (manufactured by TAYCA)
-Indigo pigment: FASTPGEN BLUE LA5380 (manufactured by DIC Corporation)
・コポリマー(A1):合成例2で作成したコポリマーを有するコアシェル型アクリルエマルジョン(A1)
・コポリマー(A2):合成例3で作成したコポリマーを有するコアシェル型アクリルエマルジョン(A2)
・コポリマー(A3):合成例5で作成したコポリマーを有するコアシェル型スチレンアクリルエマルジョン(A3)
・コポリマー(B):合成例6で作成したコポリマー(B)
・コポリマーを有するコアシェル型アクリルエマルジョン(C):エマポリーDG-197(ガラス転移温度マイナス30℃、酸価38mgKOH/g、(株)岐阜セラック製造所製)
・アセチレン系界面活性剤:サーフィノール420(アルキレンオキサイド変性アセチレングリコール系界面活性剤 Cas番号:9014-85-1 日信化学工業(株)社製)
・アルコールアルコキシレート系界面活性剤:DYNWET800アルコールアルコキシレート系界面活性剤 ビックケミー・ジャパン社製)
・水
・ノルマルプロパノール
・ポリエチレンワックス
・消泡剤
・アンモニア水
・エポキシ硬化剤:デナコールEX-612(ソルビトールポリグリシジルエーテル ナガセケムテックス(株)社製)
・ポリウレタン(Pu):合成例7で作成したポリウレタン樹脂(Pu)
・アクリルウレタン(Au):合成例8で作成したアクリルウレタン樹脂(Au)
・顔料分散樹脂:スチレン・マレイン酸系顔料分散樹脂
・酸化チタン(IV):JR-800(テイカ社製)
・藍顔料:FASTPGEN BLUE LA5380(DIC社製)
The abbreviations in the table are as follows.
-Copolymer (A1): A core-shell acrylic emulsion (A1) having the copolymer prepared in Synthesis Example 2.
-Copolymer (A2): A core-shell acrylic emulsion (A2) having the copolymer prepared in Synthesis Example 3.
-Copolymer (A3): Core-shell type styrene acrylic emulsion (A3) having the copolymer prepared in Synthesis Example 5.
-Copolymer (B): The copolymer (B) prepared in Synthesis Example 6
-Core-shell acrylic emulsion (C) with copolymer: Emmapoly DG-197 (glass transition temperature -30 ° C, acid value 38 mgKOH / g, manufactured by Gifu Shellac Manufacturing Co., Ltd.)
-Acetylene-based surfactant: Surfinol 420 (alkylene oxide-modified acetylene glycol-based surfactant Cas No .: 9014-85-1 manufactured by Nisshin Chemical Industry Co., Ltd.)
-Alcohol alkoxylate-based surfactant: DYNWET800 Alcohol alkoxylate-based surfactant manufactured by Big Chemie Japan Co., Ltd.)
・ Water ・ Normal propanol ・ Polyethylene wax ・ Defoamer ・ Ammonia water ・ Epoxy curing agent: Denacol EX-612 (sorbitol polyglycidyl ether Nagase ChemteX Co., Ltd.)
-Polyurethane (Pu): Polyurethane resin (Pu) prepared in Synthesis Example 7.
-Acrylic urethane (Au): Acrylic urethane resin (Au) prepared in Synthesis Example 8
-Pigment dispersion resin: Styrene-maleic acid-based pigment dispersion resin-Titanium oxide (IV): JR-800 (manufactured by TAYCA)
-Indigo pigment: FASTPGEN BLUE LA5380 (manufactured by DIC Corporation)
表1~7に各インキ、ニスの実施例を示す。なお表中空欄は未配合であることを示す。
Tables 1 to 7 show examples of each ink and varnish. The hollow column in the table indicates that the mixture is not blended.
表7に記載の参考例1,2の藍インキは、詳細の説明に記載の汎用印刷層に使用される印刷インキB等を示すものである。
The indigo inks of Reference Examples 1 and 2 shown in Table 7 indicate the printing ink B and the like used for the general-purpose printing layer described in the detailed description.
<印刷インキ積層体の作製>
[実施例]
コロナ処理ポリプロピレン二軸延伸フィルム(東洋紡績(株)製 パイレンP2161 厚さ20μm)に、縦240mm×横80mmのベタ絵柄を、Flexoproof100テスト印刷機(Testing Machines,Inc.社製、アニロックス200線/inch)を用い、アニロックスロールおよび樹脂版により、実施例または比較例で得たOPニス又は水性リキッドインキを、各々印刷速度100m/分で印刷し、得られた印刷物を40℃にて20時間エージングを行い、印刷インキ積層体を得た。
OPニス又は水性リキッドインキの印刷順序は、表8~47に従い、第一印刷層→第二印刷層→第三印刷層→第四印刷層の順となるようにした。 <Preparation of printing ink laminate>
[Example]
A solid pattern of 240 mm in length x 80 mm in width is printed on a corona-treated polypropylene biaxially stretched film (Piperen P2161 manufactured by Toyobo Co., Ltd., 20 μm in thickness) with a Flexoprof100 test printing machine (Testing Machines, Inc., Anilox 200 line / inch). ) Was used to print the OP varnish or water-based liquid ink obtained in Examples or Comparative Examples with an Anilox roll and a resin plate at a printing speed of 100 m / min, and the obtained printed matter was aged at 40 ° C. for 20 hours. This was carried out to obtain a printing ink laminate.
The printing order of the OP varnish or the water-based liquid ink was set to be in the order of the first printing layer → the second printing layer → the third printing layer → the fourth printing layer according to Tables 8 to 47.
[実施例]
コロナ処理ポリプロピレン二軸延伸フィルム(東洋紡績(株)製 パイレンP2161 厚さ20μm)に、縦240mm×横80mmのベタ絵柄を、Flexoproof100テスト印刷機(Testing Machines,Inc.社製、アニロックス200線/inch)を用い、アニロックスロールおよび樹脂版により、実施例または比較例で得たOPニス又は水性リキッドインキを、各々印刷速度100m/分で印刷し、得られた印刷物を40℃にて20時間エージングを行い、印刷インキ積層体を得た。
OPニス又は水性リキッドインキの印刷順序は、表8~47に従い、第一印刷層→第二印刷層→第三印刷層→第四印刷層の順となるようにした。 <Preparation of printing ink laminate>
[Example]
A solid pattern of 240 mm in length x 80 mm in width is printed on a corona-treated polypropylene biaxially stretched film (Piperen P2161 manufactured by Toyobo Co., Ltd., 20 μm in thickness) with a Flexoprof100 test printing machine (Testing Machines, Inc., Anilox 200 line / inch). ) Was used to print the OP varnish or water-based liquid ink obtained in Examples or Comparative Examples with an Anilox roll and a resin plate at a printing speed of 100 m / min, and the obtained printed matter was aged at 40 ° C. for 20 hours. This was carried out to obtain a printing ink laminate.
The printing order of the OP varnish or the water-based liquid ink was set to be in the order of the first printing layer → the second printing layer → the third printing layer → the fourth printing layer according to Tables 8 to 47.
作製した2層構造の印刷インキ積層体(P1)、3層構造の印刷インキ積層体(P2)を用い、基材密着性、耐摩擦性、耐水摩擦性、耐スクラッチ性の評価を行い、また作成した本発明のアクリル樹脂系のインキ、ニスについて粘度安定性についても評価を行った。
Using the produced two-layer structure printing ink laminate (P1) and three-layer structure printing ink laminate (P2), the substrate adhesion, abrasion resistance, water friction resistance, and scratch resistance were evaluated, and also. The viscosity stability of the prepared acrylic resin-based ink and varnish of the present invention was also evaluated.
<基材密着性>
得られた印刷インキ積層体に対し、インキ塗工面にセロファンテープ(ニチバン製)を貼ったのち、強く引き剥がしてインキの剥離度合いを目視判定した。
尚、実用レベルは○△以上である。
◎ :インキが全く剥離しなかったもの
○ :インキがフィルムから僅かに剥離するもの(20%未満)
○△:インキがフィルムから剥離するもの(20%以上、40%未満)
△ :インキがフィルムから剥離するもの(40%以上、60%未満)
× :インキがフィルムから著しく剥離するもの(60%以上)
<Adhesion to base material>
A cellophane tape (manufactured by Nichiban Co., Ltd.) was attached to the ink-coated surface of the obtained printing ink laminate, and then the ink was strongly peeled off to visually determine the degree of ink peeling.
The practical level is ○ △ or higher.
◎: Ink did not peel off at all ○: Ink slightly peeled off from the film (less than 20%)
○ △: Ink peels off from the film (20% or more, less than 40%)
Δ: Ink peels off from the film (40% or more, less than 60%)
X: Ink peels significantly from the film (60% or more)
得られた印刷インキ積層体に対し、インキ塗工面にセロファンテープ(ニチバン製)を貼ったのち、強く引き剥がしてインキの剥離度合いを目視判定した。
尚、実用レベルは○△以上である。
◎ :インキが全く剥離しなかったもの
○ :インキがフィルムから僅かに剥離するもの(20%未満)
○△:インキがフィルムから剥離するもの(20%以上、40%未満)
△ :インキがフィルムから剥離するもの(40%以上、60%未満)
× :インキがフィルムから著しく剥離するもの(60%以上)
<Adhesion to base material>
A cellophane tape (manufactured by Nichiban Co., Ltd.) was attached to the ink-coated surface of the obtained printing ink laminate, and then the ink was strongly peeled off to visually determine the degree of ink peeling.
The practical level is ○ △ or higher.
◎: Ink did not peel off at all ○: Ink slightly peeled off from the film (less than 20%)
○ △: Ink peels off from the film (20% or more, less than 40%)
Δ: Ink peels off from the film (40% or more, less than 60%)
X: Ink peels significantly from the film (60% or more)
<耐摩耗性>
得られた印刷インキ積層体を、学振型耐摩擦性試験機を用いて、上質紙にて摩擦し、インキ層の剥離度合いを目視判定した。(荷重 500gにて往復500回)
尚、実用レベルは△以上である。
◎: インキが全く剥離しなかったもの
○: インキがフィルムから僅かに剥離するもの(15%未満)
○△:インキがフィルムから剥離するもの(15%以上、30%未満)
△: インキがフィルムから剥離するもの(30%以上、50%未満)
×: インキがフィルムから著しく剥離するもの(50%以上)
<Abrasion resistance>
The obtained printed ink laminate was rubbed with high-quality paper using a Gakushin-type friction resistance tester, and the degree of peeling of the ink layer was visually determined. (500 round trips with a load of 500 g)
The practical level is Δ or higher.
⊚: Ink did not peel off at all ○: Ink slightly peeled off from the film (less than 15%)
○ △: Ink peels off from the film (15% or more, less than 30%)
Δ: Ink peels off from the film (30% or more, less than 50%)
X: Ink peels significantly from the film (50% or more)
得られた印刷インキ積層体を、学振型耐摩擦性試験機を用いて、上質紙にて摩擦し、インキ層の剥離度合いを目視判定した。(荷重 500gにて往復500回)
尚、実用レベルは△以上である。
◎: インキが全く剥離しなかったもの
○: インキがフィルムから僅かに剥離するもの(15%未満)
○△:インキがフィルムから剥離するもの(15%以上、30%未満)
△: インキがフィルムから剥離するもの(30%以上、50%未満)
×: インキがフィルムから著しく剥離するもの(50%以上)
<Abrasion resistance>
The obtained printed ink laminate was rubbed with high-quality paper using a Gakushin-type friction resistance tester, and the degree of peeling of the ink layer was visually determined. (500 round trips with a load of 500 g)
The practical level is Δ or higher.
⊚: Ink did not peel off at all ○: Ink slightly peeled off from the film (less than 15%)
○ △: Ink peels off from the film (15% or more, less than 30%)
Δ: Ink peels off from the film (30% or more, less than 50%)
X: Ink peels significantly from the film (50% or more)
<耐水摩擦性>
得られた印刷インキ積層体を、学振型耐摩擦性試験機を用いて、含水黒綿布にて摩擦し、インキ層の剥離度合いを目視判定した。(荷重 200gにて往復500回)
尚、実用レベルは△以上である。
◎: インキが全く剥離しなかったもの
○: インキがフィルムから僅かに剥離するもの(15%未満)
○△:インキがフィルムから剥離するもの(15%以上、30%未満)
△: インキがフィルムから剥離するもの(30%以上、50%未満)
×: インキがフィルムから著しく剥離するもの(50%以上)
<Water friction resistance>
The obtained printed ink laminate was rubbed with a water-containing black cotton cloth using a Gakushin type friction resistance tester, and the degree of peeling of the ink layer was visually determined. (500 round trips with a load of 200 g)
The practical level is Δ or higher.
⊚: Ink did not peel off at all ○: Ink slightly peeled off from the film (less than 15%)
○ △: Ink peels off from the film (15% or more, less than 30%)
Δ: Ink peels off from the film (30% or more, less than 50%)
X: Ink peels significantly from the film (50% or more)
得られた印刷インキ積層体を、学振型耐摩擦性試験機を用いて、含水黒綿布にて摩擦し、インキ層の剥離度合いを目視判定した。(荷重 200gにて往復500回)
尚、実用レベルは△以上である。
◎: インキが全く剥離しなかったもの
○: インキがフィルムから僅かに剥離するもの(15%未満)
○△:インキがフィルムから剥離するもの(15%以上、30%未満)
△: インキがフィルムから剥離するもの(30%以上、50%未満)
×: インキがフィルムから著しく剥離するもの(50%以上)
<Water friction resistance>
The obtained printed ink laminate was rubbed with a water-containing black cotton cloth using a Gakushin type friction resistance tester, and the degree of peeling of the ink layer was visually determined. (500 round trips with a load of 200 g)
The practical level is Δ or higher.
⊚: Ink did not peel off at all ○: Ink slightly peeled off from the film (less than 15%)
○ △: Ink peels off from the film (15% or more, less than 30%)
Δ: Ink peels off from the film (30% or more, less than 50%)
X: Ink peels significantly from the film (50% or more)
<耐スクラッチ性>
得られた印刷インキ積層体に対し、爪でインキ塗工面を引掻き、塗膜の傷つき程度から耐スクラッチ性を目視評価した。
尚、実用レベルは○△以上である。
◎ :傷が生じなかったもの
○ :僅かに傷を生ずるもの
○△:○と△の中位の傷を生ずるもの
△: 傷を生ずるもの
×: 著しく傷を生ずるもの(爪を縦にしても剥がれるもの)
<Scratch resistance>
The ink-coated surface of the obtained printed ink laminate was scratched with a nail, and the scratch resistance was visually evaluated from the degree of damage to the coating film.
The practical level is ○ △ or higher.
◎: No scratches ○: Slight scratches ○ △: Medium scratches of ○ and △ △: Scratches ×: Significant scratches (even if the nail is vertical) Things that come off)
得られた印刷インキ積層体に対し、爪でインキ塗工面を引掻き、塗膜の傷つき程度から耐スクラッチ性を目視評価した。
尚、実用レベルは○△以上である。
◎ :傷が生じなかったもの
○ :僅かに傷を生ずるもの
○△:○と△の中位の傷を生ずるもの
△: 傷を生ずるもの
×: 著しく傷を生ずるもの(爪を縦にしても剥がれるもの)
<Scratch resistance>
The ink-coated surface of the obtained printed ink laminate was scratched with a nail, and the scratch resistance was visually evaluated from the degree of damage to the coating film.
The practical level is ○ △ or higher.
◎: No scratches ○: Slight scratches ○ △: Medium scratches of ○ and △ △: Scratches ×: Significant scratches (even if the nail is vertical) Things that come off)
<粘度安定性>
作成した本発明のアクリル樹脂系のインキ・ニスに関して、25℃にて標準を15秒とした場合の6時間後の粘度をザーンカップ#4(離合社製)を用いて評価した。
◎ :インキが全く増粘しなかったもの(+1秒未満)
○ :インキが僅かに増粘したもの(+3秒未満)
○△:インキが僅かに増粘したもの(+5秒未満)
△ :インキが増粘したもの(+10秒未満)
× :インキが著しく増粘したもの(+10秒以上)
<Viscosity stability>
With respect to the prepared acrylic resin-based ink / varnish of the present invention, the viscosity after 6 hours at 25 ° C. for 15 seconds was evaluated using Zahn Cup # 4 (manufactured by Rigosha).
◎: Ink did not thicken at all (less than +1 second)
◯: Ink slightly thickened (less than +3 seconds)
○ △: Ink slightly thickened (less than +5 seconds)
Δ: Ink thickened (less than +10 seconds)
X: Ink is significantly thickened (+10 seconds or more)
作成した本発明のアクリル樹脂系のインキ・ニスに関して、25℃にて標準を15秒とした場合の6時間後の粘度をザーンカップ#4(離合社製)を用いて評価した。
◎ :インキが全く増粘しなかったもの(+1秒未満)
○ :インキが僅かに増粘したもの(+3秒未満)
○△:インキが僅かに増粘したもの(+5秒未満)
△ :インキが増粘したもの(+10秒未満)
× :インキが著しく増粘したもの(+10秒以上)
<Viscosity stability>
With respect to the prepared acrylic resin-based ink / varnish of the present invention, the viscosity after 6 hours at 25 ° C. for 15 seconds was evaluated using Zahn Cup # 4 (manufactured by Rigosha).
◎: Ink did not thicken at all (less than +1 second)
◯: Ink slightly thickened (less than +3 seconds)
○ △: Ink slightly thickened (less than +5 seconds)
Δ: Ink thickened (less than +10 seconds)
X: Ink is significantly thickened (+10 seconds or more)
得られた印刷インキ積層体の構成と、評価結果を表8~47に示す。なお表中「第一印刷層、第ニ印刷層、第三印刷層、第四印刷層」における空欄は、印刷層がないことを示す。例えば表8の積層体実施例1は、コロナ処理ポリプロピレン二軸延伸フィルム上に、第一印刷層として藍インキPU-藍を印刷し、次に第二印刷層としてOPニスA1-OP1を印刷した積層体である。また例えば表8の積層体実施例8は、コロナ処理ポリプロピレン二軸延伸フィルム上に、第一印刷層として藍インキPU-藍を印刷し、次に第二印刷層として白インキA1-白1を印刷し、次に第三印刷層としてOPニスA1-OP1を印刷した積層体である。
Tables 8 to 47 show the composition of the obtained printing ink laminate and the evaluation results. In the table, blanks in "first print layer, second print layer, third print layer, fourth print layer" indicate that there is no print layer. For example, in Example 1 of the laminate shown in Table 8, indigo ink PU-indigo was printed as the first printing layer and then OP varnish A1-OP1 was printed as the second printing layer on the corona-treated polypropylene biaxially stretched film. It is a laminated body. Further, for example, in Example 8 of the laminate shown in Table 8, indigo ink PU-indigo is printed as the first printing layer on the corona-treated polypropylene biaxially stretched film, and then white ink A1-white 1 is printed as the second printing layer. It is a laminate obtained by printing and then printing OP varnish A1-OP1 as a third printing layer.
この結果、次の知見が得られる。
・バインダーとしてコポリマー(A3)を使用すると、耐摩擦性に優れる。これは本発明のOPニスまたは本発明の水性インキが最表層にくる場合に顕著に表れる。
・本発明のOPニスまたは本発明の水性インキの印刷層の効果は、印刷層を複数層有する積層体の場合に特に顕著であり、基材との密着性が弱い汎用インキAU-藍を使用した場合であっても、基材密着性に特に優れる。
・本発明のOPニスまたは本発明の水性インキとして、架橋剤を併用すると、基材密着性、摩擦性、スクラッチ性に特に優れる。
・本発明の顔料が入った白インキは、架橋剤を有していても有さなくても、密着性、摩擦性、スクラッチ性に優れる。 As a result, the following findings can be obtained.
-When a copolymer (A3) is used as a binder, it has excellent abrasion resistance. This is noticeable when the OP varnish of the present invention or the water-based ink of the present invention comes to the outermost layer.
-The effect of the printing layer of the OP varnish of the present invention or the water-based ink of the present invention is particularly remarkable in the case of a laminate having a plurality of printing layers, and the general-purpose ink AU-indigo, which has weak adhesion to the substrate, is used. Even in this case, the adhesion to the base material is particularly excellent.
-When a cross-linking agent is used in combination with the OP varnish of the present invention or the water-based ink of the present invention, the substrate adhesion, frictional property, and scratch property are particularly excellent.
-The white ink containing the pigment of the present invention is excellent in adhesion, friction, and scratch property regardless of whether or not it has a cross-linking agent.
・バインダーとしてコポリマー(A3)を使用すると、耐摩擦性に優れる。これは本発明のOPニスまたは本発明の水性インキが最表層にくる場合に顕著に表れる。
・本発明のOPニスまたは本発明の水性インキの印刷層の効果は、印刷層を複数層有する積層体の場合に特に顕著であり、基材との密着性が弱い汎用インキAU-藍を使用した場合であっても、基材密着性に特に優れる。
・本発明のOPニスまたは本発明の水性インキとして、架橋剤を併用すると、基材密着性、摩擦性、スクラッチ性に特に優れる。
・本発明の顔料が入った白インキは、架橋剤を有していても有さなくても、密着性、摩擦性、スクラッチ性に優れる。 As a result, the following findings can be obtained.
-When a copolymer (A3) is used as a binder, it has excellent abrasion resistance. This is noticeable when the OP varnish of the present invention or the water-based ink of the present invention comes to the outermost layer.
-The effect of the printing layer of the OP varnish of the present invention or the water-based ink of the present invention is particularly remarkable in the case of a laminate having a plurality of printing layers, and the general-purpose ink AU-indigo, which has weak adhesion to the substrate, is used. Even in this case, the adhesion to the base material is particularly excellent.
-When a cross-linking agent is used in combination with the OP varnish of the present invention or the water-based ink of the present invention, the substrate adhesion, frictional property, and scratch property are particularly excellent.
-The white ink containing the pigment of the present invention is excellent in adhesion, friction, and scratch property regardless of whether or not it has a cross-linking agent.
以上の結果から、本発明の水性リキッドインキは、粘度安定性に優れ、硬化塗膜の基材密着性、各種塗膜強度をも兼備する積層体を提供することが出来る。
更に、硬化剤を添加した系でも同様に、粘度安定性に遜色なく、硬化塗膜の基材密着性、各種塗膜強度を更に強靭とする積層体を提供することができる。 From the above results, the water-based liquid ink of the present invention can provide a laminate having excellent viscosity stability, substrate adhesion of a cured coating film, and various coating film strengths.
Further, even in a system to which a curing agent is added, it is possible to provide a laminate having a viscosity stability comparable to that of the cured coating film, which further enhances the adhesion of the cured coating film to the substrate and the strength of various coating films.
更に、硬化剤を添加した系でも同様に、粘度安定性に遜色なく、硬化塗膜の基材密着性、各種塗膜強度を更に強靭とする積層体を提供することができる。 From the above results, the water-based liquid ink of the present invention can provide a laminate having excellent viscosity stability, substrate adhesion of a cured coating film, and various coating film strengths.
Further, even in a system to which a curing agent is added, it is possible to provide a laminate having a viscosity stability comparable to that of the cured coating film, which further enhances the adhesion of the cured coating film to the substrate and the strength of various coating films.
本発明のリキッド印刷インキ積層体は、各種グラビア、フレキソ印刷物として、食品包材・サニタリー・コスメ・電子部品等工業製品向け用途に幅広く展開され得る。
The liquid printing ink laminate of the present invention can be widely used as various gravure and flexographic printed matter for industrial products such as food packaging materials, sanitary products, cosmetics, and electronic parts.
Claims (6)
- 1種又は2種以上の(メタ)アクリレート系モノマー及び/又は1種又は2種以上のビニル系モノマーから形成され、ガラス転移温度が0℃~55℃である酸価を有するコポリマーと、
アセチレン系界面活性剤及び/又はアルコールアルコキシレート系界面活性剤をインキ全量に対し0.1~1質量%と、ワックスをインキ全量に対し0.5~5質量%を含有することを特徴とする水性リキッドインキ。 A copolymer formed from one or more (meth) acrylate-based monomers and / or one or more vinyl-based monomers and having an acid value having a glass transition temperature of 0 ° C. to 55 ° C.
The acetylene-based surfactant and / or the alcohol alkoxylate-based surfactant is contained in an amount of 0.1 to 1% by mass based on the total amount of the ink, and the wax is contained in an amount of 0.5 to 5% by mass based on the total amount of the ink. Aqueous liquid ink. - 前記酸価を有するコポリマーが、酸価を有する(メタ)アクリルコポリマー又は酸価を有するスチレン(メタ)アクリルコポリマーである請求項1に記載の水性リキッドインキ。 The water-based liquid ink according to claim 1, wherein the copolymer having an acid value is a (meth) acrylic copolymer having an acid value or a styrene (meth) acrylic copolymer having an acid value.
- 前記アセチレン系界面活性剤が、アルキレンオキサイド変性アセチレングリコール系界面活性剤である請求項1又は2に記載の水性リキッドインキ。 The aqueous liquid ink according to claim 1 or 2, wherein the acetylene-based surfactant is an alkylene oxide-modified acetylene glycol-based surfactant.
- 酸と反応しうる硬化剤を含有する請求項1~3のいずれかに記載の水性リキッドインキ。 The aqueous liquid ink according to any one of claims 1 to 3, which contains a curing agent capable of reacting with an acid.
- フレキソ印刷またはグラビア印刷に適用する請求項1~4のいずれかに記載の水性リキッドインキ。 The water-based liquid ink according to any one of claims 1 to 4, which is applied to flexographic printing or gravure printing.
- 基材上に1層または複数層の印刷層を有する積層体であって、前記印刷層の少なくとも1つが、請求項1~5のいずれかに記載の水性リキッドインキの印刷層であることを特徴とする積層体。 A laminate having one or a plurality of printing layers on a base material, wherein at least one of the printing layers is the printing layer of the water-based liquid ink according to any one of claims 1 to 5. Laminated body.
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JP2001329182A (en) * | 2000-05-22 | 2001-11-27 | Nippon Shokubai Co Ltd | Water-based quick-drying resin composition |
WO2003087239A2 (en) * | 2002-04-10 | 2003-10-23 | Sun Chemical Corporation | Viscosity stabilizing blend vehicles for preparing water based flexographic printing inks |
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JP7195494B1 (en) * | 2021-03-30 | 2022-12-23 | Dicグラフィックス株式会社 | Laminate with printed layer of water-based liquid ink |
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