CN110804341A - Alcohol-water type ink, preparation method and application thereof - Google Patents
Alcohol-water type ink, preparation method and application thereof Download PDFInfo
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- CN110804341A CN110804341A CN201911261286.8A CN201911261286A CN110804341A CN 110804341 A CN110804341 A CN 110804341A CN 201911261286 A CN201911261286 A CN 201911261286A CN 110804341 A CN110804341 A CN 110804341A
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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
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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
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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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
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
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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
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
Abstract
The invention relates to an alcohol-water type ink, a preparation method and application thereof. The alcohol water type ink comprises the following components in percentage by weight: 3-25 parts of water-soluble resin, 10-60 parts of emulsion type resin, 0.05-2 parts of wetting agent, 0-4 parts of scratch-resistant auxiliary agent and 8-35 parts of dispersion medium. The dispersion medium is a mixture of alcohols and water, and the emulsion resin contains emulsion styrene-acrylic resin.
Description
Technical Field
The invention belongs to the technical field of printing ink, and particularly relates to alcohol water type ink, a preparation method and application thereof.
Background
The volatilization of the dispersion medium in the ink causes problems such as air pollution, and most seriously, the ink for gravure printing, which contains a large amount of the organic dispersion medium. The long-term atmosphere of the organic dispersion medium with a high concentration causes great damage to the human body, and a part of the organic dispersion medium undergoes a photochemical reaction with nitrogen oxides in the air, causing air pollution. Therefore, with the enhancement of the social environmental protection consciousness and the food safety consciousness in China, people pay considerable attention to the problems of environmental hazards and human hazards of dispersing media such as benzene, ketone, ester and the like in the printing and using processes of food packaging. Therefore, the popularization of the alcohol-water type ink becomes a necessary result of the trend and the market demand.
Many products currently appearing on the market, which are self-called aqueous gravure inks or alcohol water type gravure inks, are actually added with organic dispersion media such as esters and ethers in order to improve the printability of the inks; or even if organic dispersion media such as esters and ethers are not added to the ink itself, in practical use, users usually need to add the dispersion media by themselves to improve the drying property and the printability of the ink, and the above types of inks cannot be considered as green environment-friendly ink materials. Further, in the case of an ink for gravure printing, an ink containing a dispersion medium of all alcohols is unstable and unsafe, and a dispersion medium of all water is difficult to meet the requirements for gravure printing on a non-absorbent substrate.
At present, patents and articles using only ethanol and water in combination as a dispersion medium have also been reported. However, such inks generally use emulsion type acrylic resins alone as a vehicle for an alcoholic water type ink, and have problems that: the use of emulsion acrylic resins alone cannot satisfy requirements for good fast-drying properties, good resolubility (generally, poor resolubility is considered to easily block a printing plate, resulting in a decrease in production efficiency), good resistance (i.e., friction/scratch resistance), and the like at the same time. In addition, the ink often has specific needs in actual use for printing equipment, which brings inconvenience to printing enterprises, for example, the printing enterprises are required to change to shallow screen printing (the depth of the cells of a printing plate for shallow screen printing is about 30-35 microns, the defects that the service life of the printing plate is shortened, the color of the printed product is not bright and the like exist), the length of the oven is increased, and the like.
For example, patent document 1 discloses an aqueous eco-friendly ink for gravure printing, which is prepared from the following raw materials in parts by weight: 18-22 parts of pigment, 15-23 parts of ethanol, 15-23 parts of water, 35-40 parts of water-based acrylic resin liquid, 0.5-1 part of polyethylene wax powder, 0.5-1.5 parts of water-based dispersant taking sodium dodecyl sulfate as a main component and 0.5-1.5 parts of surfactant taking sodium dicyanosuccinsulfonate as a main component. As analyzed by the present inventors, patent document 1 cannot satisfy requirements such as quick-drying property, good re-solubility, and resistance at the same time because it uses an aqueous acrylic resin alone as a binder for an alcoholic ink.
Patent document 2 discloses a novel environment-friendly water-washing ink and a preparation method thereof, wherein the ink comprises the following components in percentage by weight: 20 to 60 percent of water-soluble resin, 10 to 50 percent of acrylic acid copolymer resin emulsion, 10 to 15 percent of titanium dioxide, 0.5 to 1.5 percent of dispersant, 0 to 0.5 percent of defoamer, 0.1 to 1.5 percent of wetting agent, 0.1 to 1 percent of silicon dioxide, 5 to 18 percent of alcohol-water mixed dispersion medium and 0.1 to 1 percent of amination reagent; the water-soluble resin is one or two of water-soluble acrylic resin or water-soluble polyurethane. As analyzed by the present inventors, the ink of patent document 2 is a water-soluble water-washable ink, and it is apparent that the ink is poor in water resistance, and is not particularly suitable for the field of gravure printing, and the range of application is limited.
Patent documents:
patent document 1: CN107286731A
Patent document 2: CN109401434A
Disclosure of Invention
Problems to be solved by the invention
Based on the above-described technical problems in the art, the present invention aims to provide an alcohol aqueous ink which is effective in reducing emission of Volatile Organic Compounds (VOCs), is suitable for various substrates, has excellent printability, quick-drying property, re-solubility and an ink film (printed matter) formed therefrom has excellent adhesion, water resistance and excellent rub/scratch resistance, and is particularly suitable for gravure printing (hereinafter sometimes simply referred to as gravure).
Means for solving the problems
After the intensive research of the inventor, the technical problems can be solved by implementing the following technical scheme:
[1] an alcohol-water type ink comprises the following components in weight conversion:
3 to 25 parts of a water-soluble resin,
10 to 60 parts of an emulsion type resin,
0.05 to 2 parts of a wetting agent,
0-4 parts of scratch-resistant auxiliary agent,
8 to 35 parts of a dispersion medium,
wherein the dispersion medium is a mixture of alcohols and water, and the emulsion resin comprises emulsion styrene-acrylic resin.
[2] The alcohol-water type ink according to [1], wherein the water-soluble resin contains at least a water-soluble acrylic resin;
the concentration of the resin in the water-soluble resin, that is, the solid content of the water-soluble resin is 10 to 50 mass%; the resin concentration in the emulsion-type resin, i.e., the solid content of the emulsion-type resin, is 10 to 80 mass%.
[3] The alcohol-water type ink according to [1] or [2], the emulsion resin further comprising at least one of other emulsion acrylic resin and emulsion polyurethane resin.
[4] The alcohol-water type ink according to any one of [1] to [3], wherein a ratio of the alcohol to water in the dispersion medium is 6/4 to 9/1.
[5] The alcohol-water type ink according to any one of [1] to [4], wherein the alcohol is at least one of ethanol, n-propanol, isopropanol, and butanol.
[6] The alcohol aqueous ink according to any one of [1] to [5], wherein the scratch resistant auxiliary is silica.
[7] The alcohol-water type ink according to any one of [1] to [6], wherein the particle size of the emulsion type resin is not more than 100nm, the viscosity is 6-40 s (coated in a 4# cup), and the fineness is not more than 10 μm.
[8] The alcohol aqueous ink according to any one of [1] to [7], which comprises the following components by weight: 3-20 parts of water-soluble resin, 10-50 parts of emulsion type resin, 10-40 parts of colorant, 10-25 parts of dispersing medium, 0-3 parts of dispersing agent, 0-1.5 parts of defoaming agent, 0.2-2 parts of wetting agent, 0-5 parts of slip additive and 0.5-4 parts of scratch-resistant additive.
[9] A method for producing the alcohol-water type ink according to [1] to [8], comprising the steps of:
mixing, namely adding raw materials comprising water-soluble resin, emulsion resin, a scratch-resistant auxiliary agent and a wetting agent, and dispersing and grinding;
filtering, namely filtering and subpackaging after dispersing and defoaming the components in the mixing step;
a step of dilution, in which a dispersion medium is added to the mixture obtained in the step of filtration.
[10] Use of the alcohol water type ink according to [1] to [8] for gravure printing of a non-absorbent substrate.
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention provides an alcohol-water type ink which is effective in reducing emission of VOC. By using an emulsion type resin as a main resin, a water-soluble acrylic resin as an auxiliary resin and combining the two with a specific amount of a wetting agent, a scratch resistant aid, and a dispersion medium, the alcohol-water type ink of the present invention is suitable for various substrates including non-absorbent substrates such as PP, PET, PE substrates, and the like, has excellent printability, quick-drying properties, and an ink film formed therefrom has excellent adhesion, rubbing/scratch resistance, and water resistance; particularly by further using a scratch resistant auxiliary agent, the ink film (printed matter) formed from the alcohol-water type ink of the present invention can also have more excellent rubbing/scratch resistance. The viscosity of the alcohol-water type ink of the present invention may be 11s to 25 s.
In addition, the alcohol-water type ink is particularly suitable for gravure printing, conventional printing equipment and printing plates for gravure printing can be adopted, the printing equipment does not need to be replaced (a shallow net is used) or the length of an oven is not needed to be increased, the depth of the gravure printing plate is 20-45 mu m, and the printing speed can reach 60-200 m/min.
Detailed Description
The present invention will be described in detail below. The technical features described below are explained based on typical embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples.
It should be noted that:
in the present specification, the numerical range represented by "numerical value a to numerical value B" means a range including the end point numerical value A, B.
In this specification, the use of "at least" to indicate a range of values is meant to include the present number, and ranges greater than the present number, for example, "at least one" indicates a range of values of one, two, three … …; the numerical ranges indicated are one or more than one.
In the present specification, the use of "plural" means two or more.
In the present specification, the meaning of "may" or "may" includes both the meaning of performing a certain process and the meaning of not performing a certain process.
In this specification, "optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
In the present specification, reference to "some particular/preferred embodiments," "other particular/preferred embodiments," "embodiments," and the like, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments.
In the present specification, the term "acrylic" encompasses (meth) acrylic acid, (meth) acrylate salts, (meth) acrylate esters, and the like.
< alcohol Water type ink >
The invention provides alcohol-water type ink which comprises 3-25 parts of water-soluble resin, 10-60 parts of emulsion type resin, 0.05-2 parts of wetting agent, 0-4 parts of scratch-resistant auxiliary agent and 8-35 parts of dispersion medium in terms of weight. In the present invention, the dispersion medium is a mixture of alcohols and water, and the emulsion resin includes an emulsion styrene-acrylic resin.
From the viewpoint of more preferably obtaining the effects of the present invention, the ratio of the water-soluble resin to the emulsion-type resin in the alcohol-water ink of the present invention is preferably 0.8/9.2 to 5.0/5.0, more preferably 1.0/9.0 to 4.0/6.0, and still more preferably 1.2/8.8 to 2.5/7.5 by weight.
< Water-soluble resin >
In order to achieve the effects of the present invention, the alcohol-water type ink of the present invention contains 3 to 25 parts by weight, preferably 5 to 20 parts by weight, and more preferably 6 to 18 parts by weight of a water-soluble resin.
The term "water-soluble type" in the present specification means a state in which each component is dissolved in water. For example, the term "water-soluble resin" refers to a resin that contains a resin and water and is in a state in which the resin is dissolved in water. The resin concentration in the water-soluble resin of the present invention may be within a range known in the art. The resin concentration (solid content of the water-soluble resin) in the water-soluble resin of the present invention is preferably 10 to 50% by mass, more preferably 15 to 45% by mass, from the viewpoint of providing the water-soluble resin with more appropriate viscosity and better processability.
The water-soluble resin of the present invention is not particularly limited, and may be a water-soluble resin known in the art, and specific examples include, but are not limited to, water-soluble acrylic resins, water-soluble urethane resins, water-soluble polyester resins, water-soluble amino resins, and the like. These water-soluble resins may be used alone or in combination of two or more.
From the viewpoint of more preferably obtaining the effects of the present invention, the water-soluble resin of the present invention preferably contains at least a water-soluble acrylic resin. More preferably, the water-soluble resin of the present invention is only a water-soluble acrylic resin.
The concentration of the resin in the water-soluble acrylic resin of the present invention is preferably 20 to 45% by mass from the viewpoint of obtaining better blending property.
Specifically, examples of the method for producing the water-soluble acrylic resin of the present invention include, but are not limited to, resins obtained by introducing a functional monomer, such as acrylic acid, methacrylic acid, maleic anhydride, itaconic acid, β -hydroxyethyl acrylate, β -hydroxypropyl acrylate, acrylamide, methacrylamide, glycidyl acrylate, etc., into a polymer main chain, resins obtained by partially hydrolyzing an acrylate copolymer in an alkaline medium, resins obtained by introducing-OH, -CONH, and CONH onto a resin side chain2Or a hydrophilic group such as-O-; and the like. These copolymers may be used alone or in combination of two or more.
In some specific embodiments of the present invention, the number average molecular weight of the water-soluble acrylic resin of the present invention is in the range of 6000 to 50000 from the viewpoint of better achieving the effects of the present invention and obtaining good miscibility. The number average molecular weight is a value measured by Gel Permeation Chromatography (GPC) in terms of polystyrene.
< emulsion type resin >
In order to achieve the effects of the present invention, the content of the emulsion type resin in the alcohol-water type ink of the present invention is 10 to 60 parts by weight, preferably 12 to 55 parts by weight, and more preferably 15 to 50 parts by weight. In addition, the emulsion-type resin of the present invention is not particularly limited and may be one known in the art as long as it contains an emulsion-type styrene-acrylic resin.
In some embodiments, the emulsion type styrene-acrylic resin preferably accounts for 15% by weight or more of the emulsion type resin, more preferably 20% by weight or more of the emulsion type resin, from the viewpoint of better obtaining the effects of the present invention. In other embodiments, from the viewpoint of better obtaining the effects of the present invention, it is preferable that the emulsion type styrene-acrylic resin of the present invention is a self-crosslinking resin system. Herein, the term "self-crosslinking resin system" means: the polymer chains can be crosslinked into a network structure by self when the resin is made into a film. The self-crosslinking resin system can significantly further improve water resistance and solvent resistance and also improve mechanical strength and heat resistance.
The term "emulsion type" in the present specification means in an emulsified state. For example, the term "emulsion-type resin" refers to a resin that comprises a resin and water and is in an emulsified state. The solid content (concentration of the resin contained) of the emulsion-type resin of the present invention may be within a range known in the art, for example, 10 to 80% by mass. In order to obtain the effects of the present invention more favorably and easily obtain an emulsion resin, the solid content of the emulsion resin of the present invention is preferably 15 to 70 mass%, more preferably 25 to 65 mass%, and still more preferably 30 to 60 mass%.
The particle diameter of the resin particles in the emulsion-type resin of the present invention is preferably 120nm or less, more preferably 100nm or less, and still more preferably 80nm or less, from the viewpoint of being more suitable for gravure use. From the same viewpoint, the viscosity of the emulsion type resin of the present invention is preferably 6 to 40s (coat 4# cup) (coat 4# cup is a viscosity cup for measuring the viscosity of a liquid, and is suitable for measuring a liquid sample having a viscosity of less than 150 seconds); the fineness of the emulsion-type resin of the present invention is preferably 10 μm or less, which is measured by a blade fineness gauge (0 to 25 μm).
From the viewpoint of more preferably obtaining the effects of the present invention, it is preferable that the emulsion resin of the present invention further contains at least one of other emulsion acrylic resin and emulsion urethane resin in addition to the emulsion styrene-acrylic resin. Meanwhile, the content of other emulsion type acrylic resin and/or emulsion type urethane resin may be arbitrarily adjusted as needed as long as the content of the emulsion type resin in the alcohol water type ink and the ratio of the emulsion type styrene-acrylic resin in the emulsion type resin are satisfied.
The other emulsion type acrylic resin of the present invention is not particularly limited, and may be one known in the art except for emulsion type styrene-acrylic resins, and may be obtained in a known manner and may be linear, branched or cyclic. Specific examples include, without limitation, homopolymers of acrylic monomers, copolymers of different acrylic monomers, and copolymers of acrylic monomers with other copolymerizable monomers such as acrylonitrile, vinyl toluene, (meth) acrylamide, and the like. These polymers may be used alone or in combination of two or more. More preferably, from the viewpoint of further improving the suitability with the emulsion type styrene-acrylic resin of the present invention, the other emulsion type acrylic resin of the present invention is a homopolymer of an acrylic monomer or a copolymer of different acrylic monomers, that is, an emulsion type acrylic resin formed only of an acrylic monomer (sometimes referred to herein as an emulsion type pure acrylic resin).
The emulsion type polyurethane resin of the present invention is a resin including a urethane bond in the main chain. The emulsion type polyurethane resin of the present invention is not particularly limited, and may be obtained in a known manner and may be linear, branched or cyclic. Examples of the emulsion type polyurethane resin of the present invention include, but are not limited to, polyether type emulsion type polyurethane resins, polyester type emulsion type polyurethane resins, polyether-polyester hybrid type emulsion type polyurethane resins. From the viewpoint of better obtaining the effects of the present invention and further improving the suitability with the emulsion type styrene-acrylic resin of the present invention, more preferably, the emulsion type polyurethane resin of the present invention is a polyether type emulsion type polyurethane resin.
Most preferably, the emulsion-type resin of the present invention is composed of only the above-mentioned emulsion-type styrene-acrylic resin, at least one selected from the other emulsion-type acrylic resins described above and the above-mentioned emulsion-type polyurethane resins.
< wetting agent >
In order to achieve the effects of the present invention, in the alcohol-water type ink of the present invention, the content of the wetting agent of the present invention is 0.05 to 2 parts by weight, preferably 0.1 to 1.5 parts by weight, and more preferably 0.1 to 1 part by weight.
The main function of the wetting agent is to improve the stability of the ink and to improve the leveling and wetting of the ink, thereby achieving good film formation during printing, resulting in a smooth surface effect.
The wetting agent of the present invention may be any wetting agent known in the art; preferably, examples of wetting agents of the present invention include, but are not limited to, one or more of polyacrylates, silicones, acetylenic diols.
The wetting agent of the present invention may be a commercially available product, examples of which include 425, 381, WE3221, 346, 347, 349 (manufacturer: BYK); GA-100, E360, SE-F, D960, D800, 420 (manufacturer: air chemistry); WT-105A, W-461 (manufacturer: Hamming). These wetting agents may be used alone or in combination of two or more.
< scratch resistance Assistant >
In order to achieve the effects of the present invention, the content of the scratch resistant aid of the present invention in the alcohol-water type ink of the present invention is 0 to 4 parts by weight, preferably 0 to 3.5 parts by weight, and more preferably 0.5 to 3 parts by weight. Among them, it is to be noted that the content of the scratch resistant auxiliary agent of 0 part by weight means that the alcohol aqueous ink of the present invention does not contain the scratch resistant auxiliary agent.
The scratch-resistant auxiliary agent mainly has the function of improving the friction resistance and scratch resistance of printed matters.
The scratch resistance aid of the present invention is any scratch resistance aid known in the art. Specific examples include, without limitation: organic scratch-resistant auxiliaries such as organosilicone-based scratch-resistant auxiliaries, polystyrene-based scratch-resistant auxiliaries, polyvinyl chloride-based scratch-resistant auxiliaries, poly (meth) acrylate-based scratch-resistant auxiliaries, polypropylene-based scratch-resistant auxiliaries, polyethylene-based scratch-resistant auxiliaries, wax-based scratch-resistant auxiliaries and the like; inorganic scratch-resistant auxiliaries, such as silica, titanium dioxide, alumina, calcium silicate, calcium carbonate, clay, mica, talc and the like. These scratch resistance aids may be used alone or in combination of two or more. In the present invention, the scratch resistance aid is preferably silica.
In some embodiments of the invention, the silica is preferably nanoscale silica (hereinafter sometimes referred to simply as nanosilica). Further, in order to more preferably achieve the effect of the present invention, the particle size of the nano-silica is preferably 5nm to 80nm, more preferably 8nm to 60nm, and still more preferably 10nm to 30 nm.
< Dispersion Medium >
In order to achieve the effects of the present invention, in the alcohol-water type ink of the present invention, the content of the dispersion medium of the present invention is 8 to 35 parts by weight, preferably 10 to 30 parts by weight, and more preferably 12 to 25 parts by weight.
The dispersion medium mainly functions to carry the resin and various agents in the ink, to adjust the drying property and viscosity of the ink, and the like.
In order to achieve the effects of the present invention, particularly to reduce VOC as much as possible, the dispersion medium of the present invention is a mixture of water and alcohols. In general, the alcohol used is not particularly limited. In some specific embodiments of the present invention, the alcohol of the present invention is preferably at least one of ethanol, n-propanol, isopropanol, butanol. The alcohol of the present invention is preferably ethanol from the viewpoint of reducing the cost and further improving the performance of the ink.
The ratio of the alcohol to water in the dispersion medium of the present invention is not particularly limited and may be adjusted according to the properties of the support and the requirements of the print pattern, and it is generally considered that the more the alcohol, the higher the drying speed of the ink, but the more unfavorable is the print stability, the film forming property of the ink, and the like. In some specific embodiments of the present invention, the ratio of the alcohol to the water in the dispersion medium of the present invention is 6/4 to 9/1, and more preferably 6.5/3.5 to 8.5/1.5, from the viewpoint of better achieving the effects of the present invention.
< other auxiliary Agents >
The alcohol aqueous ink of the present invention may contain, in addition to the above components, other auxiliaries known in the art, for example, resins other than the above resins, wax emulsions, dispersants, antifoaming agents, slip aids, preservatives, mildewcides, bactericides, antioxidants, anti-reducing agents, ultraviolet absorbers, colorants (dyes, pigments, and the like), pH adjusters, and the like, within a range that does not impair the technical effects of the present invention. These auxiliaries may be used alone or in combination of two or more.
More preferably, neither the water-soluble resins nor the emulsion resins of the present invention react with an auxiliary. In other words, the ink of the present invention more preferably does not contain an auxiliary agent such as a crosslinking agent, an amination auxiliary agent, or the like which is easily reacted with various resins.
The following examples illustrate several adjuvants commonly used.
Dispersing agent
The dispersing agent mainly has the functions of entering particle gaps through wetting and permeating, generating directional adsorption on the particle surface, improving the particle surface performance, preventing the particles from being aggregated again, fully wetting the solid particles, easily dispersing and keeping the system stable.
The dispersant of the present invention is not particularly limited, and may be a dispersant known in the art. The dispersant of the present invention may be a commercially available product, examples of which include, but are not limited to, 2774, 4100, PCE, 4387, PTS, PL30, PL20 (manufacturer: clariant); 170. 179, 182, 3100, 3600 (manufacturer: air chemistry). These dispersants may be used alone or in combination of two or more.
In some embodiments of the present invention, the content of the dispersant is preferably 0.5 to 5 parts by weight, and more preferably 1 to 3 parts by weight.
Defoaming agent
It is generally believed that inks in which the dispersion medium contains water tend to foam, may hinder the dispersion of the pigment, may cause drying problems and color problems in the printed matter during printing and may cause pinholes or matte appearance in the printed matter. The main function of the antifoaming agent is to significantly improve the foaming phenomenon of the alcohol-water type ink.
In the present invention, the defoaming agent of the present invention is not particularly limited, and may be a defoaming agent known in the art. Specific examples include, but are not limited to, one or more of silicones, non-silicones.
The defoaming agent of the present invention may be a commercially available product, examples of which include, but are not limited to 845, 830, 825, 810 (manufacturer: digao); 093. 028, 024, 019, 012, 011 (manufacturer: BYK); DF110D, 107L, A5600 (manufacturer: air chemistry). These antifoaming agents may be used alone or in combination of two or more.
In some embodiments of the present invention, the content of the defoaming agent is preferably 0 to 1.5 parts by weight, more preferably 0.1 to 1 part by weight.
Slip aid
The main function of the slipping auxiliary agent is to further improve the adhesion, the rubbing resistance and the scratch resistance of the obtained ink film.
In the present invention, the slip aid of the present invention is not particularly limited, and may be any known slip aid in the art. Specific examples include, without limitation, one or more of a nonionic polyethylene wax microdispersion/emulsion, an aqueous wax slurry.
The slip aid of the present invention may be a commercially available product, examples of which include, but are not limited to, V-2000N, V-815A (manufacturer: Longtou); AQUATIX8421 (manufacturer: BYK); WE-5118B, WE-518B52 (manufacturer: Shanghai Xinnuo chemical Co., Ltd.); d-806, WE1, E-842N (manufacturer: Univak); JONCRYL Wax4, JONCRYL Wax 26 (manufacturer: BASF).
In some embodiments of the present invention, the slip aid is preferably present in an amount of 0 to 5 parts by weight, more preferably 1 to 4 parts by weight, and still more preferably 1 to 3.5 parts by weight.
Coloring agent
The colorant is a coloring material, and may be a pigment or a dye known in the art. The pigment or dye may be those well known in the art, for example, titanium dioxide, carbon black, iron oxide red, cobalt green, cobalt blue, condensed azo compounds, azo metal complexes, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, perylene compounds, methine compounds (meth compounds), allylamide compounds, pearlescent pigments, magnetic or magnetizable particle pigments, and the like.
Indices of colorants of the present invention include, but are not limited to, c.i.p.y.12, 13, 14, 15, 17, 42, 62, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 128, 129, 138, 147, 150, 151, 154, 155, 168, 180, 185, 214; c.i.p.r.2, 3, 5, 6, 7, 23, 48:2, 48:3, 48:4, 49:1, 53:1, 57:1, 81:1, 101, 122, 123, 146, 149, 166, 169, 170, 177, 184, 185, 202, 206, 220, 221, 238, 254, 269; c.i.p.v.3, 19, 23, 29, 30, 37, 40, 50; c.i.p.b.1, 7, 15:1, 15:2, 15:3, 15:4, 15:6, 22, 60, 62, 64, 66; c.i.p.bk.7.
In some embodiments of the present invention, the content of the colorant is preferably 10 to 40 parts by weight, more preferably 12 to 35 parts by weight, and still more preferably 15 to 30 parts by weight.
For example, in some embodiments of the present invention, the alcohol-water type ink comprises the following components by weight: 3-20 parts of water-soluble resin, 10-50 parts of emulsion type resin, 10-40 parts of colorant, 10-25 parts of dispersing medium, 0-3 parts of dispersing agent, 0-1.5 parts of defoaming agent, 0.2-2 parts of wetting agent, 0-5 parts of slip additive and 0.5-4 parts of scratch-resistant additive.
< preparation method of alcohol-water type ink >
The invention further provides a preparation method of the alcohol-water type ink, which comprises the following steps:
mixing, namely adding raw materials comprising water-soluble resin, emulsion resin, a scratch-resistant auxiliary agent and a wetting agent, and dispersing and grinding;
filtering, namely filtering and subpackaging after dispersing and defoaming the components in the mixing step;
a step of dilution, in which a dispersion medium is added to the mixture obtained in the step of filtration.
In the step of mixing, the dispersion grinding device includes a sand mill, a ball mill, a hammer mill, a homogenizer, a paint shaker, an ultrasonic dispersion device, a stirrer having a stirring blade, a magnetic stirrer, a high-speed dispersion device, and the like. In the present invention, the mixing step is preferably carried out at a dispersion rate of 1000-. In addition, the order of addition of the components is not particularly limited, and the components may be added simultaneously or in any order; each component can be added by a one-step process or in portions.
In the step of filtering, various filtering devices known in the art may be used.
In the step of dilution, the manner of addition of the dispersion medium is not particularly limited, and may be added in a one-step process or in portions.
After the step of filtering and before the step of diluting, a step of dispensing may be further included. In this step, various dispensing devices known in the art may be used.
< use of alcohol Water-based ink >
The alcohol water type ink of the present invention can be applied to various printing methods as needed, but is particularly suitable for gravure use. Particularly, the alcohol-water type ink is suitable for conventional printing equipment and printing plates, the depth of the printing plate is 20-45 mu m, and the printing speed is 60-200 m/min.
In the present invention, the alcohol water type ink can be widely used for various substrates, particularly PP, PET, PE substrates, and exhibits excellent adhesion, water resistance, and further excellent rub/scratch resistance on these substrates.
Examples
The present invention is described in detail below by way of examples, however, the scope of the present application is not limited to these examples. Unless otherwise specified, "part" means "part by weight" (sometimes also referred to as "part by mass"), "%" means "% by weight" (sometimes also referred to as "% by mass") hereinafter.
Example 1:
(1) dispersing and grinding 20 parts of water-soluble acrylic resin, 0.1 part of wetting agent (420), 1 part of dispersing agent (170) and 0.2 part of defoaming agent (845) at 1500 rpm, adding 15 parts of pigment (P.Y.12) after uniformly mixing, continuing to disperse and grind for 40-60min, and adding 35 parts of emulsion type resin (27 parts of emulsion type styrene-acrylic resin and 8 parts of emulsion type polyurethane resin), 0.1 part of wetting agent (346), 0.1 part of defoaming agent (028), 0.5 part of inorganic nano silicon dioxide and 1.5 parts of slip additive (E-842N).
Continuously dispersing and grinding for 30 min;
(2) filtering after the dispersed and ground original ink is completely defoamed, and subpackaging;
(3) before use, 25 parts of an alcohol-water mixture (a mixture of ethanol and water, the same shall apply hereinafter) was directly added to the base ink, with an alcohol-water ratio of 9/1.
Example 2:
(1) dispersing and grinding 8 parts of water-soluble acrylic resin, 0.6 part of wetting agent (420), 3 parts of dispersing agent (170), 0.5 part of defoaming agent (845: 0.2 part; 028:0.3 part) at 1500 rpm, adding 15 parts of pigment (P.Y.12) after uniformly mixing, continuing to disperse and grind for 40-60min, and adding 50 parts of emulsion type resin (30 parts of emulsion type pure acrylic resin, 12 parts of emulsion type styrene-acrylic resin and 8 parts of emulsion type polyurethane resin), 0.4 part of wetting agent (346), 0.5 part of defoaming agent (028), 3 parts of inorganic nano silicon dioxide and 2.5 parts of slip additive (E-842N). Continuously dispersing and grinding for 30 min;
(2) filtering after the dispersed and ground original ink is completely defoamed, and subpackaging;
(3) before use, 20 parts of an alcohol-water mixture was added directly to the base ink, the alcohol-water ratio being 7/3.
Example 3:
(1) dispersing and grinding 8 parts of water-soluble acrylic resin, 0.6 part of wetting agent (420), 3 parts of dispersing agent (170), 0.5 part of defoaming agent (845: 0.2 part; 028:0.3 part) at 1500 rpm, adding 15 parts of pigment (P.Y.12) after uniformly mixing, continuing to disperse and grind for 40-60min, adding 50 parts of emulsion type resin (30 parts of emulsion type pure acrylic resin, 12 parts of emulsion type styrene-acrylic resin and 8 parts of emulsion type polyurethane resin), 0.4 part of wetting agent (346), 0.5 part of defoaming agent (028), 1 part of inorganic nano silicon dioxide and 2.5 parts of slip additive (E-842N);
(2) filtering after the dispersed and ground original ink is completely defoamed, and subpackaging;
(3) before use, 20 parts of an alcohol-water mixture was added directly to the base ink, the alcohol-water ratio being 7/3.
Example 4:
(1) dispersing and grinding 8 parts of water-soluble acrylic resin, 0.6 part of wetting agent (420), 3 parts of dispersing agent (170), 0.5 part of defoaming agent (845: 0.2 part; 028:0.3 part) at 1500 rpm, adding 15 parts of pigment (P.Y.12) after uniformly mixing, continuing to disperse and grind for 40-60min, and adding 50 parts of emulsion type resin (30 parts of emulsion type pure acrylic resin, 12 parts of emulsion type styrene-acrylic resin and 8 parts of emulsion type polyurethane resin), 0.4 part of wetting agent (346), 0.5 part of defoaming agent (028) and 2.5 parts of slip additive (E-842N). Continuously dispersing and grinding for 30 min;
(2) filtering after the dispersed and ground original ink is completely defoamed, and subpackaging;
(3) before use, 20 parts of an alcohol-water mixture was added directly to the base ink, the alcohol-water ratio being 7/3.
Example 5:
(1) dispersing and grinding 10 parts of water-soluble acrylic resin, 0.5 part of wetting agent (GA-100), 2.5 parts of dispersing agent (PTS) and 0.3 part of defoaming agent (825) at 1500 rpm, adding 15 parts of pigment (P.R.53:1) after uniformly mixing, continuing to disperse and grind for 40-60min, and adding 40 parts of emulsion type resin (25 parts of emulsion type styrene-acrylic resin and 15 parts of emulsion type polyurethane resin), 0.3 part of wetting agent (D960), 0.3 part of defoaming agent (845: 0.2 part, 028: 0.1 part), 1.5 parts of inorganic nano silicon dioxide and 2.5 parts of slip additive (WE-518B 52). Continuously dispersing and grinding for 30 min;
(2) filtering after the dispersed and ground original ink is completely defoamed, and subpackaging;
(3) before use, 20 parts of an alcohol-water mixture was added directly to the base ink, the alcohol-water ratio being 8/2.
Example 6:
(1) dispersing and grinding 10 parts of water-soluble acrylic resin, 0.5 part of wetting agent (GA-100), 2.5 parts of dispersing agent (PTS) and 0.3 part of defoaming agent (825) at 1500 rpm, adding 15 parts of pigment (P.R.53:1) after uniformly mixing, continuing to disperse and grind for 40-60min, adding 40 parts of emulsion type resin (25 parts of emulsion type pure acrylic resin and 15 parts of emulsion type styrene-acrylic resin), 0.3 part of wetting agent (D960), 0.3 part of defoaming agent (845: 0.2 part, 028: 0.1 part), 1.5 parts of inorganic nano silicon dioxide and 2.5 parts of slip additive (WE-518B 52). Continuously dispersing and grinding for 30 min;
(2) filtering after the dispersed and ground original ink is completely defoamed, and subpackaging;
(3) before use, 20 parts of an alcohol-water mixture was added directly to the base ink, the alcohol-water ratio being 8/2.
Example 7:
an alcohol-water type ink was prepared in the same manner as in example 6, except that in step (3), the alcohol-water ratio was changed to 9/1.
Example 8:
an alcohol-water type ink was prepared in the same manner as in example 6, except that in step (3), the alcohol-water ratio was changed to 7/3.
Example 9:
an alcohol-water type ink was prepared in the same manner as in example 6, except that in step (3), the alcohol-water ratio was changed to 5/5.
Example 10:
an alcohol-water type ink was prepared in the same manner as in example 6, except that in step (3), 12.5 parts of the alcohol-water mixture (alcohol-water ratio of 8/2) was changed to be added.
Example 11:
(1) dispersing and grinding 10 parts of water-soluble acrylic resin, 1.2 parts of wetting agent (W461), 3 parts of dispersing agent (3100) and 0.6 part of defoaming agent (DF110D) at 1500 rpm, adding 30 parts of pigment (titanium dioxide) after uniformly mixing, continuing to disperse and grind for 40-60min, and adding 15 parts of emulsion type resin (15 parts of emulsion type styrene-acrylic resin), 0.8 part of wetting agent (E360), 0.4 part of defoaming agent (810), 1.5 parts of inorganic nano-silica and 2.5 parts of slip additive (JONCRYL Wax 4). Continuously dispersing and grinding for 30 min;
(2) filtering after the dispersed and ground original ink is completely defoamed, and subpackaging;
(3) before use, 20 parts of an alcohol-water mixture was added directly to the base ink, the alcohol-water ratio being 8/2.
Example 12:
an aqueous alcoholic ink was prepared in the same manner as in example 3, except that in step (1), 50 parts of emulsion type resin (36 parts of emulsion type pure acrylic resin, 6 parts of emulsion type styrene-acrylic resin, and 8 parts of emulsion type urethane resin) was changed to be added.
Example 13:
an aqueous alcoholic ink was prepared in the same manner as in example 3, except that in step (1), 50 parts of emulsion type resin (34 parts of emulsion type pure acrylic resin, 8 parts of emulsion type styrene-acrylic resin, and 8 parts of emulsion type urethane resin) was changed to be added.
Example 14:
an aqueous alcoholic ink was prepared in the same manner as in example 3, except that in step (1), 58 parts of an emulsion type resin (30 parts of an emulsion type pure acrylic resin, 20 parts of an emulsion type styrene-acrylic resin, and 8 parts of an emulsion type urethane resin) was changed to be added.
Example 15:
an alcoholic water type ink was prepared in the same manner as in example 6 except that in step (1), 20 parts of a water-soluble acrylic resin was changed to be added.
Comparative example 1:
an ink was prepared in the same manner as in example 6, except that in step (3), the addition of 20 parts of the alcohol-water mixture was changed to the addition of 20 parts of water.
Comparative example 2:
an alcohol-water type ink was prepared in the same manner as in example 6, except that in step (3), the addition of 20 parts of the alcohol-water mixture was changed to the addition of 40 parts of the alcohol-water mixture.
Comparative example 3:
an aqueous alcoholic ink was prepared in the same manner as in example 3, except that in step (1), 65 parts of an emulsion type resin (30 parts of an emulsion type pure acrylic resin, 27 parts of an emulsion type styrene-acrylic resin, and 8 parts of an emulsion type urethane resin) was changed to be added.
Comparative example 4:
an alcoholic water type ink was prepared in the same manner as in example 6 except that in step (1), 28 parts of a water-soluble acrylic resin was changed to be added.
Comparative example 5:
an aqueous alcoholic ink was prepared in the same manner as in example 11, except that 15 parts of the emulsion type styrene-acrylic resin was changed to 15 parts of the emulsion type pure acrylate in the step (1).
The kinds and/or amounts (based on parts by weight) of the respective components used for preparing the alcohol-water type inks of the respective examples and comparative examples are shown in table 1.
TABLE 1
In the present invention, the viscosity of the ink was measured according to the method of GB/T13217.4-2008.
In the present invention, the fineness of the ink was measured by the method of GB/T13217.3-2008.
In the present invention, the adhesion of the ink to PP, PET, PE was measured according to the method of GBT 13217.7-2009.
In the present invention, the abrasion resistance of the ink was measured according to ISO 12137-1: 1997. In the present invention, the larger the value of "abrasion resistance (%)" is, the better.
In the present invention, the water resistance of the ink was measured according to the water resistance test method of paint film in GB1733-1993, and when the water resistance satisfies the requirements of the present invention and evaluated as excellent, the water resistance was marked as √ where the water resistance satisfies the requirements of the present invention and evaluated as good, the water resistance was marked as ○, and when the water resistance does not satisfy the requirements of the present invention, the water resistance was marked as × ".
In the present invention, the drying rate of the ink was measured. The specific determination process is as follows: using a 0-50 mu m double-groove scraper fineness instrument, respectively dropping a standard ink sample and a test ink sample into the deepest part of a chute, wherein the dropping amount is suitable for filling the slightly redundant surface of the chute, transversely placing a scraper on the upper end of the scraper by using a thumb, an index finger and a middle finger of two hands, forming an angle of 85 degrees between the scraper and the scraper, quickly and uniformly scraping the scraper on the whole surface to one end with zero groove depth within 3s, aligning one end of a film with a 50 mu m groove of the scraper after sample scraping is finished, slightly pressing the film with a hand to ink the film and immediately taking the film up, simultaneously timing, and measuring the time for drying the ink at the position of 50 mu m, namely the drying property, which is expressed by s. In the present invention, the shorter the drying time, the better.
In the present invention, the maximum printing speed of the ink was measured. The specific determination process is as follows: the test was carried out on a gravure press (oven temperature 60 ℃, oven tunnel length 1.2 m, plate cell depth 30-35 μm) with a corona treated PP, PET or PE substrate. In the present invention, the higher the maximum printing speed, the better.
The results of various performance evaluations in each example and comparative example are shown in table 2.
TABLE 2
The above embodiments are merely examples for clearly illustrating the present invention and do not limit the present invention. It will be apparent to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications are therefore intended to be included within the scope of the invention as claimed.
Claims (10)
1. An alcohol-water type ink is characterized by comprising the following components in weight conversion:
3 to 25 parts of a water-soluble resin,
10 to 60 parts of an emulsion type resin,
0.05 to 2 parts of a wetting agent,
0-4 parts of scratch-resistant auxiliary agent,
8 to 35 parts of a dispersion medium,
wherein the dispersion medium is a mixture of alcohols and water, and the emulsion resin comprises emulsion styrene-acrylic resin.
2. The alcohol-water type ink according to claim 1, wherein the water-soluble resin contains at least a water-soluble acrylic resin;
the concentration of the resin in the water-soluble resin, that is, the solid content of the water-soluble resin is 10 to 50 mass%; the resin concentration in the emulsion-type resin, i.e., the solid content of the emulsion-type resin, is 10 to 80 mass%.
3. The alcohol-water type ink according to claim 1 or 2, wherein the emulsion type resin further comprises at least one of other emulsion type acrylic resin and emulsion type urethane resin.
4. The alcohol-water type ink according to any one of claims 1 to 3, wherein a ratio of the alcohol to the water in the dispersion medium is 6/4 to 9/1.
5. The alcohol-water type ink according to any one of claims 1 to 4, wherein the alcohol is at least one of ethanol, n-propanol, isopropanol, and butanol.
6. The alcohol water type ink according to any one of claims 1 to 5, wherein the scratch resistance auxiliary agent is silica.
7. The alcohol-water type ink according to any one of claims 1 to 6, wherein the emulsion type resin has a particle diameter of 100nm or less, a viscosity of 6 to 40s (in a 4# cup), and a fineness of 10 μm or less.
8. The alcohol-water type ink according to claim 1, wherein the alcohol-water type ink comprises the following components by weight: 3-20 parts of water-soluble resin, 10-50 parts of emulsion type resin, 10-40 parts of colorant, 10-25 parts of dispersing medium, 0-3 parts of dispersing agent, 0-1.5 parts of defoaming agent, 0.2-2 parts of wetting agent, 0-5 parts of slip additive and 0.5-4 parts of scratch-resistant additive.
9. A method for preparing an alcohol-water type ink according to claims 1 to 8, comprising the steps of:
mixing, namely adding raw materials comprising water-soluble resin, emulsion resin, a scratch-resistant auxiliary agent and a wetting agent, and dispersing and grinding;
filtering, wherein the components in the mixing step are filtered after being dispersed and defoamed;
a step of dilution, in which a dispersion medium is added to the mixture obtained in the step of filtration.
10. Use of the alcohol water type ink according to claims 1-8 for gravure printing of non-absorbent substrates.
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