WO2013047491A1 - インクジェットインク用記録媒体、インクジェット印刷物及びその製造方法 - Google Patents
インクジェットインク用記録媒体、インクジェット印刷物及びその製造方法 Download PDFInfo
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- WO2013047491A1 WO2013047491A1 PCT/JP2012/074505 JP2012074505W WO2013047491A1 WO 2013047491 A1 WO2013047491 A1 WO 2013047491A1 JP 2012074505 W JP2012074505 W JP 2012074505W WO 2013047491 A1 WO2013047491 A1 WO 2013047491A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
- B32B27/325—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polycycloolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
- B32B27/327—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polyolefins obtained by a metallocene or single-site catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
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- B41M5/0023—Digital printing methods characterised by the inks used
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- B41M5/0041—Digital printing on surfaces other than ordinary paper
- B41M5/0064—Digital printing on surfaces other than ordinary paper on plastics, horn, rubber, or other organic polymers
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/04—Monomers containing three or four carbon atoms
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
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- C08F12/02—Monomers containing only one unsaturated aliphatic radical
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- C08F18/02—Esters of monocarboxylic acids
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- C08F18/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F18/14—Esters of polycarboxylic acids
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- 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
- C09D11/30—Inkjet printing 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
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J107/00—Adhesives based on natural rubber
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
- C09J109/06—Copolymers with styrene
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- B32B2307/40—Properties of the layers or laminate having particular optical properties
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- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
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Definitions
- the present invention relates to an ink jet recording medium that enables ink jet printing even on a plastic substrate. Specifically, the adhesion between the ink jet ink and the plastic substrate is excellent, and there is no peeling of the printed surface after printing.
- the present invention relates to a recording medium for inkjet ink and a printed matter thereof.
- Inkjet printers have become widespread regardless of business use or consumer use. Inkjet printers have many features such as easy multicoloring and large image size, printing on uneven surfaces as well as smooth surfaces, and on-demand printing. is doing.
- the ink-jet recording material that uses paper as a support has a problem that the appearance is deteriorated due to occurrence of a phenomenon called cockling in which the support is waved when touched with water or tearing.
- an ink jet recording medium having a plastic film itself as a support and an ink receiving layer thereon, and to perform printing (for example, Patent Document 1). See ⁇ 4.
- Such a medium is excellent in water resistance and can be used as an outdoor advertisement, a poster, a label, wallpaper, or the like.
- the surface of the plastic film has poor adhesion to the ink-jet ink, and a layer usually called an anchor layer, primer layer, undercoat layer, adhesive layer, etc.
- An object of the present invention is to provide a recording medium for ink-jet ink that does not cause problems such as peeling after ink-jet printing, and a printed matter thereof.
- the present inventors have found that a single layer or a multilayer having a layer (A) containing the cyclic polyolefin resin (a1) and / or the acid-modified polyolefin resin (a2). It has been found that the above problems can be solved by using the film (I) as an ink jet recording medium, and the present invention has been completed.
- the present invention provides an ink jet on the layer (A) in the single layer or multilayer film (I) having the layer (A) containing the cyclic polyolefin resin (a1) and / or the acid-modified polyolefin resin (a2).
- the present invention provides a printed matter obtained by printing, a method for producing the printed matter, and an ink jet recording medium suitable for producing the printed matter.
- the ink-jet printed matter obtained by the present invention can be easily obtained by directly performing ink-jet printing on a plastic film.
- the design can be easily changed by multilayering the film according to the target performance (transparency, rigidity, workability, etc.) and application (packaging material, poster, label, etc.) and selecting the layer configuration. Excellent versatility.
- the printed matter obtained has good adhesion between the ink and the film, so that even if it is stored for a long time, the printed part does not peel off. It is also possible to have a shape or the like.
- the plastic film that functions as a support for the inkjet printed matter of the present invention has a layer (A) containing at least a cyclic polyolefin resin (a1) and / or an acid-modified polyolefin resin (a2).
- This layer (A) functions not only as a support but also as an easy adhesion layer with ink.
- “main component” means that the specific resin is contained in an amount of 80% by mass or more based on the total amount of the resin composition forming the layer, and preferably 85% by mass. The above is a specific resin.
- “containing” means that the specific resin is contained in an amount of 1% by mass or more with respect to the total amount of the resin composition forming the layer, and preferably 20% by mass or more. Say that it is a specific resin.
- Examples of the cyclic polyolefin resin (a1) include a norbornene polymer, a vinyl alicyclic hydrocarbon polymer, and a cyclic conjugated diene polymer. Among these, norbornene-based polymers are preferable.
- the norbornene-based polymer includes a ring-opening polymer of a norbornene-based monomer (hereinafter referred to as “COP”), a norbornene-based copolymer obtained by copolymerizing a norbornene-based monomer and an olefin such as ethylene (hereinafter, referred to as “COP”). , “COC”). Furthermore, COP and COC hydrogenates are particularly preferred.
- the weight average molecular weight of the cyclic olefin-based resin is preferably 5,000 to 500,000, more preferably 7,000 to 300,000.
- the norbornene polymer and the norbornene monomer used as a raw material are alicyclic monomers having a norbornene ring.
- Examples of such norbornene-based monomers include norbornene, tetracyclododecene, ethylidene norbornene, vinyl norbornene, ethylidene tetracyclododecene, dicyclopentadiene, dimethanotetrahydrofluorene, phenyl norbornene, methoxycarbonyl norbornene, methoxycarbonyl And tetracyclododecene.
- These norbornene monomers may be used alone or in combination of two or more.
- the norbornene-based copolymer is a copolymer of the norbornene-based monomer and an olefin copolymerizable with the norbornene-based monomer.
- olefin include the number of carbon atoms such as ethylene, propylene, and 1-butene.
- examples thereof include olefins having 2 to 20; cycloolefins such as cyclobutene, cyclopentene, and cyclohexene; and non-conjugated dienes such as 1,4-hexadiene. These olefins can be used alone or in combination of two or more.
- examples of the ring-opening polymer (COP) of the norbornene monomer include “ZEONOR” manufactured by Nippon Zeon Co., Ltd., and norbornene.
- examples of the system copolymer (COC) include “Appel” manufactured by Mitsui Chemicals, Inc., “TOPAS” manufactured by Polyplastics Co., Ltd., and the like.
- the content ratio of the cyclic polyolefin resin (a1) to the resin component forming the layer (A) can easily increase the surface treatment degree of the resulting single layer or multilayer film (recording medium) (I), and inkjet ink. From the viewpoint of adhesiveness, it is preferably 50% by mass or more, and particularly preferably 80% by mass or more.
- the glass transition point (Tg) of the cyclic polyolefin resin (a1) is preferably 60 ° C. or higher from the viewpoint of the rigidity of the obtained film (I).
- Tg is preferably 200 ° C. or lower.
- the temperature is particularly preferably 70 ° C to 180 ° C.
- the content ratio of the norbornene monomer is preferably in the range of 30 to 90% by mass, more preferably 40 to 90% by mass, and still more preferably. 50 to 85% by mass. If the content ratio is within this range, the rigidity and processing stability of the film are improved.
- fusing point in this invention are measured by differential scanning calorimetry (DSC).
- norbornene copolymers with a high glass transition point (Tg) have low tensile strength, are extremely easy to break, and may tear easily. In view of this balance, it is also preferable to blend a high Tg product and a low Tg product having a glass transition point of less than 100 ° C.
- a multilayer film (I) in which (B) is laminated is preferred.
- the rigidity is too high and tearing or tearing easily due to dropping during transportation, or the sealing start temperature when used as a package becomes too high, or improvement in strength maintenance (hot tackiness) immediately after heat sealing,
- COC having a Tg of less than 100 ° C.
- the falling bag strength and the packaging machine suitability can be improved. It is also effective to blend a polyolefin resin that does not contain a cyclic structure and is compatible with COC, or a rubber elastomer resin having a low melting point and a low Tg.
- the layer (A) in the present invention may be a layer containing an acid-modified polyolefin resin (a2).
- the olefin component which is the main component of the acid-modified polyolefin resin (a2) is not particularly limited, but has 2 to 6 carbon atoms such as ethylene, propylene, isobutylene, 2-butene, 1-butene, 1-pentene, 1-hexene and the like. Alkenes are preferred and mixtures of these may be used. Of these, alkenes having 2 to 4 carbon atoms such as ethylene, propylene, isobutylene and 1-butene are more preferred, ethylene and propylene are more preferred, and ethylene is most preferred.
- the acid-modified polyolefin resin (a2) needs to contain a (meth) acrylic acid ester component.
- (Meth) acrylic acid ester components include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylic acid Examples include octyl, decyl (meth) acrylate, lauryl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, and the like.
- the (meth) acrylic acid ester component may be copolymerized with the olefin component, and the form thereof is not limited. Examples of the copolymerization state include random copolymerization, block copolymerization, and graft copolymerization. (Graft modification) and the like. (Note that “(meth) acrylic acid” means “acrylic acid or methacrylic acid”).
- ethylene- (meth) acrylic acid ester copolymers include Elvalloy ( Product name: Mitsui-DuPont Polychemical Co., Ltd.), Aklift (trade name: Sumitomo Chemical Co., Ltd.), etc. These may be used alone or in combination of two or more.
- the acid-modified polyolefin resin (a2) may be acid-modified with an unsaturated carboxylic acid component.
- unsaturated carboxylic acid components include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid, and the like, as well as unsaturated dicarboxylic acid half esters and half amides. It is done. Of these, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are preferable, and acrylic acid and maleic anhydride are particularly preferable.
- the unsaturated carboxylic acid component may be copolymerized with the olefin component, and the form thereof is not limited.
- copolymerization state examples include random copolymerization, block copolymerization, and graft copolymerization (grafting). Modification).
- ethylene-acrylic acid copolymer examples include Nucrel (trade name: Mitsui, manufactured by DuPont Polychemical Co., Ltd.) and the like can be mentioned.
- ethylene- (meth) acrylic acid ester-maleic anhydride copolymer examples include bondine (trade name: manufactured by Tokyo Materials Co., Ltd.). These may be used alone or in combination of two or more.
- the acid modification rate of the acid-modified polyolefin resin (a2) includes adhesion to inkjet ink, suppression of blocking when the film (I) is wound and stored, and suppression of appearance defects such as wrinkles after printing. From the viewpoint of excellent balance, it is preferable to use 0.5 to 40%, more preferably 0.5 to 35%, and particularly preferably 0.5 to 30%.
- the layer (A) in the present invention may further contain other resins.
- the layer can be easily mixed with the acid-modified polyolefin resin (a2) and, as will be described later, a multilayer film (I) having a layer (B) mainly composed of the polyolefin resin (b).
- a polyolefin resin in combination.
- the acid-modified olefin resin (a2) is preferably contained in an amount of 20 parts by mass or more, particularly preferably 50 parts by mass or more in 100 parts by mass of the resin component forming the layer (A).
- the above-mentioned cyclic polyolefin resin (a1) and acid-modified polyolefin resin (a2) may be used in combination, and at this time, the resin component forming the layer (A) From 100 mass parts, it is preferable to contain 50 mass parts or more as a total mass of the said cyclic polyolefin resin (a1) and the said acid-modified polyolefin resin (a2) from the point which adhesiveness with an ink is more excellent.
- Examples of the polyolefin resin that can be used in combination with the cyclic polyolefin resin (a1) or the acid-modified polyolefin resin (a2) in the resin layer (A) include homopolymers or copolymers of ⁇ -olefins having 2 to 6 carbon atoms. Can be mentioned.
- the copolymerization type may be a block copolymer or a random copolymer.
- Examples of the polyolefin resin include a polyethylene resin and a polypropylene resin.
- the density is preferably 0.900 to 0.950 g / cm 3 , and more preferably the density is 0.905 to 0.945 g / cm 3 .
- polyethylene resin examples include polyethylene resins such as very low density polyethylene (VLDPE), linear low density polyethylene (LLDPE), and low density polyethylene (LDPE), and ethylene-vinyl acetate copolymer (EVA). These may be used alone or in combination of two or more. Among these, VLDPE, LDPE, LLDPE, and MLDPE are preferable because of a good balance of sealing properties, rigidity, and adhesion to ink.
- VLDPE very low density polyethylene
- LLDPE linear low density polyethylene
- LDPE low density polyethylene
- EVA ethylene-vinyl acetate copolymer
- the LDPE may be a branched low density polyethylene obtained by a high pressure radical polymerization method, and is preferably a branched low density polyethylene obtained by homopolymerizing ethylene by a high pressure radical polymerization method.
- LLDPE and MLDPE an ethylene monomer as a main component and a comonomer such as butene-1, hexene-1, octene-1, and 4-methylpentene are produced by a low-pressure radical polymerization method using a single site catalyst. -Copolymerized olefin.
- the comonomer content in LLDPE is preferably in the range of 0.5 to 20 mol%, more preferably in the range of 1 to 18 mol%.
- the single site catalyst examples include various single site catalysts such as a metallocene catalyst system such as a combination of a metallocene compound of Group IV or V transition metal of the periodic table and an organoaluminum compound and / or an ionic compound.
- the single-site catalyst has a uniform active site, so the molecular weight distribution of the resulting resin is sharper than a multi-site catalyst with a non-uniform active site. This is preferable because a resin having physical properties excellent in stability of sealing strength and anti-blocking property can be obtained.
- the density of the polyethylene resin is preferably 0.900 to 0.950 g / cm 3 . If the density is within this range, it has moderate rigidity, excellent mechanical strength such as heat seal strength and pinhole resistance, and film film formability and extrusion suitability are improved.
- the melting point is preferably in the range of 60 to 130 ° C., more preferably 70 to 125 ° C. When the melting point is within this range, the processing stability and the extrusion processability when used by mixing with the cyclic polyolefin resin (a1) and the acid-modified polyolefin resin (a2) are improved.
- the melt flow rate of the polyethylene resin hereinafter referred to as “190 ° C. MFR”; measured at 190 ° C.
- 21.18 N in accordance with JIS K7210: 1999 is 2 to 20 g / 10 min. It is preferably 3 to 10 g / 10 min. If MFR of 190 degreeC is this range, the extrusion moldability of a film will improve.
- polypropylene resin examples include propylene homopolymer, propylene / ⁇ -olefin random copolymer, such as propylene-ethylene copolymer, propylene-butene-1 copolymer, propylene-ethylene-butene-1 A copolymer, a metallocene catalyst type
- a propylene- ⁇ -olefin random copolymer is desirable, and a propylene / ⁇ -olefin random polymer polymerized using a metallocene catalyst is particularly preferable.
- the heat resistance of the film is improved and the softening temperature can be increased, so that steam such as boiling at 100 ° C. or lower, hot filling, or retort sterilization at 100 ° C. or higher is used.
- -It can also be used as a packaging material with excellent high-pressure heat sterilization characteristics.
- These polypropylene resins preferably have an MFR at 230 ° C. of 0.5 to 30.0 g / 10 min and a melting point of 110 to 165 ° C., more preferably an MFR at 230 ° C. of 2.0 The melting point is 115 to 162 ° C. at ⁇ 15.0 g / 10 min. If MFR and melting
- the cyclic polyolefin resin (a1) and / or the acid is used for improving heat sealability and further providing easy-openability.
- a multilayer film (I) obtained by further laminating a layer (B) containing a polyolefin resin (b) as a main component on the layer (A) containing a modified polyolefin resin can also be obtained.
- Examples of the polyolefin resin (b) that can be used in the layer (B) include homopolymers or copolymers of ⁇ -olefins having 2 to 6 carbon atoms.
- the copolymerization type may be a block copolymer or a random copolymer.
- the polyolefin resin (b) it is preferable to use a resin having a melting point of 110 ° C. or more from the viewpoint of maintaining the appearance during molding after recording and suppressing the warpage of the film itself.
- polystyrene resin (b) for example, any of those known as a polypropylene resin (b-1), a polyethylene resin (b-2) and the like can be used.
- a polypropylene resin (b-1) propylene homopolymer, propylene-ethylene copolymer, propylene-butene-1 copolymer, propylene-ethylene-butene-1 copolymer, ethylene-propylene block copolymer
- group polypropylene, etc. are mentioned. These may be used alone or in combination of two or more.
- crystallinity means having a peak of 0.5 J / g or more in the range of 95 to 250 ° C. in DSC (differential scanning calorimetry).
- the polypropylene resin (b-1) preferably has an MFR at 230 ° C. of 0.5 to 30.0 g / 10 min and a melting point of 120 to 165 ° C., more preferably 230 ° C.
- the MFR is 2.0-15.0 g / 10 min and the melting point is 125-162 ° C. If the MFR and the melting point are in this range, the film shrinkage is small even when the printed matter is subjected to thermoforming, etc., so that the appearance of the printed surface can be maintained and the warp of the medium itself is not generated, and the coextrusion multilayer
- the film formability when a film is formed is also improved.
- the density is preferably 0.890 to 0.910 g / cm 3 and more preferably 0.895 to 0.905 g / cm 3 .
- the surface is modified to a satin finish, and the generation of wrinkles when the multilayer film is wound into a roll can be suppressed, and the roll can be stored in a roll. Can reduce blocking.
- the propylene-ethylene block copolymer is a resin obtained by block polymerization of propylene and ethylene.
- propylene obtained by performing polymerization of ethylene or polymerization of ethylene and propylene in the presence of a propylene homopolymer. -Ethylene block copolymers and the like.
- the surface of the layer (B) can be easily modified into a satin finish. Can do.
- a mixed resin of crystalline propylene resin and ethylene / propylene rubber hereinafter referred to as “EPR”
- the surface of the layer (B) can be easily modified into a satin finish. Can do.
- the crystalline propylene-based resin used at this time a highly versatile propylene homopolymer is preferable.
- the EPR used at this time those having a weight average molecular weight in the range of 400,000 to 1,000,000 are preferable in that irregularities can be formed on the film surface and the surface can be modified into a satin finish. A range is more preferable.
- the content of EPR in the mixed resin is preferably in the range of 5 to 35% by mass from the viewpoint that the film surface can be uniformly modified into a satin finish.
- the MFR at 230 ° C. of the mixed resin of the crystalline propylene polymer and EPR is preferably in the range of 0.5 to 15 g / 10 minutes from the viewpoint of easy extrusion.
- the weight average molecular weight of the EPR was obtained by calculating a component extracted from the mixed resin by a cross fractionation method at 40 ° C. using orthodichlorobenzene as a solvent by GPC (gel permeation chromatography). It is.
- the content of EPR in the mixed resin is obtained from the amount of EPR extracted by cross-fractionation at 40 ° C. using orthodichlorobenzene as a solvent.
- the method for producing the mixed resin of the crystalline propylene-based resin and EPR is not particularly limited.
- a propylene homopolymer and ethylene / propylene rubber are separately mixed using a Ziegler type catalyst.
- a propylene homopolymer is produced in the first stage by a method of mixing both with a mixer or a two-stage polymerization method, and then the second stage. And a method of generating EPR in the presence of this polymer.
- the Ziegler-type catalyst is a so-called Ziegler-Natta catalyst, and is obtained by supporting a transition metal compound such as a titanium-containing compound or a transition metal compound on a support such as a magnesium compound.
- a transition metal compound such as a titanium-containing compound or a transition metal compound
- a support such as a magnesium compound.
- the combination with the promoter of an organometallic compound is mentioned.
- Examples of the polyethylene resin (b-2) include medium density polyethylene (MDPE) and high density polyethylene (HDPE).
- MDPE medium density polyethylene
- HDPE high density polyethylene
- the density is preferably 0.92 to 0.97 g / cm 3 .
- the 190 ° C. MFR of the polyethylene resin (b-2) is preferably 2 to 20 g / 10 minutes, more preferably 3 to 10 g / 10 minutes. When the MFR is within this range, the extrudability of the film is improved, the generation of wrinkles that are likely to occur when the multilayer film is rolled up can be suppressed, and the roll-out property from the roll is excellent.
- these polyethylene resins (b-2) preferably have a melting point of 110 to 135 ° C, more preferably a melting point of 115 to 130 ° C. When the melting point is within this range, the film shrinks little even when heated by molding after printing, etc., so that the appearance of the recording surface can be maintained, and warping of the film itself can be suppressed. These may be used alone or in combination of two or more.
- the layer (B) containing the polyolefin resin (b) as a main component may be a single layer or may have a multilayer structure of two or more layers.
- a film having a single layer or multilayer structure mainly composed of polypropylene resin (b-1) is preferable.
- the outermost layer on the surface opposite to the printed surface is 1-butene having 1-butene and propylene as essential components as described in JP-A-2006-213065.
- an adhesive layer on the layer (B) [the surface opposite to the above-mentioned layer (A)]
- an ink-jet printed matter (label) that can be attached to a signboard, a vehicle or the like can be obtained.
- the type of the adhesive is not particularly limited.
- the pressure-sensitive adhesive layer may contain, for example, a terpene resin such as ⁇ -pinene, ⁇ -pinene polymer, diterpene polymer, ⁇ -pinene / phenol copolymer, Appropriate tackifiers such as aromatic resins, aromatic resins, aliphatic / aromatic copolymer systems, other rosin resins, coumarone indene resins, (alkyl) phenol resins and xylene resins Can be blended.
- a terpene resin such as ⁇ -pinene, ⁇ -pinene polymer, diterpene polymer, ⁇ -pinene / phenol copolymer
- Appropriate tackifiers such as aromatic resins, aromatic resins, aliphatic / aromatic copolymer systems, other rosin resins, coumarone indene resins, (alkyl) phenol resins and xylene resins Can be blended.
- an anti-fogging agent for each of the layers (A) and (B), an anti-fogging agent, an antistatic agent, a thermal stabilizer, a nucleating agent, an antioxidant, a lubricant, an antiblocking agent, a release agent, and an ultraviolet absorber, if necessary.
- Components such as a colorant and a colorant can be added within a range that does not impair the object of the present invention.
- the surface friction coefficient is preferably 1.5 or less, more preferably 1.0 or less in order to impart processing suitability when forming a film or packaging suitability when a printed material is used as a packaging material. It is preferable to add a lubricant, an antiblocking agent or an antistatic agent to the layer corresponding to.
- the thickness of the film (I) of the present invention can be appropriately set according to the use of the printed matter.
- the thickness is 20 to 50 ⁇ m
- the label In the case of a poster it is preferably a multilayer film, and in that case, it is preferably in the range of 70 to 1000 ⁇ m.
- the thickness of the layer (B) is preferably in the range of 5 to 85%, particularly preferably in the range of 10 to 40%.
- the thickness of the layer (B) is 2 to 2 in the case of a packaging material (bag or lid). A range of 30 ⁇ m is preferred.
- the multilayer film (I) as a method of laminating the layer (A) and the layer (B), a coextrusion lamination molding method in which the layer (A) and the layer (B) are laminated adjacent to each other.
- the layers (A) and (B) are melted by various coextrusion methods such as a coextrusion multilayer die method and a feed block method, which are melt-extruded using two or more extruders.
- a method of processing into a long wound film by a method such as inflation or T-die / chill roll method is preferable, and a co-extrusion method using a T-die is more preferable.
- the surface of the layer (A) is continuously subjected to surface treatment using a corona discharge or a plasma discharge in an atmosphere of an inert gas during the production of the multilayer film.
- a corona discharge or a plasma discharge in an atmosphere of an inert gas during the production of the multilayer film.
- it does not specifically limit as a processing method It is desirable to surface-treat the surface of a layer (A) continuously using a corona discharge or a plasma discharge etc. under the atmosphere of heating or an inert gas.
- the method of corona treatment is not particularly limited.
- JP-B-39-12838, JP-A-47-19824, JP-A-48-28067, and JP-A-52-42114 It can be performed by the processing method described in the above.
- a solid state corona treatment machine manufactured by Pillar a LEPEL type surface treatment machine, a VETAPHON type treatment machine, or the like can be used.
- the treatment can be performed at normal pressure in air.
- the discharge frequency during the treatment is 5 kV to 40 kV, more preferably 10 kV to 30 kV, and the waveform is preferably an alternating sine wave.
- the gap transparent lance between the electrode and the dielectric roll is 0.1 mm to 10 mm, more preferably 1.0 mm to 2.0 mm.
- the discharge is processed above a dielectric support roller provided in the discharge zone, and the treatment amount is 0.34 kV ⁇ A ⁇ min / m 2 to 0.4 kV ⁇ A ⁇ min / m 2 , more preferably 0.344 kV.
- the degree of treatment in such corona treatment is the treatment of the polyolefin resin having no cyclic structure.
- the degree of treatment can be determined by, for example, measuring the surface tension with a wetting reagent, and when the cyclic polyolefin resin (a1) is used, it can be easily set to 40 dyne / cm or more. It can also be 50 dyne / cm or more.
- a high degree of corona treatment is presumed to contribute to the development of adhesion to inkjet inks and to suppress peeling of the printing surface. Is preferably increased.
- a polyester film that is known to increase the degree of corona treatment has an upper limit of about 45 dyne / cm. Further, its deterioration with time is large, and it is difficult to maintain a high degree of surface treatment over a long period of time.
- the surface of the film (I) using the cyclic polyolefin-based resin (a1) is very little deteriorated with time after corona treatment, and can be subjected to inkjet printing after being stored for several months as the film (I). .
- the printed matter obtained by the present invention is obtained by inkjet printing on the layer (A) of the film (I) obtained above.
- the inkjet ink used in the present invention is not particularly limited, and various inks can be used.
- Ink-jet inks include water-based inks using water or a mixed solvent of water and water-soluble organic solvents as the main solvent, non-aqueous (oil-based) inks using organic solvents as the main solvent, or UV curable inks that do not use these solvents.
- the film used in the present invention may be an oil-based ink having good adhesion to a plastic film, a UV curable ink, or a water-based ink that usually causes problems such as repellency. It can be used without any problem because of its excellent adhesion.
- pigments and dyes are usually used, but it is preferable to use pigments from the viewpoint of durability of printed matter.
- the dye include direct dyes, acid dyes, food dyes, basic dyes, reactive dyes, disperse dyes, vat dyes, soluble vat dyes, reactive disperse dyes, and various dyes that are usually used in inkjet recording. .
- inorganic pigments such as barium sulfate, lead sulfate, titanium oxide, yellow lead, bengara, chromium oxide, carbon black, anthraquinone pigments, perylene pigments, disazo pigments, phthalocyanine pigments, isoindoline pigments And dioxazine pigments, quinacridone pigments, perinone pigments, and benzimidazolone pigments.
- pigments such as barium sulfate, lead sulfate, titanium oxide, yellow lead, bengara, chromium oxide, carbon black, anthraquinone pigments, perylene pigments, disazo pigments, phthalocyanine pigments, isoindoline pigments And dioxazine pigments, quinacridone pigments, perinone pigments, and benzimidazolone pigments.
- black ink, cyan ink, magenta ink, and yellow ink using black pigment, cyan pigment, magenta pigment, and yellow pigment are used.
- the black pigment it is preferable to use furnace black, lamp black, acetylene black, channel black or other carbon black having excellent light resistance and high hiding power, titanium black, or the like.
- cyan pigments include C.I. I. Pigment Blue 1, C.I. I. Pigment Blue 2, C.I. I. Pigment blue 3, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 16, C.I. I. Pigment blue 22, C.I. I. Pigment blue 60, and the like.
- magenta pigments examples include C.I. I. Pigment Red 5, C.I. I. Pigment Red 7, C.I. I. Pigment Red 12, C.I. I. Pigment Red 48, C.I. I. Pigment Red 48: 1, C.I. I. Pigment Red 57, C.I. I. Pigment Red 112, C.I. I. Pigment Red 122, C.I. I. Pigment Red 123, C.I. I. Pigment Red 146, C.I. I. Pigment Red 168, C.I. I. Pigment Red 184, C.I. I. Pigment Red 202, C.I. I. Pigment Bio Red 19, etc.
- yellow pigments examples include C.I. I. Pigment Yellow 1, C.I. I. Pigment Yellow 2, C.I. I. Pigment Yellow 3, C.I. I. Pigment Yellow 12, C.I. I. Pigment Yellow 13, C.I. I. Pigment Yellow 14, C.I. I. Pigment yellow 16, C.I. I. Pigment Yellow 17, C.I. I. Pigment Yellow 73, C.I. I. Pigment Yellow 74, C.I. I. Pigment Yellow 75, C.I. I. Pigment Yellow 83, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 95, C.I. I. Pigment Yellow 97, C.I. I. Pigment Yellow 98, C.I. I.
- Pigment Yellow 109 C.I. I. Pigment Yellow 114, C.I. I. Pigment Yellow 128, C.I. I. Pigment Yellow 129, C.I. I. Pigment yellow 138, C.I. I. Pigment Yellow 151, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, and the like.
- the particle diameter of the pigment is preferably such that the primary particle diameter is in the range of 1 to 500 nm, and more preferably in the range of 20 to 200 nm. Further, the particle diameter of the pigment after being dispersed in the medium is preferably in the range of 10 to 300 nm, and more preferably in the range of 50 to 150 nm.
- the primary particle diameter of the pigment can be measured by an electron microscope, a gas or solute adsorption method, an air flow method, an X-ray small angle scattering method, and the like.
- the pigment particle diameter after dispersion can be measured by a centrifugal sedimentation method, a laser diffraction method (light scattering method), an ESA method, a capillary method, an electron microscope method, or the like.
- the water used in the water-based ink is preferably pure water or ultrapure water that has undergone a purification process such as ion exchange or distillation.
- water-soluble organic solvents include ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, and methyl isobutyl ketone; methanol, ethanol, 2-propanol, 2-methyl-1-propanol, 1-butanol, 2-methoxy Alcohols such as ethanol; ethers such as tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane; dimethylformamide, N-methylpyrrolidone, 2-pyrrolidone, LEG-1, glycerol, diethylene glycol, trimethylolpropane And / or the like can be used.
- the water-based ink is obtained by dispersing a coloring material such as the pigment in the water or a mixed solvent of water and a water-soluble organic solvent.
- the pigment is dispersed using a dispersing resin.
- the stirring / dispersing device for dispersing the pigment include various types such as an ultrasonic homogenizer, a high-pressure homogenizer, a paint shaker, a ball mill, a bead mill, a roll mill, a sand mill, a sand grinder, a dyno mill, a dispar mat, an SC mill, and a nanomizer.
- a disperser can be used.
- a binder resin can also be used for the purpose of film formation and film adhesion.
- the dispersing resin and binder resin may be the same or several types may be used in combination. In general, water-soluble or water-dispersible urethane resins, acrylic resins, polyester resins and the like are used. If necessary, it is prepared by adding a drying inhibitor, a penetrant, a surfactant or other additives. It can also be prepared by preparing a high-concentration pigment dispersion (mill base) in advance and then appropriately diluting and adding additives.
- the aqueous ink preferably contains a resin having a polar group.
- Resins having polar groups used in the present invention include, for example, proteins such as glue, gelatin, casein and albumin; natural rubbers such as gum arabic and tragacanth; glucosides such as saponin; alginic acid and propylene glycol alginate ester, alginic acid Alginate derivatives such as triethanolamine and ammonium alginate; natural polymers such as cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, and ethylhydroxyethylcellulose; polyvinyl alcohols; polyvinylpyrrolidones; polyacrylic acid and acrylic acid-acrylonitrile Polymer, potassium acrylate-acrylonitrile copolymer, vinyl acetate-acrylic ester copolymer, acrylic acid-acrylic Acrylic resin such as alkyl ester copolymer; styrene-acrylic acid copolymer
- a polymer compound having a carboxyl group (preferably in the form of a salt) (for example, the styrene-acrylic acid resin, styrene-maleic acid, styrene-maleic anhydride, vinylnaphthalene-acrylic acid copolymer) Polymer, vinyl naphthalene-maleic acid copolymer, vinyl acetate acrylic acid copolymer), copolymer of monomer having hydrophobic group and monomer having hydrophilic group, and hydrophobic group and hydrophilic group Polymers consisting of monomers with a combination of alkali metal, diethylamine, ammonia, ethylamine, triethylamine, propylamine, isopropylamine, dipropylamine, butylamine, isobutylamine, triethanolamine, diethanolamine, aminomethylpropanol Morpholine Salt and is preferable.
- These copolymers preferably have a weight average molecular weight of
- aqueous dispersions in which the polymer is dispersed in water in the form of fine particles.
- aqueous dispersions can be obtained by appropriately neutralizing a synthetic polymer containing the acid monomer such as acrylic acid or methacrylic acid.
- the content of the acid monomer is preferably 1% by weight to 15% by weight of the total monomer, and can provide an ink-jet ink that is relatively stable for a relatively long period of time and resistant to aggregation.
- fine particles having a crosslinked structure can be obtained by using 0.1% by mass to 3% by mass of the total monomer as a bifunctional or higher functional crosslinkable monomer. Since the crosslinkable monomer may cause gelation if used in a large amount, it is preferable to use it so that it does not exceed 3% by weight.
- aqueous dispersion examples include, for example, synthetic polymers using styrene, (meth) acrylate having 1 to 8 carbon atoms, ethylene glycol di (meth) acrylate, (meth) acrylic acid, and the like as appropriate.
- An aqueous dispersion obtained by neutralization is mentioned.
- the molecular weight of the resin having a polar group is preferably in the range of 10,000 to 2,000,000, more preferably in the range of 20,000 to 250,000, in terms of weight average molecular weight.
- the glass transition temperature is preferably in the range of ⁇ 20 ° C. to + 30 ° C.
- the particle diameter of the fine particles is in the range of 20 nm to 500 nm, more preferably in the range of 100 nm to 300 nm, and an ink having no problem in ejection properties can be obtained.
- the particle diameter can be measured by a centrifugal sedimentation method, a laser diffraction method (light scattering method), an ESA method, a capillary method, an electron microscope method, or the like.
- a centrifugal sedimentation method a laser diffraction method (light scattering method), an ESA method, a capillary method, an electron microscope method, or the like.
- Preferable is measurement by Microtrac UPA using a dynamic light scattering method.
- a surfactant or low surface tension organic solvent can be added to the water-based ink.
- the surfactant is not particularly limited, and examples include various anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. Among these, anionic surfactants are included. Agents and nonionic surfactants are preferred.
- anionic surfactant examples include alkylbenzene sulfonate, alkylphenyl sulfonate, alkylnaphthalene sulfonate, higher fatty acid salt, sulfate of higher fatty acid ester, sulfonate of higher fatty acid ester, higher alcohol ether. Sulfate salts and sulfonates of the above, higher alkyl sulfosuccinates, polyoxyethylene alkyl ether carboxylates, polyoxyethylene alkyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, etc.
- dodecylbenzene sulfonate isopropyl naphthalene sulfonate, monobutylphenylphenol monosulfonate, monobutylbiphenyl sulfonate, dibutylphenylphenol disulfate.
- phosphate salt can be mentioned.
- Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester , Polyoxyethylene glycerin fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, fatty acid alkylolamide, alkyl alkanolamide, acetylene glycol, oxyethylene adduct of acetylene glycol, Polyethylene glycol polypropylene glycol block copolymer, alkylphenol et Sylates, etc.
- polyoxyethylene nonyl phenyl ether polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid Esters, polyoxyethylene sorbitan fatty acid esters, fatty acid alkylol amides, acetylene glycol, oxyethylene adducts of acetylene glycol, polyethylene glycol polypropylene glycol block copolymers, and alkylphenol ethoxylates are preferred.
- surfactants include silicone surfactants such as polysiloxane oxyethylene adducts; fluorine surfactants such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and oxyethylene perfluoroalkyl ethers.
- Biosurfactants such as spicrispolic acid, rhamnolipid, lysolecithin and the like can also be used.
- the HLB is preferably in the range of 7-20.
- fluorosurfactants include Novec FC-4430, FC-4432 (manufactured by Sumitomo 3M), Zonyl FSO-100, FSN-100, FS-300, FSO (manufactured by DuPont), F-Top EF- 122A, EF-351, 352801, 802 (manufactured by Gemco), Megafac F-470, F-1405, F474, F-444 (manufactured by DIC), Surflon S-111, S-112, S-113, S121, S131 , S132, S-141, S-145 (manufactured by Asahi Glass), footage series (manufactured by Neos), Fluorad FC series (manufactured by Minnesota Mining and Manufacturing Company), Monflor (Imperial) (Chemical Industry) Rikobetto (Licowet) VPF series (manufactured by Farubeberuke Hoechst), and the like.
- silicon-based surfactants examples include KF-351A, KF-642, Olphine PD-501, Olphine PD-502, Olphine PD-570 (manufactured by Shin-Etsu Chemical Co., Ltd.), BYK347, BYK348 (manufactured by BYK Japan).
- the polyoxyethylene alkyl ether activators include BT series (Nikko Chemicals), Nonipol series (Sanyo Kasei), D-, P-series (Takemoto Yushi), EMALEX DAPE series (Japan emulsion), Pegnol series (Toho) Chemical industry).
- An example of the polyethylene glycol alkyl ester system is peganol (Toho Chemical Industries).
- acetylene glycol surfactants include Olphine E1010, STG, Y (from Nissin Chemical Co., Ltd.), Surfinol 104, 82, 420, 440, 465, 485, and TG (manufactured by Air Products and Chemicals Inc.). Can be mentioned.
- glycol ether compounds include diethylene glycol mono (C 1-8 alkyl) ether, triethylene glycol mono (C 1-8 alkyl) ether, propylene glycol mono (C 1-6 alkyl) ether, diethylene glycol, Mention may be made of propylene glycol mono (alkyl having 1 to 6 carbon atoms) ethers, and these may be used as one kind or a mixture of two or more kinds.
- ethylene glycol monomethyl ether ethylene glycol monoethyl ether, ethylene glycol mono-iso-propyl ether, ethylene glycol monobutyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl Ether, diethylene glycol mono-iso-propyl ether, diethylene glycol monobutyl ether, diethylene glycol mono-t-butyl ether, diethylene glycol monopentyl ether, diethylene glycol monohexyl ether, diethylene glycol monoheptyl ether, diethylene glycol monooctyl ether, triethylene Recall monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, triethylene glycol monopentyl ether, triethylene glycol monohexyl ether, triethylene glycol monohe
- Glycol ethers and surfactants can be used to adjust the surface tension of the ink.
- the ink can be appropriately added so that the surface tension of the ink is 15 mN / m to 30 mN / m or less, and the addition amount of the surfactant is preferably in the range of about 0.1 to 10% by mass with respect to the ink composition. More preferably, it is 0.3 to 2% by mass.
- the surface tension is more preferably in the range of 16 to 28, and most preferably in the range of 18 to 25.
- a wetting agent can be similarly added to the water-based ink for the purpose of preventing the ink from drying.
- the content of the wetting agent in the ink for the purpose of preventing drying is preferably 3 to 50% by mass.
- the wetting agent is not particularly limited, but a wetting agent that is miscible with water and can prevent clogging of an inkjet printer head is preferable.
- glycerin ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol having a molecular weight of 2000 or less, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propylene glycol, isopropylene glycol, isobutylene glycol, 1,2-butane Diol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 2-methylpentane-2,4-diol, 1, Diol compounds such as 2-heptanediol, 1,2-nonanediol, 1,2-octanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-nonanediol, 1,2-octanediol 1,4-butane
- a penetrant can be added to the water-based ink for the purpose of improving the permeability to a film as a recording medium and adjusting the dot diameter on the recording medium.
- the penetrant include lower alcohols such as ethanol and isopropyl alcohol, ethylene oxide adducts of alkyl alcohols such as ethylene glycol hexyl ether and diethylene glycol butyl ether, and propylene oxide adducts of alkyl alcohols such as propylene glycol propyl ether.
- the content of the penetrant in the ink is preferably 0.01 to 10% by mass.
- a water-based ink having a surface tension at 25 ° C. in the range of 15 mN / m to 30 mN / m and a viscosity of 5 mPa ⁇ s or less is used from the viewpoint of good ink jet printing. It is preferable.
- the method for producing the water-based ink is not limited at all.
- a coloring material such as the pigment, a resin having the polar group, water or a water-soluble organic solvent, and an additive such as a surfactant as necessary may be charged and dispersed to form a water-based ink.
- a water-based ink may be prepared by preparing a mill base having a high concentration of coloring material and diluting and appropriately adding additives. In the following, a method for forming the latter mill base and making it a water-based ink will be described.
- a method of preparing an aqueous pigment dispersion by adding a coloring material to an aqueous medium containing a pigment dispersant and water and then dispersing the coloring material in the aqueous medium using a stirring / dispersing device.
- the coloring material and the pigment dispersant are kneaded using a kneader such as two rolls or a mixer, and the obtained kneaded material is added to an aqueous medium containing water, and the mixture is aqueous using a stirring / dispersing device.
- a method for preparing a pigment dispersion A method for preparing a pigment dispersion.
- Examples of the agitation / dispersing device include an ultrasonic homogenizer, a high-pressure homogenizer, a paint shaker, a ball mill, a roll mill, a sand mill, a sand grinder, a dyno mill, a disper mat, an SC mill, and a nanomizer. May be used alone, or two or more kinds of apparatuses may be used in combination.
- Oil-based ink The oil-based ink is preferably used based on a solvent having a high boiling point in order to prevent clogging of the head.
- Nonpolar solvents include long chain fatty acid esters, vegetable oil esters, higher fatty acids, vegetable oils, hydrocarbons, higher alcohols, and the like.
- highly polar solvents include lower alcohols, glycols, glycol ethers, glycol esters, lower alcohol esters, pyrrolidones and the like.
- Non-polar solvents include, for example, methyl oleate, ethyl oleate, isopropyl oleate, isobutyl oleate, methyl linoleate, isobutyl linoleate, ethyl linoleate, soy oil methyl, soy oil isobutyl, linseed oil butyl, large Bean oil, linseed oil, castor oil, Nippon Oil Corporation “Nisseki Naphthezol H, No.
- Examples of the highly polar solvent include ethylene glycol, diethylene glycol, glycerin, xylitol, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol diethyl ether, triethylene glycol monobutyl ether, tetra
- Examples include ethylene glycol dimethyl ether, propylene glycol monomethyl ether monoacetate, dipropylene glycol monomethyl ether, isopropyl acetate, pyrrolidone, and N-methylpyrrolidone.
- more volatile solvents for example, alkyl alcohols such as ethanol and 2-propanol; ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons such as toluene and xylene; Esters such as ethyl acetate; amides such as dimethylformamide and dimethylacetamide; ethers such as dioxane and tetrahydrofuran can be mixed with the above solvents or used alone.
- alkyl alcohols such as ethanol and 2-propanol
- ketones such as acetone and methyl ethyl ketone
- aromatic hydrocarbons such as toluene and xylene
- Esters such as ethyl acetate
- amides such as dimethylformamide and dimethylacetamide
- ethers such as dioxane and tetrahydrofuran can be mixed with the above solvents or used alone.
- solvents suitable for so-called eco solvent ink not containing cyclohexanone include, for example, cyclic esters such as ⁇ -butyrolactone, dioxane, trioxane, furan, tetrahydrofuran, methyltetrahydrofuran, methylfuran, tetrahydro Cyclic ethers such as pyran and furflate, butyl formate, isoamyl formate, isobutyl formate, hexyl formate, butyl acetate, propyl acetate, isopropyl acetate, isobutyl acetate, isoamyl acetate, pentyl acetate, ethyl propionate, propyl propionate, isopropyl propionate, Butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate,
- cyclic esters such as
- Oil-based inks are obtained by dispersing color materials such as pigments in an organic solvent in the same manner as water-based inks. Even in the case of oil-based inks, the pigment is usually dispersed using a dispersing resin.
- a dispersing resin As the stirring / dispersing device for dispersing the pigment, the same device as the water-based ink can be used.
- a binder resin can also be used for the purpose of film formation and film adhesion.
- the dispersing resin and binder resin may be the same or several types may be used in combination. In general, oil-soluble urethane resin, acrylic resin, polyester resin, vinyl chloride resin, vinyl acetate resin and the like are used.
- antioxidants such as antioxidants and ultraviolet absorbers, surfactants, binder resins and the like can be added.
- antioxidants include BHA (2,3-butyl-4-oxyanisole), BIT (2,6-di-tert-butyl-P-cresol), etc .
- UV absorbers such as benzophenone and benzotriazole
- any of anionic, cationic amphoteric and nonionic compounds can be used.
- resins that can be used as the binder resin include acrylic resins, styrene acrylic resins, rosin-modified resins, phenol resins, terpene resins, polyester resins, polyamide resins, and epoxy resins.
- UV curable ink Since the UV curable ink cures the printed film with ultraviolet rays or the like, an ultraviolet curable compound or a photopolymerization initiator is used. Any of these compounds can be used, but if the viscosity is too high, there is a possibility that the ejection properties may be hindered. Therefore, it is preferable to appropriately select a low-viscosity ultraviolet curable compound. There are a radical polymerization type and a cationic polymerization type depending on the reaction mechanism. In order to obtain an ink having a fast curing and drying rate, it is preferable to use a compound having an ethylenic double bond such as (meth) acrylate as the ultraviolet curable compound.
- a compound having an ethylenic double bond such as (meth) acrylate
- the compound having an ethylenic double bond include a monofunctional monomer having one ethylenic double bond and a polyfunctional monomer having two or more ethylenic double bonds. Can be used in combination. Further, it is preferable to contain a (meth) acrylate oligomer or a trifunctional or higher polyfunctional acrylate, but these have a high viscosity, and in particular, the (meth) acrylate oligomer has a higher viscosity than the monomer. It is preferably used in the range of 2 to 20% by mass relative to the total amount of compounds having a bond.
- Examples of the monofunctional monomer include methyl, ethyl, propyl, butyl, amyl, 2-ethylhexyl, isooctyl, nonyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, benzyl, methoxyethyl, butoxyethyl, phenoxyethyl, nonylphenoxyethyl, (Meth) acrylate having a substituent such as glycidyl, dimethylaminoethyl, diethylaminoethyl, isobornyl, dicyclopentanyl, dicyclopentenyl, dicyclopentenyloxyethyl, vinyl caprolactam, vinyl pyrrolidone, N-vinylformamide, etc. It is done. Two or more of these can be used in combination.
- polyfunctional monomer examples include 1,3-butylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neo Di (meth) acrylates such as pentyl glycol, 1,8-octanediol, 1,9-nonanediol, tricyclodecane dimethanol, ethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, Di (meth) acrylate of tris (2-hydroxyethyl) isocyanurate, di (meth) acrylate of diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of neopentyl glycol, bis Diol of diol obtained by adding 2 mol of ethylene oxide or propylene oxide to 1 mol of
- Examples of the (meth) acrylate oligomer include urethane (meth) acrylate oligomers, epoxy (meth) acrylate oligomers, polyester (meth) acrylate oligomers, and the like.
- photopolymerization initiator examples include benzoin isobutyl ether, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, benzyl, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 6-trimethylbenzoyldiphenylphosphine oxide, 2-benzyl- 2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, etc.
- molecular cleavage types include 1-hydroxycyclohexyl phenyl ketone, benzoin ethyl ether, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylpheny ) -2-Hydroxy-2-methylpropan-1-one and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, etc. may be used in combination.
- Photopolymerization initiators such as benzophenone, 4-phenylbenzophenone, isophthalphenone, 4-benzoyl-4′-methyl-diphenyl sulfide, etc. can be used in combination.
- photopolymerization initiator for example, trimethylamine, methyldimethanolamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, N, N
- An amine that does not cause an addition reaction with the polymerizable component such as dimethylbenzylamine and 4,4′-bis (diethylamino) benzophenone can also be used in combination.
- Ink jet inks contain a polymerization inhibitor such as hydroquinone, methoquinone, di-t-butylhydroquinone, P-methoxyphenol, butylhydroxytoluene, nitrosamine salt, etc. in the ink in order to increase the storage stability of the ink. You may add in the range of the mass%.
- a polymerization inhibitor such as hydroquinone, methoquinone, di-t-butylhydroquinone, P-methoxyphenol, butylhydroxytoluene, nitrosamine salt, etc.
- a dispersant for the purpose of increasing the dispersion stability of the pigment.
- the dispersant include Ajimoto PB821, PB822, and PB817 manufactured by Ajinomoto Fine-Techno Co., Ltd., Solspers 24000GR, 32000, 33000, and 39000 manufactured by Abyssia, and Disparon DA-703-50, DA-705, and DA-725 manufactured by Enomoto Kasei Co., Ltd.
- the amount of the dispersant used is preferably in the range of 10 to 80% by mass, particularly preferably in the range of 20 to 60% by mass with respect to the pigment. When the amount used is less than 10% by mass, the dispersion stability tends to be insufficient, and when it exceeds 80% by mass, the viscosity of the ink tends to increase, and the ejection stability tends to decrease.
- non-reactive resins such as acrylic resin, epoxy resin, terpene phenol resin, rosin ester, etc. can be blended for the purpose of imparting adhesion to the recording medium.
- the UV curable ink contains, for example, a pigment and an ultraviolet curable compound, and the pigment is dispersed by using a stirring / dispersing device such as a bead mill, in which a polymer dispersant and a resin are added as necessary. Then, it can prepare by adding a photoinitiator and also adding additives, such as a surface tension regulator, if necessary, and stirring and dissolving. It can also be prepared by preparing a high-concentration pigment dispersion (mill base) in advance and then appropriately diluting and adding additives.
- a stirring / dispersing device such as a bead mill
- the printing method is preferably ink jet printing, but printing may be performed by other printing methods such as offset printing, letterpress printing, gravure printing, silk screen printing, or a combination of these two or more printing methods. It doesn't matter.
- inkjet printing was performed on the (A) surface of the recording medium using an inkjet printer “HP DESIGNJET L25500” (manufactured by Hured Packard).
- cyan pigment Fastogen Blue TGR CI Pigment Blue 15: 3, manufactured by DIC Corporation
- dispersant Ajisper PB821 manufactured by Ajinomoto Fine Techno Co., Ltd.
- diethylene glycol diethyl ether polyethylene together with zirconia beads
- UV curable ink As the UV curable ink, a commercially available cyan ink (UFJ-605C, manufactured by Mimaki Engineering Co., Ltd.) was used, and ink coating suitability was evaluated.
- the ink jet printer “VJ-1608HSJ” (manufactured by Muto Kogyo Co., Ltd.) and “Ramiles III: PJ-1634NX” (Muto Kogyo Co., Ltd.) are used for the (A) side of the recording medium.
- Inkjet printing was carried out using Regarding the preparation of printed matter using UV curable ink, inkjet printing was performed on the (A) surface of the recording medium using an inkjet printer “UFJ-605C” (manufactured by Mimaki Engineering Co., Ltd.).
- Example 1 As a resin for the layer, a ring-opening polymer of a norbornene-based monomer [“Apel APL6015T” manufactured by Mitsui Chemicals, MFR: 10 g / 10 min (260 ° C., 21.18 N), glass transition point: 145 ° C .; "COC (1)”. ] 20 parts and a ring-opening polymer of a norbornene-based monomer [“Apel APL8008T” manufactured by Mitsui Chemicals, MFR: 15 g / 10 min (260 ° C., 21.18 N), glass transition point: 70 ° C .; 3) ". A resin mixture of 80 parts was used.
- This resin is supplied to a (A) layer extruder (50 mm diameter) and melted at 200 to 230 ° C., and the melted resin is fed into a T-die / chill roll coextrusion multilayer film production apparatus (feed). Block and T die temperature: 250 ° C.), and melt extrusion is performed to obtain a film having a single layer configuration of (A) and a total layer thickness of 70 ⁇ m. ) Corona treatment was applied to the layer surface. The surface tension with a wetting reagent (Wako Pure Chemical Industries, Ltd., mixed liquid for wet tension test) was 45 mN / m.
- Example 2 As the layer resin, a resin mixture of 50 parts of COC (1) and 50 parts of COC (3) was used. In the same manner as in Example 1, after obtaining a film having a single layer configuration of (A) and a thickness of all layers of 30 ⁇ m, the surface of the (A) layer was subjected to corona treatment. The surface tension by the wetting reagent was 45 mN / m.
- Example 3 60 parts of COC (1) and 30 parts of COC (3) and linear medium density polyethylene [density: 0.930 g / cm 3 , melting point 125 ° C., MFR: 5 g / 10 min (190] Hereinafter referred to as “LMDPE”. A resin mixture with 10 parts was used. After performing melt extrusion in the same manner as in Example 1 to obtain a film having a single layer configuration of (A) and a total thickness of 30 ⁇ m, (A) the surface of the layer was subjected to corona treatment. gave. The surface tension by the wetting reagent was 45 mN / m.
- Example 4 As a layer resin, 60 parts of COC (1) and 30 parts of COC (3) and a propylene- ⁇ -olefin random copolymer polymerized using a metallocene catalyst [density: 0.900 g / cm 3 , melting point 135 ° C., MFR: 4 g / 10 min (230 ° C., 21.18 N); hereinafter referred to as “MRCP”. ) 10 parts resin mixture was used. After performing melt extrusion in the same manner as in Example 1 to obtain a film having a single layer configuration of (A) and a total thickness of 20 ⁇ m, (A) the surface of the layer is subjected to corona treatment. gave. The surface tension by the wetting reagent was 45 mN / m.
- Example 5 As the layer resin, a resin mixture of 40 parts of COC (1), 40 parts of COC (3) and 20 parts of LMDPE was used. After melt extrusion was performed in the same manner as in Example 1 to obtain a film having a single layer configuration of (A) and a total thickness of 50 ⁇ m, (A) the surface of the layer was subjected to corona treatment. gave. The surface tension by the wetting reagent was 45 mN / m.
- Example 6 As a layer resin, a ring-opening polymer of norbornene-based monomer [“Appel AP6013T” manufactured by Mitsui Chemicals, MFR: 15 g / 10 min (260 ° C., 21.18 N), glass transition temperature: 125 ° C .; "COC (2)”. ] 60 parts and high density polyethylene [density: 0.960 g / cm 3 , melting point 128 ° C., MFR: 10 g / 10 minutes (190 ° C., 21.18 N); hereinafter referred to as “HDPE”. 40 parts of the resin mixture was used.
- HDPE high density polyethylene
- Example 8 As the layer resin, a resin mixture of 50 parts of COC (1) and 50 parts of COC (3) was used. MRCP is used as the resin for the intermediate layer (B), and the resin mixture of 50 parts of COC (1) and 50 parts of COC (3) is used as the resin for the outermost layer (hereinafter, the outermost layer is referred to as layer (C)).
- layer (C) the outermost layer is referred to as layer (C)).
- These resins are supplied to (A) layer extruder (50 mm diameter), (B) layer extruder (50 mm diameter), and (C) layer extruder (50 mm diameter) and melted at 230 to 250 ° C.
- the melted resin is supplied to a T-die / chill roll co-extrusion multi-layer film production apparatus (feed block and T-die temperature: 250 ° C.) having a feed block, and co-melt extrusion is performed to form a layer structure of the film.
- (A) / (B) / (C) 10 ⁇ m / 30 ⁇ m / 10 ⁇ m, and a coextruded multilayer film having a total thickness of 50 ⁇ m was obtained.
- the surface of the layer (A) was subjected to corona treatment.
- the surface tension by the wetting reagent was 42 mN / m.
- Example 9 A resin mixture of 40 parts of COC (1) and 60 parts of COC (3) was used as the layer resin.
- LMDPE as the resin for the layer (B)
- a resin mixture of 40 parts of COC (1) and 60 parts of COC (3) as the resin for the layer (C)
- the thickness of the film layer is 10 ⁇ m /
- a coextruded multilayer film was obtained in the same manner as in Example 8 so as to be 30 ⁇ m / 10 ⁇ m (total 50 ⁇ m), and then the surface of layer (A) was subjected to corona treatment.
- the surface tension by the wetting reagent was 43 mN / m.
- Example 10 70 parts of COC (1) as the resin for the layer and ethylene- (meth) acrylate methyl copolymer as the acid-modified polyolefin resin fat [density: 0.940 g / cm 3 , MA content 18%; Hereinafter referred to as “MA1”] 30 parts of the resin mixture was used.
- the resin for the layer (B) a resin mixture of 80 parts of LMDPE and 20 parts of COC (3) was used.
- a resin for the layer (C) a resin mixture of 70 parts of COC (1), 20 parts of LMDPE and 10 parts of HDPE was used so that the thickness of the film layer was 20 ⁇ m / 30 ⁇ m / 20 ⁇ m (total 70 ⁇ m).
- the surface of the layer (A) was subjected to corona treatment.
- the surface tension by the wetting reagent was 43 mN / m.
- Example 11 60 parts of COC (1) and 20 parts of COC (3) as the resin for the layer and ethylene-methyl acrylate-maleic anhydride copolymer [density: 1.00 g / cm as the acid-modified polyolefin resin fat 3. Copolymer content 15%; hereinafter referred to as “MA2”] 20 parts of resin mixture were used.
- the thickness of the film layer is 20 ⁇ m / 30 ⁇ m / 20 ⁇ m (total 70 ⁇ m) and Example 8 Similarly, after obtaining a coextruded multilayer film, the surface of the layer (A) was subjected to corona treatment. The surface tension by the wetting reagent was 43 mN / m.
- Example 12 As the layer resin, a resin mixture of 50 parts of COC (1) and 50 parts of COC (3) was used. As the resin for the layer (B), a resin mixture of 50 parts of LMDPE and 50 parts of MRCP was used. Furthermore, using a resin mixture of 20 parts of COC (1), 60 parts of COC (2) and 20 parts of LMDPE as the resin for the layer (C), the thickness of the film layer becomes 20 ⁇ m / 30 ⁇ m / 20 ⁇ m (total 70 ⁇ m). Thus, in the same manner as in Example 8, after obtaining a coextruded multilayer film, the surface of the layer (A) was subjected to corona treatment. The surface tension by the wetting reagent was 43 mN / m.
- Example 13 MA1 was used as the resin for the layer (A).
- HOPP melting point: 163 ° C .
- a coextruded multilayer film having a film layer thickness of 24 ⁇ m / 96 ⁇ m (total of 120 ⁇ m) was obtained.
- the surface of the layer (A) was subjected to corona treatment.
- the surface tension by the wetting reagent was 40 mN / m.
- Example 14 A recording medium for inkjet ink was produced in the same manner as in Example 13 except that the thickness of each layer of the layer constitution (A) / (B) of Example 13 was 14 ⁇ m / 56 ⁇ m (total 70 ⁇ m).
- Example 15 A recording medium for inkjet ink was produced in the same manner as in Example 13 except that the thickness of each layer of the layer structure (A) / (B) of Example 13 was changed to 6 ⁇ m / 24 ⁇ m (total 30 ⁇ m).
- Example 16 A recording medium for ink-jet ink was prepared in the same manner as in Example 13 except that the acid-modified olefin resin in the layer (A) of Example 13 was replaced with MA2.
- Example 17 The acid-modified olefin resin of the layer (A) of Example 13 is an ethylene-methyl acrylate-maleic anhydride copolymer [density: 1.00 g / cm 3 , copolymer content 15%; hereinafter referred to as “MA3”.
- a recording medium for inkjet ink was produced in the same manner as in Example 13 except that the above was replaced.
- Example 18 50% of resin MA1 for layer (A) of Example 13 and propylene-ethylene copolymer [density: 0.900 g / cm 3 , MFR: 7-9 g / 10 min (230 ° C., 21.18 N), melting point : 150 ° C .; hereinafter referred to as “COPP”]
- a recording medium for ink-jet ink was prepared in the same manner as in Example 13 except that the composition was replaced with 50%.
- Example 19 A recording medium for ink-jet ink was prepared in the same manner as in Example 13 except that the resin MA1 for layer (A) of Example 13 was replaced with a blend of 20% and COPP of 80%.
- Example 20 A recording medium for inkjet ink was produced in the same manner as in Example 18 except that HOPP in the layer (B) of Example 19 was replaced with HDPE.
- Example 21 The HOPP of the layer (B) of Example 19 was changed to medium density polyethylene [density: 0.934 g / cm 3 , MFR: 5.3 g / 10 min (190 ° C., 21.18 N), melting point 119 ° C .; hereinafter, “MDPE”
- MDPE medium density polyethylene
- Example 22 Example except that the acrylic acid-modified resin of Example 13 was replaced with an ethylene- (meth) acrylic acid copolymer (density: 0.940 g / cm 3 , acid modification rate: 12%; hereinafter referred to as “MA4”). In the same manner as in Example 13, a recording medium for inkjet ink was produced.
- MA4 ethylene- (meth) acrylic acid copolymer
- Example 23 A recording medium for inkjet ink was produced in the same manner as in Example 13 except that the thickness of each layer of the layer structure (A) / (B) of Example 13 was 6 ⁇ m / 114 ⁇ m (total of 120 ⁇ m).
- Example 24 A recording medium for inkjet ink was produced in the same manner as in Example 13 except that the thickness of each layer of the layer structure (A) / (B) of Example 13 was changed to 30 ⁇ m / 90 ⁇ m (total of 120 ⁇ m).
- Comparative Example 1 As a layer resin, HOPP was used to obtain a 30 ⁇ m monolayer film, and then one surface was subjected to corona treatment. The surface tension by the wetting reagent was 43 mN / m.
- Comparative Example 2 As a resin for layers, linear low density polyethylene [density: 0.905 g / cm 3 , melting point 90 ° C., MFR: 5 g / 10 min (190 ° C., 21.18 N); hereinafter referred to as “LLDPE”. ] To obtain a 30 ⁇ m monolayer film, and then subjected to corona treatment on one surface. The surface tension by the wetting reagent was 40 mN / m.
- Comparative Example 3 A recording medium for ink-jet ink was produced in the same manner as in Example 13 except that the acid-modified polyolefin resin in the layer (A) of Example 13 was replaced with COPP.
- Comparative Example 4 A recording medium for inkjet ink was produced in the same manner as in Example 13 except that the acid-modified polyolefin resin in the layer (A) of Example 13 was replaced with HDPE.
- the ink-jet printed matter of the present invention can be used for various purposes such as outdoor advertisement (poster, banner, etc.), label, wallpaper, packaging film, postcard, OHP sheet, jet paper, lottery ticket, form, and the like.
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Abstract
Description
本発明で使用するインクジェットインクは、特に限定されるものではなく、種々のものを使用することができる。インクジェットインクには、主溶剤として水または水と水溶性有機溶剤の混合溶媒を用いた水性インク、主溶剤として有機溶剤を用いた非水系(油性)インク、あるいは、これら溶剤を使用しないUV硬化型インク等が知られているが、本発明で使用するフィルムは、プラスチックフィルムへの密着性の良好な油性インク、UV硬化型インクは勿論、通常はじき等の問題が生じる水性インクであっても良好な密着性を示すので問題なく使用することができる。
これらのインクジェットインクに使用される色材は、通常顔料や染料が使用されるが、印刷物の耐久性の点から顔料を使用することが好ましい。染料としては、直接染料、酸性染料、食用染料、塩基性染料、反応性染料、分散染料、建染染料、可溶性建染染料、反応分散染料、など通常インクジェット記録に使用される各種染料が挙げられる。また、顔料としては、硫酸バリウム、硫酸鉛、酸化チタン、黄色鉛、ベンガラ、酸化クロム、カーボンブラック等の無機顔料、アントラキノン系顔料、ペリレン系顔料、ジスアゾ系顔料、フタロシアニン系顔料、イソインドリン系顔料、ジオキサジン系顔料、キナクリドン系顔料、ペリノン系顔料、ベンズイミダゾロン系顔料等が挙げられる。これらを単独または混合して用いることができる。
シアンの顔料としては、たとえば、C.I.ピグメント ブルー 1、C.I.ピグメント ブルー 2、C.I.ピグメント ブルー 3、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 15:3、C.I.ピグメント ブルー 15:4、C.I.ピグメント ブルー 16、C.I.ピグメント ブルー 22、C.I.ピグメント ブルー 60、などが挙げられる。
水性インクに使用される水は、イオン交換、蒸留等の精製工程を経た純水または超純水が望ましい。また水溶性有機溶剤としては、例えば、アセトン、メチルエチルケトン、メチルブチルケトン、メチルイソブチルケトン、等のケトン類;メタノール、エタノール、2-プロパノール、2-メチル-1-プロパノール、1-ブタノール、2-メトキシエタノール、等のアルコール類;テトラヒドロフラン、1,4-ジオキサン、1,2-ジメトキシエタン、等のエーテル類;ジメチルホルムアミド、N-メチルピロリドン、2-ピロリドン、LEG-1、グリセロール、ジエチレングリコール、トリメチロールプロパン、及び/又はその類を使用することができる。
水性インクには表面張力を適宜調整するため、界面活性剤または低表面張力有機溶媒を添加することができる。界面活性剤は特に限定されるものではなく、各種のアニオン性界面活性剤、ノニオン性界面活性剤、カチオン性界面活性剤、両性界面活性剤などが挙げられ、これらの中では、アニオン性界面活性剤、ノニオン性界面活性剤が好ましい。
さらに水性インクには、インクの乾燥防止を目的として、湿潤剤を同様に添加することができる。乾燥防止を目的とする湿潤剤のインク中の含有量は3~50質量%であることが好ましい。前記湿潤剤としては特に限定はないが、水との混和性がありインクジェットプリンターのヘッドの目詰まり防止効果が得られるものが好ましい。例えば、グリセリン、エチレングリコール、ジエチレングリコール、トリエチレングリコール、分子量2000以下のポリエチレングリコール、プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール、1,3-プロピレングリコール、イソプロピレングリコール、イソブチレングリコール、1,2-ブタンジオール、1,4-ブタンジオール、1,2-ペンタンジオール、1,5-ペンタンジオール、1,2-ヘキサンジオール、1,6-ヘキサンジオール、2-メチルペンタン-2,4-ジオール、1,2-ヘプタンジオール、1,2-ノナンジオール、1,2-オクタンジオール、1,2-ヘキサンジオール、1,2-ヘプタンジオール、1,2-ノナンジオール、1,2-オクタンジオール等のジオール化合物、1,4-ブタンジオール、1,3-ブタンジオール、メソエリスリトール、ペンタエリスリトール、N-メチル-2-ピロリドン、N-ヒドロキシエチル-2-ピロリドン、2-ピロリドン、1,3-ジメチルイミダゾリジノン、ε-カプロラクタム等の含窒素複素環化合物等が挙げられる。中でも、プロピレングリコール、1,3-ブチルグリコールを含むことが安全性を有し、かつインク乾燥性、吐出性能に優れた効果が見られる。
さらに水性インクは、被記録媒体であるフィルムへの浸透性改良や記録媒体上でのドット径調整を目的として浸透剤を添加することができる。浸透剤としては、例えばエタノール、イソプロピルアルコール等の低級アルコール、エチレングリコールヘキシルエーテルやジエチレングリコールブチルエーテル等のアルキルアルコールのエチレンオキシド付加物やプロピレングリコールプロピルエーテル等のアルキルアルコールのプロピレンオキシド付加物等が挙げられる。インク中の浸透剤の含有量は0.01~10質量%であることが好ましい。
水性インクの製造方法には何ら限定されるものではない。前記顔料等の色材と、前記極性基を有する樹脂と、水または水溶性有機溶媒と、必要に応じて界面活性剤等の添加剤と仕込み分散させて水性インクとしてもよいし、予め顔料等色材の濃度の高いミルベースを作成し、希釈・適宜添加剤を添加して水性インクとしてもよい。以下、後者のミルベースを作成した後水性インクとする方法について述べる。
(1)顔料分散剤及び水を含有する水性媒体に色材を添加した後、攪拌・分散装置を用いて色材を該水性媒体中に分散させることにより、水性顔料分散液を調製する方法。
(2)色材、及び顔料分散剤を2本ロール、ミキサー等の混練機を用いて混練し、得られた混練物を水を含む水性媒体中に添加し、攪拌・分散装置を用いて水性顔料分散液を調製する方法。
(3)メチルエチルケトン、テトラヒドロフラン等のような水と相溶性を有する有機溶剤中に顔料分散剤を溶解して得られた溶液に色材を添加した後、攪拌・分散装置を用いて白色顔料を有機溶液中に分散させ、次いで水性媒体を用いて転相乳化させた後、前記有機溶剤を留去し水性顔料分散液を調製する方法。
などが挙げられる。
油性インクはヘッドのつまり等を防ぐために高沸点の溶媒をベースとしたものが好ましく用いられる。非極性な溶剤としては、長鎖脂肪酸エステル、植物油エステル類、高級脂肪酸、植物油、炭化水素類、高級アルコール類などが挙げられる。極性の高い溶剤として、低級アルコール、グリコール類、グリコールエーテル類、グリコールエステル類、低級アルコールエステル、ピロリドン類などが挙げられる。
UV硬化型インクは、紫外線等で印刷被膜を硬化させることから、紫外線硬化性化合物や光重合開始剤等を使用する。これらはいずれも種々のものを使用することができるが、あまり高粘度では吐出性に支障がでるおそれがあることから、低粘度の紫外線硬化性化合物を適宜選択することが好ましい。また、その反応機構によりラジカル重合型とカチオン重合型がある。硬化乾燥速度の速いインクを得るためには、紫外線硬化性化合物として(メタ)アクリレート等のエチレン性二重結合を有する化合物を使用することが好ましい。
バーコーター(No.6)でA4サイズのフィルムに各種インクを塗工し、目視にてはじきの数を計測した。
○:はじきが無い。
×:はじきが一箇所以上ある。
印刷後、90℃で1分間乾燥させた時のフィルムの外観について目視にて評価した。
○:よれ、皺、フィルムの変形等の外観不良がほとんど無い。
△:若干のよれ、皺、フィルムの変形等の外観不良が見られる。
×:著しいよれ、皺、フィルムの変形等の外観不良が見られる。
記録媒体の(A)面に対して安定したインク転移(印刷)が行われたか否かを目視にて評価した。
○:印刷がかすれたり、印字できない部分等が無く、良好に印刷された。
×:印刷がかすれたり、印字できない部分等が有り、印刷不良がある。
セロハンテープ(ニチバン製)剥離試験を行い、目視にて評価した。
○:剥離無し。
×:剥離有り。
水性インクは、市販のシアン色インク(ヒューレッドパッカード社製、HP DESIGNJET L25500)を用い、インク塗工適性評価を行った。インクを表面張力計(協和界面科学製:CBVP-A3)を用いて、白金プレート法により温度25℃における表面張力を測定した結果、18.2mN/mであった。同様に、粘度計(東亜ディーケーケー製:TVE-25Lを用いて、25℃における粘度測定した結果、3.22mPa・sであった。
シアン顔料Fastogen Blue TGR(C.I.ピグメント ブルー15:3、DIC株式会社製)20部、分散剤アジスパーPB821(味の素ファインテクノ株式会社製)6部、ジエチレングリコールジエチルエーテル74部を、ジルコニアビーズとともにポリエチレン容器に入れ、ペイントコンディショナーで2時間震盪し、顔料濃度20%のシアン顔料分散液Aを得た。この分散液Aを12.5部、樹脂VROH(ダウ・ケミカル日本株式会社製)6.5部、エポサイザーW100EL(DIC株式会社製)0.5部、KF54(信越シリコーン株式会社製)0.5部、溶剤としてジエチレングリコールジエチルエーテル46部、ジプロピレングリコールモノメチルエーテル15部、γ-ブチロラクトン20部を撹拌しながら、60℃に加熱した。均一に溶解・混合後、室温まで冷却し、1.2μmのメンブレンフィルターでろ過し溶剤型インク1を作製した。このインク1を用い、インクの塗工適性評価を行った。
溶剤型インク1の調整例 において、溶剤をエチレングリコールモノブチルエーテルアセテート41部、シクロヘキサン40部とする以外はインク1の調整例と同様にして、溶剤型インク2を作製した。このインクを用い、インクの塗工適性評価を行った。
UV硬化型インクは、市販シアン色インク(ミマキエンジニアリング株式会社製、UFJ-605C)を用い、インク塗工適性評価を行った。
(A)層用樹脂として、ノルボルネン系モノマーの開環重合体〔三井化学株式会社製「アペル APL6015T」、MFR:10g/10分(260℃、21.18N)、ガラス転移点:145℃;以下、「COC(1)」という。〕20部及びノルボルネン系モノマーの開環重合体〔三井化学株式会社製「アペル APL8008T」、MFR:15g/10分(260℃、21.18N)、ガラス転移点:70℃;以下、「COC(3)」という。〕80部との樹脂混合物を用いた。この樹脂を、(A)層用押出機(口径50mm)に供給して200~230℃で溶融し、その溶融した樹脂をフィードブロックを有するTダイ・チルロール法の共押出多層フィルム製造装置(フィードブロック及びTダイ温度:250℃)に供給して溶融押出を行って、フィルムの層構成が(A)の単層構成で、全層の厚さが70μmであるフィルムを得た後、(A)層表面にコロナ処理を施した。濡れ試薬(和光純薬工業株式会社製、ぬれ張力試験用混合液)による表面張力は45mN/mであった。
(A)層用樹脂として、COC(1)50部及びCOC(3)50部の樹脂混合物を用いた。実施例1と同様にして、フィルムの層構成が(A)の単層構成で、全層の厚さが30μmであるフィルムを得た後、(A)層表面にコロナ処理を施した。濡れ試薬による表面張力は45mN/mであった。
(A)層用樹脂として、COC(1)60部及びCOC(3)30部及び直鎖状中密度ポリエチレン〔密度:0.930g/cm3、融点125℃、MFR:5g/10分(190℃、21.18N);以下、「LMDPE」という。〕10部との樹脂混合物を用いた。実施例1と同様に溶融押出を行って、フィルムの層構成が(A)の単層構成で、全層の厚さが30μmであるフィルムを得た後、(A)層表面にコロナ処理を施した。濡れ試薬による表面張力は45mN/mであった。
(A)層用樹脂として、COC(1)60部及びCOC(3)30部及びメタロセン触媒を用いて重合されたプロピレン-α-オレフィンランダム共重合体〔密度:0.900g/cm3、融点135℃、MFR:4g/10分(230℃、21.18N)、;以下、「MRCP」という。)10部との樹脂混合物を用いた。実施例1と同様に溶融押出を行って、フィルムの層構成が(A)の単層構成で、全層の厚さが20μmであるフィルムを得た後、(A)層表面にコロナ処理を施した。濡れ試薬による表面張力は45mN/mであった。
(A)層用樹脂として、COC(1)40部及びCOC(3)40部及びLMDPE20部との樹脂混合物を用いた。実施例1と同様に溶融押出を行って、フィルムの層構成が(A)の単層構成で、全層の厚さが50μmであるフィルムを得た後、(A)層表面にコロナ処理を施した。濡れ試薬による表面張力は45mN/mであった。
(A)層用樹脂として、ノルボルネン系モノマーの開環重合体〔三井化学株式会社製「アペル AP6013T」、MFR:15g/10分(260℃、21.18N)、ガラス転移温度:125℃;以下、「COC(2)」という。〕60部及び高密度ポリエチレン〔密度:0.960g/cm3、融点128℃、MFR:10g/10分(190℃、21.18N);以下、「HDPE」という。〕を40部の樹脂混合物を用いた。実施例1と同様に溶融押出を行って、フィルムの層構成が(A)の単層構成で、全層の厚さが40μmであるフィルムを得た後、(A)層表面にコロナ処理を施した。濡れ試薬による表面張力は43mN/mであった。
(A)層用樹脂として、COC(1)70部及びCOC(3)10部、LMDPE10部及びMRCP10部の樹脂混合物を用いた。また、層(B)用樹脂として、MRCPを用いた。これらの樹脂を、(A)層用押出機(口径50mm)、(B)層用押出機(口径50mm)に供給して200~230℃で溶融し、その溶融した樹脂をフィードブロックを有するTダイ・チルロール法の共押出多層フィルム製造装置(フィードブロック及びTダイ温度:250℃)にそれぞれ供給して共溶融押出を行って、フィルムの層構成が(A)/(B)=20μm/20μmの多層構成で、全層の厚さが40μmである共押出多層フィルムを得た。層(A)表面にコロナ処理を施した。濡れ試薬による表面張力は40mN/mであった。
(A)層用樹脂として、COC(1)50部及びCOC(3)50部の樹脂混合物を用いた。中間層(B)用樹脂としてMRCPを用い、更に、最外層用樹脂(以下、最外層を層(C)と称する。)として、COC(1)50部及びCOC(3)50部の樹脂混合物を用いた。これらの樹脂を、(A)層用押出機(口径50mm)、(B)層用押出機(口径50mm)、(C)層用押出機(口径50mm)に供給して230~250℃で溶融し、その溶融した樹脂をフィードブロックを有するTダイ・チルロール法の共押出多層フィルム製造装置(フィードブロック及びTダイ温度:250℃)にそれぞれ供給して共溶融押出を行って、フィルムの層構成が(A)/(B)/(C)=10μm/30μm/10μmの多層構成で、全層の厚さが50μmである共押出多層フィルムを得た。実施例1と同様にして、層(A)表面にコロナ処理を施した。濡れ試薬による表面張力は42mN/mであった。
(A)層用樹脂として、COC(1)40部及びCOC(3)60部の樹脂混合物を用いた。層(B)用樹脂としてLMDPEを用い、更に、層(C)用樹脂として、COC(1)40部及びCOC(3)60部の樹脂混合物を用いて、フィルムの層の厚さが10μm/30μm/10μm(合計50μm)となるように実施例8と同様にして、共押出多層フィルムを得た後、層(A)表面にコロナ処理を施した。濡れ試薬による表面張力は43mN/mであった。
(A)層用樹脂として、COC(1)70部及び酸変性ポリオレフィン系樹脂脂として、エチレン-(メタ)アクリル酸メチル共重合体〔密度:0.940g/cm3、MA含有量18%;以下、「MA1」と記載〕30部の樹脂混合物を用いた。層(B)用樹脂としてLMDPE80部及びCOC(3)20部の樹脂混合物を用いた。更に、層(C)用樹脂として、COC(1)70部及びLMDPE20部及びHDPE10部の樹脂混合物を用いて、フィルムの層の厚さが20μm/30μm/20μm(合計70μm)となるように実施例8と同様にして、共押出多層フィルムを得た後、層(A)の表面にコロナ処理を施した。濡れ試薬による表面張力は43mN/mであった。
(A)層用樹脂として、COC(1)60部及びCOC(3)20部及び酸変性ポリオレフィン系樹脂脂として、エチレン-アクリル酸メチル-無水マレイン酸共重合体〔密度:1.00g/cm3、コポリマー含有量15%;以下、「MA2」と記載〕20部の樹脂混合物を用いた。層(B)用樹脂としてMRCP80部及びCOC(3)20部の樹脂混合物を用いた。更に、層(C)用樹脂として、COC(3)70部及びLMDPE30部の樹脂混合物を用いて、フィルムの層の厚さが20μm/30μm/20μm(合計70μm)となるように実施例8と同様にして、共押出多層フィルムを得た後、層(A)の表面にコロナ処理を施した。濡れ試薬による表面張力は43mN/mであった。
(A)層用樹脂として、COC(1)50部及びCOC(3)50部の樹脂混合物を用いた。層(B)用樹脂としてLMDPE50部及びMRCP50部の樹脂混合物を用いた。更に層(C)用樹脂として、COC(1)20部及びCOC(2)60部及びLMDPE20部の樹脂混合物を用いて、フィルムの層の厚さが20μm/30μm/20μm(合計70μm)となるように実施例8と同様にして、共押出多層フィルムを得た後、層(A)の表面にコロナ処理を施した。濡れ試薬による表面張力は43mN/mであった。
層(A)用樹脂として、MA1を用いた。層(B)用樹脂として、ホモポリプロピレン〔MFR:10g/10分(230℃、21.18N)、融点:163℃;以下、「HOPP」と記載〕を用いた。実施例7と同様にしてフィルムの層の厚さが24μm/96μm(合計120μm)である共押出多層フィルムを得た。層(A)の表面にコロナ処理を施した。濡れ試薬による表面張力は40mN/mであった。
実施例13のフィルムの層構成(A)/(B)の各層の厚さを14μm/56μm(合計70μm)とした以外は実施例13と同様にしてインクジェットインク用記録媒体を作製した。
実施例13のフィルムの層構成(A)/(B)の各層の厚さを6μm/24μm(合計30μm)とした以外は実施例13と同様にしてインクジェットインク用記録媒体を作製した。
実施例13の層(A)の酸変性オレフィン系樹脂をMA2に置き換えた以外は実施例13と同様にしてインクジェットインク用記録媒体を作製した。
実施例13の層(A)の酸変性オレフィン系樹脂をエチレン-アクリル酸メチル-無水マレイン酸共重合体〔密度:1.00g/cm3、コポリマー含有量15%;以下、「MA3」と記載〕に置き換えた以外は実施例13と同様にしてインクジェットインク用記録媒体を作製した。
実施例13の層(A)用の樹脂MA1を50%とプロピレン-エチレン共重合体〔密度:0.900g/cm3、MFR:7~9g/10分(230℃、21.18N)、融点:150℃;以下「COPP」と記載〕50%との配合物に置き換えた以外は実施例13と同様にしてインクジェットインク用記録媒体を作製した。
実施例13の層(A)用の樹脂MA1を20%とCOPPを80%との配合物に置き換えた以外は実施例13と同様にしてインクジェットインク用記録媒体を作製した。
実施例19の層(B)のHOPPをHDPEに置き換えた以外は実施例18と同様にしてインクジェットインク用記録媒体を作製した。
実施例19の層(B)のHOPPを中密度ポリエチレン〔密度:0.934g/cm3、MFR:5.3g/10分(190℃、21.18N)、融点119℃;以下、「MDPE」と記載〕に置き換えた以外は実施例18と同様にしてインクジェットインク用記録媒体を作製した。
実施例13のアクリル酸変性樹脂をエチレン-(メタ)アクリル酸共重合体〔密度:0.940g/cm3、酸変性率12%;以下、「MA4」と記載〕に置き換えた以外は実施例13と同様にしてインクジェットインク用記録媒体を作製した。
実施例13のフィルムの層構成(A)/(B)の各層の厚さを6μm/114μm(合計120μm)とした以外は実施例13と同様にしてインクジェットインク用記録媒体を作製した。
実施例13のフィルムの層構成(A)/(B)の各層の厚さを30μm/90μm(合計120μm)とした以外は実施例13と同様にしてインクジェットインク用記録媒体を作製した。
(A)層用樹脂として、HOPPを用いて、30μmの単層フィルムを得た後、片方の表面にコロナ処理を施した。濡れ試薬による表面張力は43mN/mであった。
(A)層用樹脂として、直鎖状低密度ポリエチレン〔密度:0.905g/cm3、融点90℃、MFR:5g/10分(190℃、21.18N);以下、「LLDPE」という。〕を用いて、30μmの単層フィルムを得た後、片方の表面にコロナ処理を施した。濡れ試薬による表面張力は40mN/mであった。
実施例13の層(A)の酸変性ポリオレフィン系樹脂をCOPPに置き換えた以外は実施例13と同様にしてインクジェットインク用記録媒体を作製した。
実施例13の層(A)の酸変性ポリオレフィン系樹脂をHDPEに置き換えた以外は実施例13と同様にしてインクジェットインク用記録媒体を作製した。
Claims (10)
- 環状ポリオレフィン系樹脂(a1)及び/又は酸変性ポリオレフィン系樹脂(a2)を含有する層(A)を有する単層又は多層のフィルム(I)の層(A)表面にインクジェット印刷を行なうことを特徴とするインクジェット印刷物の製造方法。
- 前記フィルム(I)が、更にポリオレフィン系樹脂(b)を主成分とする樹脂層(B)を有する多層フィルムである請求項1記載のインクジェット印刷物の製造方法。
- 前記層(A)と前記層(B)とが共押出積層法で積層されたものである請求項2記載のインクジェット印刷物の製造方法。
- 前記環状オレフィン系樹脂(a1)がノルボルネン系重合体である請求項1~3の何れか1項記載のインクジェット印刷物の製造方法。
- 前記酸変性ポリオレフィン系樹脂(a2)における変性率が0.5~40%の範囲である請求項1~3の何れか1項記載のインクジェット印刷物の製造方法。
- フィルム(I)の層(A)を形成する樹脂成分100質量部中に、前記環状ポリオレフィン系樹脂(a1)と前記酸変性ポリオレフィン系樹脂(a2)との合計質量として50質量部以上含有するものである請求項1~5の何れか1項記載のインクジェット印刷物の製造方法。
- 前記層(A)の表面処理度を40dyne/cm以上に処理してからインクジェット印刷を行うものである請求項1~6の何れか1項記載のインクジェット印刷物の製造方法。
- 環状ポリオレフィン系樹脂(a1)及び/又は酸変性ポリオレフィン系樹脂(a2)を含有する層(A)と、ポリオレフィン系樹脂(b)を含有する層(B)とが積層され、前記層(A)と前記層(B)との合計厚みに対する層(B)の比率が5~85%であり、かつ層(A)表面が40dyne/cm以上であることを特徴とするインクジェットインク用記録媒体。
- 請求項8記載のインクジェットインク用記録媒体の層(A)表面にインクジェット印刷したものであることを特徴とするインクジェット印刷物。
- 少なくとも、色材と、極性基を有する樹脂と、水または水溶性有機溶媒とを含んでなり、25℃における表面張力が15mN/m~30mN/mの範囲であり、且つ粘度が5mPa・s以下である水性インクを用い、インクジェット印刷したものである請求項9記載のインクジェット印刷物。
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EP2762321A4 (en) | 2015-07-08 |
TW201323212A (zh) | 2013-06-16 |
US20140349037A1 (en) | 2014-11-27 |
US9005726B2 (en) | 2015-04-14 |
TWI602701B (zh) | 2017-10-21 |
KR101599757B1 (ko) | 2016-03-04 |
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EP2762321B1 (en) | 2019-08-14 |
KR20140051429A (ko) | 2014-04-30 |
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