JP2017171910A - Coating agent composition for printing and printed matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating agent composition for printing which can form a coating film by printing, the coating film having excellent touch feeling and rub resistance.SOLUTION: A coating agent composition for printing comprises resin particles (A) with a glass-transition temperature of -80°C to -35°C and an average particle size of 2 μm to 20 μm, thermoplastic binder resin (B), and organic solvent (C).SELECTED DRAWING: None

Description

  The present disclosure relates to a coating agent composition for printing, which can form a coating film by printing and has a good touch feeling and friction resistance. Moreover, this indication is related with the printed matter which has a coating layer formed using the said coating agent composition for printing.

  Conventionally, electrical and electronic equipment related parts such as personal computer casings, automobile interior parts such as instrument panels, center consoles, dashboards, and door trims, chairs, armrests, handrails, window frames, and door knobs The surface of plastic products for applications such as parts and furniture-related parts, or the surface of paper products for packaging boxes such as cosmetic boxes is usually glossy from the standpoint of design such as profoundness and luxury. A matte paint film is formed using a matte paint. In recent years, it has been demanded to further improve the touch feeling of such a matte coating film.

In response to this demand, for example, a paint containing resin fine particles, a polycarbonate-based or polyester-based polyol main component, and a polyisocyanate-based curing agent is spray-coated on a plastic substrate, and then the coating film is cured. Has proposed a method of imparting a good tactile sensation to the plastic surface (Patent Documents 1 and 2). In general, as a method for forming a coating film, a printing method is superior to a spray coating method in terms of productivity and efficiency.
However, when the coating material is applied to a substrate by a printing method, the coated film after application is usually in an uncured state, and blocking occurs during winding. Therefore, the paint is unsuitable for a printing method. Even if the coating film is thermally cured to prevent blocking, an aging process is also required for thermosetting, which causes a reduction in production yield. In addition, a thermosetting paint using a polyisocyanate compound has a drawback that the pot life of the remaining paint is short because the reaction proceeds with the polyol even at room temperature.

  On the other hand, as the current mainstream technology in this field, a method is known in which resin fine particles are blended into a composition containing an acrylate group, and this is cured with active energy rays (ultraviolet rays or electron beams) after coating ( Patent Document 3). The coating film formed by such a method has a good tactile sensation, but has a complicated layer structure and requires a curing step by irradiation with ultraviolet rays or electron beams. Therefore, further improvement is desired in terms of printing speed or productivity.

  In view of the above, a coating agent that can form a coating film easily and that can form a coating film excellent in touch feeling with high productivity is desired.

JP 2008-063395 A JP2015-105298A Japanese Patent Application Laid-Open No. 2015-066731

  An object of this invention is to provide the coating agent composition for printing which can form a coating film by printing in view of said situation, and the touch feeling of a coating film and friction resistance are favorable. .

  As a result of intensive studies, the present inventor has found that the above-mentioned problems can be solved by using the printing coating composition described below, and has reached the present invention. That is, the aspect of the present invention relates to the following.

  The first aspect of the present invention comprises a resin particle (A) having a glass transition temperature in the range of −80 ° C. to −35 ° C. and an average particle diameter in the range of 2 μm to 20 μm, and a thermoplastic binder resin ( It is related with the coating agent composition for printing containing B) and the organic solvent (C).

  In one Embodiment, it is preferable that the said resin particle (A) is a polyurethane-type resin particle (a-1).

  In one embodiment, the polyurethane-based resin particles (a-1) preferably include a structural unit derived from polyester composed of adipic acid and 3-methyl-1,5-pentanediol.

  In one embodiment, the thermoplastic binder resin (B) comprises a polyurethane resin (b-1), a cellulose resin (b-2), and a vinyl chloride-vinyl acetate copolymer (b-3). It is preferably at least one selected from the group.

  In one embodiment, the polyurethane resin (b-1) is selected from the group consisting of a structural unit derived from a polyester polyol (b-1-1) and a structural unit derived from a polyether polyol (b-1-2). Preferably, at least one of the above is included.

  In one Embodiment, it is preferable that the said cellulose resin (b-2) contains a nitrocellulose resin.

  In one Embodiment, it is preferable that the said organic solvent (C) does not contain an aromatic organic solvent.

  A second aspect of the present invention relates to a printed material having a coating layer formed using the above-described coating agent composition for printing. In one embodiment, the printed matter has a substrate having a printing ink layer at least in part, and a coating layer formed using the printing coating composition on the printing ink layer of the substrate. Is preferred.

  In one embodiment, in the printed matter, the substrate is preferably a paper substrate.

  In one embodiment, the substrate is preferably a plastic substrate.

  By using the coating agent composition for printing of the present disclosure, it is possible to form a coating film having good touch feeling and friction resistance by printing, and to provide a printed matter having good touch feeling and friction resistance. can do.

  DESCRIPTION OF EMBODIMENTS Embodiments of the present invention will be described in detail below, but the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention, and the present invention includes these contents as long as the gist thereof is not exceeded. It is not limited to.

  In the present specification, the “glass transition temperature” is measured by a differential scanning calorimeter (DSC) and indicates the temperature at the midpoint of the temperature range where the glass transition occurs. The “average particle size” indicates the particle size at an integrated value of 50% (D50) in the particle size distribution obtained by the laser diffraction scattering method.

In one embodiment, the coating agent composition for printing satisfies the following (1), (2) and (3).
(1) It contains resin particles (A) having a glass transition temperature in the range of −80 ° C. to −35 ° C. and an average particle diameter in the range of 2 μm to 20 μm.
(2) Contains a thermoplastic binder resin (B).
(3) Contains an organic solvent (C).

  The weight ratio of the resin particles (A), the thermoplastic binder resin (B), and the organic solvent (C) in the coating composition for printing is (A) :( B) :( C) = 5% -15%: 5% -40%: 45% -85% is preferable (however, the sum of (A) to (C) is 100% by weight, and (A) and (B) are in terms of solid content. Value). When the weight ratio of each component is within the above range, it becomes easy to adjust the viscosity to be suitable for various printing methods.

<Resin particles (A)>
Usable resin particles (A) have a glass transition temperature in the range of −80 ° C. to 35 ° C. (hereinafter sometimes referred to as Tg) and an average particle size in the range of 2 μm to 20 μm.
If the average particle diameter of the resin particles is within the above range, a coating film having excellent unevenness that imparts a visual matte feeling can be easily formed by printing using the coating agent composition for printing. . On the other hand, when the glass transition temperature of the resin particles is within the above range, it is easy to realize a good touch feeling such as flexibility, moist feeling, and smoothness in the coating film. This is due to the fact that the resin particles constituting the convex portion of the coating film that actually touch the hand have a specific range of Tg. From these, by using resin particles having both a glass transition temperature in a specific range and an average particle diameter in a specific range, a coating film obtained by applying a coating composition for printing to a substrate is excellent. It is easy to obtain a feeling of touch.
More specifically, when the Tg of the resin particles is −35 ° C. or less, it is possible to suppress the feeling of touch becoming hard. When Tg of the resin particles is −80 ° C. or higher, deterioration of the heat resistance of the resin particles themselves can be suppressed, and further, the blocking resistance of the printed matter can be enhanced. In addition, when the average particle diameter of the resin particles is 2 μm or more, it is easy to obtain a desired touch feeling. When the average particle diameter of the resin particles is 20 μm or less, embrittlement of the coating film can be suppressed.

The glass transition temperature of the resin particles (A) is preferably −80 ° C. or higher, more preferably −75 ° C. or higher, still more preferably −70 ° C. or higher, and particularly preferably −65 ° C. or higher. On the other hand, the glass transition temperature is preferably −35 ° C. or lower, preferably −38 ° C. or lower, more preferably −40 ° C. or lower, and particularly preferably −45 ° C. or lower. In one embodiment, the glass transition temperature is more preferably in the range of −60 ° C. to −40 ° C.
The average particle diameter of the resin particles (A) is preferably 2 μm or more, more preferably 3 μm or more, further preferably 4 μm or more, and most preferably 5 μm or more. On the other hand, the average particle size is preferably 20 μm or less, more preferably 18 μm or less, still more preferably 16 μm or less, and particularly preferably 15 μm or less. In one embodiment, the average particle size is more preferably in the range of 3 μm to 18 μm, still more preferably in the range of 4 μm to 16 μm.

The resin particles (A) are not particularly limited as long as the resin particles (A) satisfy the glass transition temperature range and the average particle diameter range. Examples of resins that can constitute the resin particles (A) include polyurethane resins, polynylon resins, polyacryl resins, polysilicon resins, polystyrene resins, melamine resins, polyester resins, polyethylene resins, and the like. Can be mentioned. For example, a polyurethane resin means a resin having a urethane bond and a derivative thereof.
In order to constitute the resin particles (A), the resins exemplified above may be used alone or in combination of two or more. An example of using two or more resins in combination is a polyurethane acrylic resin. In one embodiment, the resin particles (A) are preferably composed of at least one resin selected from the group consisting of a polyurethane resin and a polyacrylic resin.
The resin particles (A) can be produced according to a known method. Moreover, you may use a commercial item. For example, the product name “SS-010T” (Tg: −44 ° C., average particle size: 10 μm) manufactured by Negami Kogyo Co., Ltd. can be used as the resin particles composed of a polyacrylic resin.
Among the exemplified resins, in one embodiment, it is more preferable to use resin particles (a-1) composed of a polyurethane resin (hereinafter referred to as polyurethane resin particles (a-1)).
The blending amount of the resin particles (A) is preferably in the range of 20 to 40% by weight based on the total weight of the solid component in the coating composition for printing, from the viewpoint of expressing a good touch feeling. The blending amount is more preferably in the range of 25 to 40% by weight, and further preferably in the range of 27 to 37% by weight.

(Polyurethane resin particles (a-1))
The polyurethane resin particles (a-1) preferably include a structural unit derived from the polyol (a1) and a structural unit derived from the polyisocyanate (a2). Such polyurethane resin particles (a-1) can be obtained by a reaction between the polyol (a1) and the polyisocyanate (a2).
Examples of the usable polyol (a1) include polyester polyol, polyether polyol, polycarbonate polyol, polycaprolactone polyol, and acrylic polyol. In the range where the glass transition temperature (Tg) of the obtained polyurethane resin particles (a-1) is from −80 ° C. to −35 ° C., the above polyol compound may be used alone or in combination of two or more. May be.

The number average molecular weight of the polyol (a1) is preferably in the range of 1,000 to 10,000, more preferably in the range of 1,500 to 8,000, and still more preferably in the range of 2,000 to 6,000. In addition, the number average molecular weight of the polyol described in the present specification is based on the number of hydroxyl groups (valence) in one molecule of polyol and the hydroxyl value in 1 g of polyol solids (converted to the amount of potassium hydroxide in terms of potassium hydroxide amount). It is calculated and is obtained by the following (formula 1).
(Formula 1)
Number average molecular weight of polyol = 1000 × 56.1 × hydroxyl number of hydroxyl group / hydroxyl value

In one embodiment, it is preferable to use at least a polyester polyol as the polyol (a1). The polyester polyol may be a condensate obtained by an esterification reaction between a dibasic acid and a diol, for example.
Dibasic acid is, for example, adipic acid, phthalic anhydride, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, pimelic acid, azelaic acid, sebacic acid, suberic acid, glutaric acid, It may be at least one selected from the group consisting of 1,4-cyclohexyl dicarboxylic acid, dimer acid, and hydrogenated dimer acid.
Examples of the diol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, and 1,8-octane. Diol, 1,9-nonanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 3,3,5-trimethylpentanediol, 2,4-diethyl -1,5-pentanediol, 1,12-octadecanediol, 1,2-alkanediol, 1,3-alkanediol, 1-monoglyceride, 2-monoglyceride, 1-monoglycerin ether, 2-monoglycerin ether, dimer Diol and hydrogenated dimer It may be at least one selected from the Canal group.
Among the polyester polyols obtained by the reaction of the dibasic acid and the diol, a polyester polyol composed of adipic acid and a diol having a branched structure from the viewpoint of reducing the Tg of the polyurethane resin particles (a-1). Is preferred. The diol having a branched structure may be neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol and the like. Among these, a polyester polyol composed of adipic acid and 3-methyl-1,5-pentanediol is more preferable.
As the polyol (a1), one of the above polyester polyols may be used alone, or two or more of them may be mixed and used. Furthermore, in addition to the dibasic acid and diol, a polyol having 3 or more hydroxyl groups and a polyvalent carboxylic acid having 3 or more carboxyl groups may be used.

The polyisocyanate (a2) may be any of yellowing type, non-yellowing type, and hardly yellowing type. Specific examples of the polyisocyanate (a2) include aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates. Although not particularly limited, typically, aromatic diisocyanates can be broadly classified as yellowing polyisocyanates, and aliphatic and alicyclic diisocyanates can be broadly classified as non-yellowing polyisocyanates.
Examples of the aromatic diisocyanate include 4,4′-diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), and the like. Examples of the aliphatic diisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), and the like. Examples of the alicyclic diisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI).
As the polyisocyanate (a2), at least one selected from the group consisting of an isocyanurate compound (trifunctional) and a uretdione compound (bifunctional) can also be used. The isocyanurate compound and uretdione compound can also be formed from the various diisocyanate compounds exemplified above. Moreover, terminal isocyanate group containing polyisocyanate (For example, adduct type polyisocyanate, biuret type polyisocyanate etc.) can also be used as polyisocyanate (a2).

  Among the polyisocyanates (a2), isocyanurate compounds or uretdione compounds are preferable because they are low in volatility and have moderate reactivity. Furthermore, an isocyanurate compound or uretdione compound (bifunctional) formed from a non-yellowing type diisocyanate monomer is more preferable, and an isocyanurate compound or uretdione formed from HDI in that the blending amount can be reduced because the molecular weight is small. Compounds are particularly preferred.

  As a method for producing the polyurethane resin particles (a-1), for example, the method (suspension polymerization) described in JP 2010-024319 A or JP 2009-197067 can be applied. It is.

<Thermoplastic binder resin (B)>
As the thermoplastic binder resin (B), a resin capable of forming a solid coating film can be appropriately selected and used after printing of the printing coating composition. Here, “solid coating film” means that the coating film is solid at room temperature and normal pressure, and does not mean a cured coating film. That is, the binder resin (B) is composed of a thermoplastic resin that has the property of being softened and molded by heating and solidifying when cooled, and is usually solid at room temperature and normal pressure (25 ° C., 1 atm). It is.
In one embodiment, the thermoplastic binder resin (B) may have rubber elasticity. In this case, the glass transition temperature of the resin is preferably in the range of −50 ° C. to 40 ° C., and the storage elastic modulus at 40 ° C. in the dynamic viscoelasticity measurement is preferably 1 to 100 MPa. In another embodiment, the thermoplastic binder resin (B) may not have rubber elasticity. In this case, the glass transition temperature of the resin is preferably 40 ° C to 200 ° C. Any of the above thermoplastic binder resins (B) are preferably soluble in the organic solvent (C) described later.

  In this specification, “rubber elasticity” means that polymer chains are partially bonded or agglomerated to form a three-dimensional network structure and behave like a solid, while Brownian motion occurs in a part of the polymer chains. Since it can take various conformations partly without stopping, it shows the property that elasticity appears remarkably.

Examples of the thermoplastic binder resin (B) include polyurethane resin (b-1), cellulose resin (b-2), vinyl chloride-vinyl acetate copolymer (b-3), vinyl chloride-acrylic resin. Copolymer resin, ethylene-vinyl acetate copolymer resin, vinyl acetate resin, acrylic resin, polyester resin, alkyd resin, polyvinyl chloride resin, rosin resin, rosin modified maleic acid resin, terpene resin, phenol modified terpene resin, Examples thereof include ketone resins, cyclized rubbers, chlorinated rubbers, butyrals, polyacetal resins, petroleum resins, and modified resins thereof. These resins can be used alone or in admixture of two or more.
Among them, at least one selected from the group consisting of a polyurethane resin (b-1), a cellulose resin (b-2), a vinyl chloride-vinyl acetate copolymer (b-3), and a ketone resin. It is preferable to use it. It is more preferable to use at least one selected from the group consisting of a polyurethane resin (b-1), a cellulose resin (b-2), and a vinyl chloride-vinyl acetate copolymer (b-3). .

  The thermoplastic binder resin (B) may have a linear structure, a branched structure, a crosslinked structure, or a graft structure. The molecular weight of the thermoplastic binder resin (B) is preferably a range of 5,000 to 100,000 in terms of weight average molecular weight. More preferably, it is the range of 10,000-80,000, More preferably, it is the range of 10,000-60,000, Most preferably, it is the range of 30,000-40,000.

Generally, in a coating composition containing a curable binder resin such as energy beam curable or thermosetting, the coating film obtained after the curing step is hard, and the compatibility between the binder resin and the resin particles having a low glass transition temperature. Tend to be low (unfamiliar). Therefore, the resin particles are peeled off from the surface of the coating film, or a rough feeling is likely to occur, resulting in problems such as poor touch. In addition, the above-mentioned curable coating agent composition is not preferable because, when printing, if it is wound before the coating curing step, blocking occurs.
On the other hand, a thermoplastic binder resin (B) is used in the printing coating composition of the present disclosure. The thermoplastic binder resin (B) has a certain degree of flexibility and can form a coating film having sufficient strength by printing. Therefore, the hardening process implemented using an ultraviolet-ray or an electron beam after printing is not required.
From such a viewpoint, in one embodiment, it is preferable that the binder resin (B) does not have an unsaturated double bond group such as a (meth) acrylate group. For the same reason, it is preferable that the thermoplastic binder resin (B) is not liquid at room temperature and pressure and does not have fluidity.
Usually, when an energy ray curable or thermosetting binder resin is used, the coating film after printing (before curing) is sticky, and it is difficult to wind up the printed material before the curing step. On the other hand, when the thermoplastic binder resin is used, a solid coating film can be easily obtained simply by drying the coating film. Therefore, it is possible to wind up the printed material after gravure printing.

Hereinafter, specific examples of resins that can be suitably used as the thermoplastic binder resin (B) will be described.
(Polyurethane resin (b-1))
The polyurethane-based resin (b-1) is not particularly limited. For example, an isocyanate terminal group-containing structural unit composed of a structural unit derived from the polyol (b1) and a polyisocyanate (b2) structural unit is derived from the amine compound (b3). It is preferable to have the structure connected with the structural unit of.

  As the polyol (b1), for example, at least one selected from the group consisting of polyester polyol, polyether polyol, polycaprolactone polyol, and polycarbonate polyol is preferable. Among these, it is more preferable to include at least one selected from the group consisting of polyester polyol (b-1-1) and polyether polyol (b-1-2). In one embodiment, the polyol (b1) further preferably includes a polyester polyol (b-1-1) and a polyether polyol (b-1-2).

In one embodiment, the content of the polyester polyol (b-1-1) is desirably 40% by weight or more and 90% by weight or less based on the total amount of the polyol (b1) component. More preferably, they are 50 weight% or more and 85 weight% or less, More preferably, they are 60 weight% or more and 80 weight% or less.
When the amount of the polyester polyol in the polyol (b1) is within the above range, it becomes easy to obtain a print coat layer having appropriate hardness and touch feeling and excellent touch feeling.

The polyester polyol (b-1-1) may be a condensate obtained by an esterification reaction between a dibasic acid and a diol, for example.
Dibasic acid is, for example, adipic acid, phthalic anhydride, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, pimelic acid, azelaic acid, sebacic acid, suberic acid, glutaric acid, It may be at least one selected from the group consisting of 1,4-cyclohexyldicarboxylic acid, dimer acid, and hydrogenated dimer acid.
Examples of the diol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, and 1,8-octane. Diol, 1,9-nonanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 3,3,5-trimethylpentanediol, 2,4-diethyl -1,5-pentanediol, 1,12-octadecanediol, 1,2-alkanediol, 1,3-alkanediol, 1-monoglyceride, 2-monoglyceride, 1-monoglycerin ether, 2-monoglycerin ether, dimer Diol and hydrogenated dimer It may be at least one selected from the group consisting of.
Among the polyester polyols obtained by the reaction of the dibasic acid and the diol, when used as a thermoplastic binder resin, adipic acid and a branched structure are used in terms of miscibility with the polyurethane resin particles (a-1). Polyester polyols composed of diols having the following are preferred. The diol having a branched structure may be, for example, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol and the like. Among these, a polyester polyol composed of adipic acid and 3-methyl-1,5-pentanediol is particularly preferable.
These polyester polyols (b-1-1) may be used alone or in combination of two or more. Furthermore, in addition to the dibasic acid and diol, a polyol having 3 or more hydroxyl groups and a polyvalent carboxylic acid having 3 or more carboxyl groups can be used.

  In one embodiment, the polyurethane resin particles (a-1) and the polyurethane resin (b-1) can be used at the same time in order to constitute the coating agent composition for printing. In this case, the compatibility between the resin particles and the binder resin and the tactile sensation of the printed coating film are improved, so that (a-1) and (b-1) contain structural units derived from the same polyol. Is preferred. The above (a-1) and (b-1) more preferably include a structural unit derived from a polyester polyol having the same structure. The polyester polyol is more preferably a polyester polyol composed of adipic acid and 3-methyl-1,5-pentanediol.

  The number average molecular weight of the polyester polyol (b-1-1) is appropriately determined in consideration of the solubility, drying property, blocking resistance and the like of the resulting polyurethane resin. The number average molecular weight is usually in the range of 500 to 10,000, preferably in the range of 1,000 to 5,000. When the number average molecular weight is 500 or more, the amount of hard segments does not become excessive, so that the solubility is improved and the printability is easily improved. Moreover, when it is 10,000 or less, the amount of hard segments does not become too small, and it is easy to obtain good drying properties and blocking resistance. In addition, the number average molecular weight of the polyol described in the present specification is calculated from the hydroxyl value with the terminal as a hydroxyl group, and is obtained by the above-described (Formula 1).

  The acid value of the polyester polyol (b-1-1) is preferably 1.0 mgKOH / g or less, and more preferably 0.5 mgKOH / g or less. When the acid value is adjusted to 1.0 mgKOH / g or less, it becomes easy to suppress the increase in viscosity of the varnish of the polyurethane resin (b-1) over time.

Examples of the polyether polyol (b-1-2) include polyether polyols that are polymers such as ethylene oxide, propylene oxide, and tetrahydrofuran, or copolymers composed of a combination of two or more of these. In particular, polytetramethylene glycol, polypropylene glycol, and polyethylene glycol are superior to an organic solvent (C) that does not contain an aromatic organic solvent (hereinafter sometimes referred to as “non-toluene organic solvent”). It has high solubility. Therefore, it is preferable in terms of improving printability, and polypropylene glycol is particularly preferable.
On the other hand, in order not to lower the water resistance, the number average molecular weight of the polyether polyol (b-1-2) is preferably in the range of 700 to 3,000, more preferably in the range of 800 to 2,500, and still more preferably. Is in the range of 1,000 to 2,500. Moreover, from the point which improves the solubility with respect to the organic solvent (C) of a polyurethane-type resin (b-1), content of polyether polyol (b-1-2) is based on all the components of a polyol (b1). It is preferably 10% by weight or more and 60% by weight or less. The content is more preferably 15% by weight or more and 50% by weight or less, and further preferably 20% by weight or more and 40% by weight or less.

Examples of the polyisocyanate (b2) include various known aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates that are generally used in the production of polyurethane resins. For example, 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1 , 3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, Cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate , Dimeryl diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, tri Examples thereof include diisocyanate, dimerisocyanate obtained by converting a diisocyanate carboxyl group into diisocyanate, bis-chloromethyl-diphenylmethane-diisocyanate, 2,6-diisocyanate-benzyl chloride, and a dimer acid carboxyl group. These diisocyanate compounds may be used alone or in combination of two or more.
Among the exemplified compounds, it is preferable to use at least one selected from the group consisting of hexamethylene diisocyanate, tolylene diisocyanate, isophorone diisocyanate, and 1,3-bis (isocyanatomethyl) cyclohexane. In one embodiment, it is preferable to use at least one selected from the group consisting of tolylene diisocyanate and isophorone diisocyanate, and it is more preferable to use at least isophorone diisocyanate.

The amine compound (b3) contains at least a polyamine compound that serves as a chain extender. In one Embodiment, the said amine compound (b3) may contain the amine compound used as a polymerization terminator as needed in addition to a polyamine compound.
In the amine compound (b3), specific examples of the polyamine compound include a diamine compound. Specific examples include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane-4,4′-diamine and the like. Other specific examples include 2-hydroxyethylethylenediamine, 2-hydroxyethylpropyldiamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylenediamine, di-2-hydroxyethylpropylenediamine, Examples thereof include amines having a hydroxyl group in the molecule, such as 2-hydroxypyrroleethylenediamine, di-2-hydroxypyrroleethylenediamine, and di-2-hydroxypropylethylenediamine. These diamine compounds may be used alone or in combination of two or more. Moreover, you may use the polyfunctional amine chain extender which has a 3 or more amino group in a molecule | numerator as a polyamine compound as needed. Specifically, diethylenetriamine, iminobispropylamine: (IBPA, 3,3′-diaminodipropylamine), N- (3-aminopropyl) butane-1,4-diamine: (spermidine), 6,6- Examples include iminodihexylamine, 3,7-diazanonane-1,9-diamine, and N, N′-bis (3-aminopropyl) ethylenediamine.
In one embodiment, the polyamine compound is preferably at least one selected from the group consisting of ethylenediamine, isophoronediamine, and iminobispropylamine.

The amine compound (b3) may include a compound having a primary or secondary monovalent amino group. These compounds function as a polymerization terminator for the purpose of stopping an excessive reaction. Examples of the compound include dialkylamines such as di-n-butylamine and amino alcohols such as 2-ethanolamine. Furthermore, amino acids such as glycine and L-alanine can be used as a polymerization terminator, particularly when it is desired to introduce a carboxyl group into a polyurethane resin.
In particular, when amino alcohols having primary and secondary amino groups are used as a polymerization terminator, it is necessary to avoid the reaction at a high temperature and to control the temperature so that only the amino group reacts. The compounds exemplified as these polymerization terminators can be used alone or in admixture of two or more.

In the synthesis method of the polyurethane resin (b-1), after reacting the polyol (b1) with the polyisocyanate (b2), this reaction product is reacted with the polyamine compound (b3) and, if necessary, a polymerization terminator. To obtain a polyurethane-based resin. More specifically, in the method for synthesizing the polyurethane resin (b-1), first, the polyol (b1) and the polyisocyanate (b2) are mixed using a solvent inert to the isocyanate group, if necessary. Further, if necessary, a urethane prepolymer having an isocyanate group at the terminal is produced by reacting at a temperature of 40 to 150 ° C. using a urethanization catalyst (urethanization reaction). Subsequently, this prepolymer may be reacted with the polyamine compound (b3) (chain extension reaction) to obtain a polyurethane-based resin (b-1).
Alternatively, the polyol (b1), the polyisocyanate (b2), and the polyamine compound (b3) (and a polymerization terminator if necessary) are reacted in a single step to obtain a polyurethane resin (b-1). Other known methods such as a shot method can also be applied. The polyamine compound (b3) can also be used in a urethanization reaction with the polyisocyanate (b2) together with the polyol (b1).

  In the production of the urethane prepolymer, the polyurethane resin obtained according to the ratio (NCO / OH) of the molar amount of the OH group derived from the polyol (b1) and the NCO group derived from the polyisocyanate (b2) The hardness (elastic modulus) of (b-1) can be adjusted. The obtained polyurethane-based resin (b-1) becomes hard when the value of NCO / OH is high, and soft when it is low. Therefore, in one embodiment, the value of NCO / OH is preferably in the range of 1.1 to 3.0. More preferably, the value of NCO / OH is in the range of 1.5 to 2.5, and more preferably in the range of 1.7 to 2.3.

  In the production of the urethane prepolymer, it is preferable to use an organic solvent in terms of reaction control. The organic solvent to be used is preferably an organic solvent which is inactive with the isocyanate group. For example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethers such as dioxane and tetrahydrofuran; aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; chlorobenzene and parkrene And halogenated hydrocarbons. These can be used alone or as a mixed solvent in which two or more kinds are mixed.

  Furthermore, you may use a catalyst for manufacture of the said urethane prepolymer. Examples of catalysts that can be used include tertiary amine catalysts such as triethylamine and dimethylaniline; metal catalysts such as tin and zinc. These catalysts can be generally used in the range of 0.001 mol% to 1 mol% with respect to the polyol compound.

  By reacting the urethane prepolymer having an isocyanate group at the terminal obtained as described above with a diamine, triamine or the like which is a polyamine compound (b3) at a temperature of 10 to 80 ° C., a polyurethane resin (b -1) can be obtained, and an amino group can also be introduced at the terminal.

  In the chain extension reaction, a polymerization terminator may be used for the purpose of preventing excessive gelation and high viscosity by reacting excessively. When a polymerization terminator is used, for example, a chain extension reaction can be performed using the polymerization terminator and the polyamine compound (b3) together. As another example, after performing a chain extension reaction to some extent using a chain extender, a polymerization termination reaction may be performed by adding a polymerization terminator alone. On the other hand, the molecular weight of the polymer can be controlled without using a polymerization terminator. In this case, it is preferable to make it react by the method of adding a prepolymer in the solution containing a chain extension agent from the point of reaction control.

  The ratio of the total number of moles of amino groups of the amine compound (b3) to the equivalents of isocyanate groups in the urethane prepolymer (NH / residual NCO) is preferably in the range of 1.01 to 2.00. It is more preferable to carry out the reaction by adjusting the blending amount so that the ratio (NH / residual NCO) is in the range of 1.03 to 1.06. When the ratio is large and the amount of the amine compound (b3) used is large, these remain unreacted and odor tends to remain. On the other hand, when the ratio is small, the molecular weight becomes too large and gelation tends to occur.

  The polyurethane resin (b-1) preferably has a weight average molecular weight of 10,000 to 100,000 since solubility in an organic solvent (C) described later is improved. The weight average molecular weight is more preferably 15,000 to 80,000, still more preferably 20,000 to 70,000. Especially preferably, it is the range of 30,000-40,000. The polyurethane-based resin (b-1) preferably has an amino group in order to improve the adhesion to the substrate or the base ink, and the amine value derived from the amino group is 1.0 to It is preferable that it is 20.0 mgKOH / g. The amine value is more preferably 1 to 15 mgKOH / g, and further preferably 2 to 10 mgKOH / g.

The polyurethane resin (b-1) has rubber elasticity at normal temperature and normal pressure, and the glass transition temperature is preferably in the range of −50 ° C. to 25 ° C., and the dynamic viscoelasticity measurement at 40 ° C. The storage elastic modulus is preferably in the range of 1 MPa to 100 MPa. The glass transition temperature is more preferably in the range of −50 ° C. to −5 ° C.
Moreover, from the point which improves the touch feeling of a coating film, in one embodiment, in the relationship between the glass transition temperature of a polyurethane-type resin particle (a-1), and the glass transition temperature of a polyurethane-type resin (b-1), It is particularly preferable that the glass transition temperature of the polyurethane resin particles (a-1) is lower and the difference from the polyurethane resin (b-1) is in the range of 5 ° C to 50 ° C. The difference in the glass transition temperature is more preferably in the range of 10 ° C to 30 ° C.

(Cellulose resin (b-2))
Examples of the cellulose resin (b-2) include nitrocellulose, hydroxyalkyl cellulose, carboxyalkyl cellulose, and the like. The alkyl group in the exemplified cellulose may be, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, or a hexyl group, and these alkyl groups further have a substituent. It may be. Of these, nitrocellulose is preferable. As a molecular weight, the range of 5,000-100,000 is preferable at a weight average molecular weight, and the range of 10,000-100,000 is still more preferable. Moreover, the thing whose glass transition temperature is 120 to 180 degreeC is preferable.

(Vinyl chloride-vinyl acetate copolymer (b-3))
The vinyl chloride-vinyl acetate copolymer (b-3) is obtained by copolymerization of at least vinyl chloride and vinyl acetate. As a molecular weight, the range of 5,000-100,000 is preferable at a weight average molecular weight, and the range of 10,000-100,000 is still more preferable. Based on the total weight of the vinyl chloride-vinyl acetate copolymer (b-3), the ratio of vinyl acetate is preferably 1% to 30%, more preferably 3% to 25%, and more preferably 5% to 20%. Further preferred.

  Among the organic solvents (C) described later, the copolymer preferably further has a hydroxyl group derived from vinyl alcohol, in order to improve the solubility in a non-toluene organic solvent. The above copolymer having a hydroxyl group can be obtained through an additional saponification reaction with respect to the vinyl acetate component or by using vinyl alcohol at the time of copolymerization. The ratio of the structural unit derived from the vinyl alcohol is preferably 1.0% to 20% based on the total weight of the vinyl chloride-vinyl acetate copolymer (b-3). The ratio is more preferably 2.0% to 17%, and still more preferably 3.0% to 15%. The glass transition temperature of the vinyl chloride-vinyl acetate copolymer (b-3) is preferably 60 ° C to 85 ° C. More preferably, it is 70 degreeC-83 degreeC, More preferably, it is 75 degreeC-83 degreeC.

In one embodiment, the vinyl chloride-vinyl acetate copolymer (b-3) may be further obtained by copolymerization with another copolymerizable monomer. An example of a copolymerizable monomer is a (meth) acrylic monomer.
Examples of the (meth) acrylic monomer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, (meth) Hexyl acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, tetradecyl (meth) acrylate, (meth ) (Meth) acrylic acid esters such as hexadecyl acrylate and octadecyl (meth) acrylate. The exemplified compounds may further have a benzene ring structure at the site of the alkyl group. These compounds may be used alone or in combination of two or more.

  In one embodiment, the (meth) acrylic acid ester may have a hydroxyl group. For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxy (meth) acrylate (Meth) acrylic acid hydroxyalkyl esters such as butyl, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, polyethylene glycol mono (meth) acrylic acid Esters, polypropylene glycol mono (meth) acrylic acid esters, glycol mono (meth) acrylic acid esters such as 1,4-cyclohexanedimethanol mono (meth) acrylic acid ester, caprolactone-modified (meth) acrylic acid ester, and hydroxy Such as acrylamide and the like. These may be used alone or in combination of two or more. In one embodiment, it is preferable to use 2-hydroxyethyl (meth) acrylate or the like.

  In another embodiment, the (meth) acrylic monomer may have a functional group other than a hydroxyl group. Examples of functional groups include a carboxyl group, an amide bond group, an amino group, and an alkylene oxide group.

  For example, carboxyl group-containing acrylic monomers include (meth) acrylic acid, monohydroxyethyl acrylate phthalate, p-carboxybenzyl acrylate, ethylene oxide modified (added moles: 2-18) phthalate acrylate , Phthalic acid monohydroxypropyl acrylate, succinic acid monohydroxyethyl acrylate, β-carboxyethyl acrylate, 2- (4-benzoyl-3-hydroxyphenoxy) ethyl acrylate, maleic acid, monoethylmaleic acid, Itaconic acid, citraconic acid, fumaric acid and the like can be mentioned.

  Examples of the (meth) acrylic monomer containing an amide bond include (meth) acrylamide, N-methylacrylamide, N-isopropylacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N, N Examples include (meth) acrylamide compounds such as dimethylaminopropyl (meth) acrylamide, diacetone acrylamide, N- (hydroxymethyl) acrylamide, and N- (butoxymethyl) acrylamide.

  Examples of the (meth) acrylic monomer containing an amino group include monomethylaminoethyl (meth) acrylate, monoethylaminoethyl (meth) acrylate, monomethylaminopropyl (meth) acrylate, and (meth) acrylic. Examples include (meth) acrylic acid monoalkylamino esters such as monoethylaminopropyl acid.

  The (meth) acrylic monomer may have an alkylene oxide unit. For example, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-phenoxyethyl acrylate, methoxypolyethylene glycol (meth) acrylic acid ester, ethoxypolyethylene glycol (meth) acrylic acid ester, methoxypolypropylene glycol (meth) acrylic Examples include acid esters, ethoxypolypropylene glycol (meth) acrylic acid esters, phenoxypolyethylene glycol (meth) acrylic acid esters, and phenoxypolypropylene glycol (meth) acrylic acid esters.

  In one embodiment, the thermoplastic binder resin (B) preferably includes a polyurethane resin (b-1) and a vinyl chloride-vinyl acetate copolymer (b-3). By appropriately changing these blending ratios, the elastic modulus of the thermoplastic binder resin (B) can be easily adjusted. In one embodiment, the weight ratio between the polyurethane resin (b-1) and the vinyl chloride-vinyl acetate copolymer (b-3) is (100% by weight) based on the total weight of these solid components (100% by weight). The range of b-1) / (b-3) = 95/5 to 40/60 is preferable. More preferably, it is the range of 90 / 10-50 / 50, More preferably, it is the range of 85 / 15-60 / 40.

<Organic solvent (C)>
A well-known organic solvent can be used for the organic solvent (C) which comprises the coating agent composition for printing. Examples of usable organic solvents include aromatic organic solvents such as toluene and xylene, ketone organic solvents such as methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate, propylene glycol monoethyl ether acetate, Examples include ester organic solvents such as propylene glycol monomethyl ether acetate, and alcohol organic solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, propylene glycol monoethyl ether, and propylene glycol monomethyl ether. These may be used alone or in admixture of two or more.
Among these, the organic solvent (C) does not contain an aromatic organic solvent such as toluene and xylene from the viewpoint of the temporal stability of the coating composition for printing due to aggregation and swelling of the low Tg resin particles (A). (Non-toluene organic solvent) is more preferable. Further, it is more preferable that the organic solvent (C) does not contain a ketone organic solvent such as methyl ethyl ketone (hereinafter referred to as “MEK”).
From such a viewpoint, in one embodiment, the organic solvent (C) is preferably at least one selected from the group consisting of an ester organic solvent and an alcohol organic solvent. In one embodiment, it is preferable to use an ester organic solvent and an alcohol organic solvent in combination as the organic solvent (C). For example, the combination of ethyl acetate and isopropyl alcohol is mentioned. In the organic solvent, the ratio of ester organic solvent: alcohol organic solvent is preferably in the range of 50:50 to 90:10, more preferably in the range of 55:45 to 85:15, and 60:40 to 80:20. A range is more preferred.

(Other ingredients)
The coating agent composition for printing may contain a resin other than the thermoplastic binder resin (A) for the purpose of improving the adhesion to the substrate. Examples of usable resins include chlorinated polypropylene resins. The content of the auxiliary resin is preferably 1 to 5% by weight, more preferably 1 to 3% by weight, based on the total weight of the coating composition for printing (100% by weight).

  The coating agent composition for printing can contain a well-known component as an additive suitably. For example, a known additive can be added as needed during the production of the coating agent composition for printing. Specific examples of components that can be used as additives include leveling agents, ultraviolet absorbers, light stabilizers, curing agents, plasticizers, wetting agents, adhesion aids, antifoaming agents, antistatic agents, trapping agents, and antiblocking agents. , Wax components, silica particles, resin particles other than the resin particles (A), preservatives, and the like. Further, oil, filler, reinforcing agent, matting agent, abrasive, inorganic fine particles and the like can be blended.

  Since the coating agent composition for printing of this embodiment can form a solid coating film after drying, a curing agent is not necessarily required. For example, for the purpose of further improving the strength of the solid coating film, an isocyanate-based coating composition is used. A curing agent such as a curing agent or a silane coupling agent may be included. When using a curing agent, it is desirable to adjust the coating so that the coating does not become too hard.

  Examples of the wax component include solid or liquid polyolefin wax, fatty acid amide wax, and the like, and solid polyolefin wax is preferable. Examples of the polyolefin wax include polyethylene wax and polypropylene wax, and polyethylene wax is preferable. The polyethylene wax includes a high density polymerization type, a low density polymerization type, an oxidation type, and a modified type, and any of them can be used. In one embodiment, it is preferable to use a low density type, and more preferable is a melting point of 90 ° C. to 130 ° C. in DSC measurement.

  The coating agent composition for printing can be produced by dissolving and / or dispersing the resin particles (A) and the thermoplastic binder resin (B) in the organic solvent (C). Other components such as additives may be added as necessary. In the production of the above coating composition for printing, if necessary, homogenization may be performed using a disperser. The disperser may be one generally used, and for example, a roller mill, a ball mill, a pebble mill, an attritor, a sand mill, or the like can be used.

  If the coating composition for printing contains air bubbles or unexpectedly coarse particles, the quality of the printed matter is deteriorated. Therefore, it is preferable to remove coarse particles from the composition by a method such as filtration. Filtration can be performed using a conventionally known filter.

  From the viewpoint of preventing sedimentation of the resin particles (A) and appropriately dispersing the resin particles (A) in other components, it is preferable to adjust the viscosity of the printing coating composition produced by the above method. In one embodiment, the viscosity is preferably 50 to 1000 mPa · s, more preferably 100 to 500 mPa · s, and still more preferably 120 to 400 mPa · s. It should be noted that the viscosity at Zaan Cup # 4 is preferably adjusted to approximately 9 to 30 seconds. From the viewpoint of work efficiency, it is more preferable to adjust to the range of 10 seconds to 25 seconds. The viscosity can be easily adjusted by adjusting the amount of the organic solvent (C) or the amount of the binder resin (B).

<Printed matter>
The said coating agent composition for printing can be used effectively in order to form the coating layer (solid coating film) which covers the surface of the various base material which has a printing ink layer in part at least. The coat layer protects the surface of the printing ink layer on the base material, and can impart an excellent feel to the surface of the printed matter. The method for producing the printed material is not particularly limited. For example, printing and drying a printing ink composition on a substrate to form a printing ink layer, and then printing and drying a printing coating composition on the printing ink layer of the substrate. And a step of forming a coating layer (solid coating film).

(Base material)
The printed matter is obtained by printing a printing coating composition on a substrate having a printing ink layer. The substrate may be, for example, a plastic substrate or a paper substrate.
Plastic base materials include, for example, polyolefins such as polyethylene and polypropylene, polyethylene terephthalate, polycarbonate, polyesters such as polylactic acid, polystyrene resins such as polystyrene, AS resin, ABS resin, nylon, polyamide, polyvinyl chloride, polyvinylidene chloride, It may be a film-like substrate made of a material such as cellophane, paper, aluminum, or a film-like substrate made of a composite material of the above materials.
The plastic substrate may be a deposited substrate obtained by depositing an inorganic compound such as silica, alumina, or aluminum on, for example, polyethylene terephthalate or a nylon film. Even in the case of such a vapor deposition substrate, in the same manner as the above printing method, by applying the coating agent composition for printing on the vapor deposition substrate having the printing ink, and fixing the film by drying in an oven, A printed matter can be obtained.
In addition, the plastic substrate may be coated with a metal oxide or the like on the surface by vapor deposition coating and / or polyvinyl alcohol. Furthermore, surface treatment such as corona treatment may be performed.
The paper substrate may be ordinary paper or cardboard.
Although there is no particular designation, it can be suitably used when the thickness of the substrate is in the range of 0.2 mm to 1.0 mm. The surface of the substrate serving as the printing surface may be corona treated. Moreover, the paper base material may be vapor-deposited with a metal such as aluminum for the purpose of imparting design properties. Furthermore, surface coating treatment may be performed with an acrylic resin, a urethane resin, a polyester resin, a polyolefin resin, or other resins. Furthermore, in addition to the surface coating treatment with the resin, a surface treatment such as a corona treatment may be performed. Examples of such a substrate include coated cardboard and marie coated paper.

(Printing ink composition)
Specific examples of the printing ink composition for forming the printing ink layer include, for example, a gravure ink composition, a flexographic ink composition, an offset ink composition, and other ink compositions, and any printing ink composition can be used. Good. Among these, a gravure ink composition and a flexographic ink composition are preferable.

  The gravure ink composition, flexographic ink composition, or offset ink composition contains a pigment, a binder, an additive, a solvent, water, or the like. Examples of the binder include fiber materials such as nitrocellulose, cellulose acetate / propionate, chlorinated polypropylene, vinyl chloride-vinyl acetate copolymer, polyester, acrylic, polyurethane and acrylic urethane, polyamide, Examples include polybutyral series, cyclized rubber series, chlorinated rubber series, rosin modified phenolic resin series, and alkyd resin series. These may be used alone or in combination of two or more.

The pigment used in the printing ink composition is not particularly limited, and may be an organic pigment or an inorganic pigment used in general inks, paints, and recording agents. These can also be used together.
Organic pigments include azo, phthalocyanine, anthraquinone, perylene, perinone, quinacridone, thioindigo, dioxazine, isoindolinone, quinophthalone, azomethine azo, dictopyrrolopyrrole, isoindoline, etc. Pigments. Moreover, although not limited to the following, for example, Carmine 6B, Lake Red C, Permanent Red 2B, Disazo Yellow, Pyrazolone Orange, Carmine FB, Chromophthal Yellow, Chromophthal Red, Phthalocyanine Blue, Phthalocyanine Green, Dioxazine Violet Quinacridone magenta, quinacridone red, indanthrone blue, pyrimidine yellow, thioindigo Bordeaux, thioindigo magenta, perylene red, perinone orange, isoindolinone yellow, aniline black, diketopyrrolopyrrole red, daylight fluorescent pigment, etc. Can be mentioned.

  Examples of the inorganic pigment that can be used as the white pigment in the printing ink composition include titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, and silica. When preparing a white ink, it is preferable to use titanium oxide as a pigment. White ink using titanium oxide is preferable in terms of coloring power, hiding power, chemical resistance, and weather resistance. From the viewpoint of printing performance, the titanium oxide is preferably treated with silica and / or alumina. The titanium oxide is preferably subjected to a polyol treatment. The titanium oxide may be subjected to a treatment with silica and / or alumina and a polyol treatment.

  Non-white inorganic pigments are not limited to the following examples. For example, carbon black, aluminum particles, mica (mica), bronze powder, chrome vermillion, chrome lead, cadmium yellow, cadmium red, ultramarine, and bitumen , Bengara, yellow iron oxide, iron black, titanium oxide, zinc oxide and the like. The aluminum particles may be in the form of a powder or a paste, but are preferably used in the form of a paste from the viewpoint of handleability and safety. Either leafing or non-leafing can be appropriately selected in terms of brightness and density.

  The printing ink composition may contain a known additive as required. When manufacturing printing ink compositions, for example, pigment derivatives, pigment dispersants, wetting agents, adhesion aids, leveling agents, antifoaming agents, antistatic agents, trapping agents, antiblocking agents, wax components, silica particles, polymerization prohibition An agent, a color separation inhibitor, and the like may be added.

<Printing method>
It does not specifically limit as a printing method of the printing ink composition for forming a printing ink layer, A well-known method can be used. For example, a gravure printing method, a flexographic printing method, etc. are mentioned. The thickness of the ink layer is preferably 0.1 μm to 15 μm. When the thickness of the printing ink layer is 0.1 μm or more, it is easy to obtain sufficient ink coloring properties. In addition, when the thickness of the printing ink layer is 15 μm or less, it is easy to suppress embrittlement of the printing ink layer.

  The printing method of the coating composition for printing to form the coating layer should be such that the coating composition for printing is applied to the surface of the printing ink layer on the substrate and a solid coating film can be formed after drying. There is no particular limitation. For example, wet coating methods such as a gravure printing method, a flexographic printing method, an ink jet printing method, a screen printing method and the like can be mentioned. Among these, the gravure printing method is most preferable from the viewpoint of the preferable viscosity range of the coating agent composition for printing.

  As for the film thickness of the coating layer (solid coating film) formed using the coating agent composition for printing, about 1-2 micrometers is preferable. On the other hand, the average particle diameter of the resin particles (A) in the composition is desirably in the range of 2 to 20 μm. When the resin particles (A) are buried in the coating film, it becomes difficult to obtain a desired good touch feeling. Therefore, when the film thickness is increased, the resin particles (A) are preferably selected as appropriate so as to have a particle diameter and a blending amount that are not buried in the coating film.

  Hereinafter, although embodiment of this invention is described in detail along an Example, this invention is not limited to these Examples. Note that “parts” and “%” described in the present specification represent parts by weight and% by weight unless otherwise noted.

1. Preparation of Thermoplastic Binder Resin (B) Measurement methods for various properties of the resin are as follows.
(Hydroxyl value)
The hydroxyl group in the resin was esterified or acetylated with excess acid anhydride, and the remaining acid was back titrated with alkali. The amount of hydroxyl group in 1 g of resin was calculated from the back titration and converted as the number of mg of potassium hydroxide. More specifically, it is a value obtained by a measurement method according to JISK0070.

(Acid value)
The acid group contained in 1 g of resin was calculated from the number of mg of potassium hydroxide required for neutralization. The measuring method may be a known method, and is generally performed according to JISK0070 (1996).

(Weight average molecular weight of resin)
Measurement was performed using GPC (gel permeation chromatography) “Shodex GPC System-21” manufactured by Showa Denko KK. GPC is a liquid chromatography that separates and quantifies substances dissolved in a solvent based on the difference in molecular size. Tetrohydrofuran is used as a solvent, and the weight average molecular weight is determined in terms of polystyrene.

(Amine number)
The equivalent amount of hydrochloric acid required to neutralize the amino group contained in 1 g of resin and the number of mg of potassium hydroxide of the same amount were measured by the following method.
[Method for measuring amine value]
0.5-2 g of the sample was precisely weighed (sample amount: Sg). To a precisely weighed sample, 30 mL of a mixed solution of toluene: isopropanol = 1: 1 was added and dissolved. The obtained solution was titrated with a 0.2 mol / L ethanolic hydrochloric acid solution (titer: f) (titer: AmL). The amine value was determined according to the following (formula 2).
(Formula 2) Amine number = (A × f × 0.2 × 56.108) / S

(Number average molecular weight of polyol)
From the hydroxyl value, it was assumed that the polymer was all diol molecules, and the value was obtained according to the above-described (Formula 1).

(Glass-transition temperature)
It was determined by DSC measurement. The measurement conditions are as follows.
Measuring instrument: DSC8000 (manufactured by PerkinElmer)
Program: Temperature rising rate 10 ° C / min, temperature range -100 ° C to 100 ° C
Evaluation: The temperature at the midpoint of the temperature range where the glass transition occurs was defined as the glass transition temperature.

  Below, the synthesis example of a polyurethane-type resin is shown as an example of a thermoplastic binder resin (B).

(Synthesis Example 1)
120 parts of polyester diol obtained from adipic acid having a number average molecular weight of 2000 and 1,2-propanediol, 80 parts of polypropylene glycol having a number average molecular weight of 2000, 23.3 parts of isophorone diisocyanate, 18.3 parts of toluene diisocyanate, and ethyl acetate 60.4 parts were reacted for 4 hours at 80 ° C. under a nitrogen stream to obtain a solution of a terminal isocyanate prepolymer.
Next, 23.3 parts of isophoronediamine and 550.4 parts of a mixed solvent of ethyl acetate / isopropanol = 50/50 were mixed, and the solution of the terminal isocyanate prepolymer prepared above was gradually added to this mixture at 40 ° C. Added and allowed to react at 80 ° C. for 1 hour.
Thus, a polyurethane resin solution PU1 having a solid content of 30%, an amine value of 6.5 mgKOH / g, and a weight average molecular weight of 32,000 was obtained. In addition, the glass transition temperature of the polyurethane-type resin calculated | required from DSC measurement was -30 degreeC.

(Synthesis Examples 2 to 5)
Using the raw materials shown in Table 1, polyurethane resin solutions PU2 to PU5 were obtained in the same manner as in Synthesis Example 1.

The raw materials described in Table 1 are as follows.
<Polyol (b1)>
Polyester polyol (b1-1-1)
PMPA: Polyester diol which is a condensate of adipic acid and 3-methyl-1,5-pentadiol, and number average molecular weights are 5000, 2000 and 1000, respectively (in order, Kuraray P5010, P2010 and P1010) use)
PPA: Polyester diol having a number average molecular weight of 2000, which is a condensate of adipic acid and 1,2-propanediol

Polyether polyol (b2-1-2)
PPG: Polypropylene glycol having a number average molecular weight of 2000 (2020 manufactured by ACG)
Other polyols PCL: polycaprolactone diol having a number average molecular weight of 2000 obtained by ring-opening polymerization of ε-caprolactone (PCL220N manufactured by Daicel)
PC: Polycarbonate diol having a number average molecular weight of 2000 (C2090 manufactured by Kuraray Co., Ltd.) in which the weight ratio of 3-methyl-1,5-pentadiol and 1,6-hexanediol is 9/1

<Isocyanate (b2)>
TDI: Toluene diisocyanate IPDI: Isophorone diisocyanate TDI mol%: Ratio of TDI based on all components of isocyanate (b2)

<Amine compound (b3)>
IPDA: Isophoronediamine IBPA: 3,3′-iminobispropylamine 2EtAm: 2-ethanolamine

<Solvent>
IPA: Isopropanol MEK: Methyl ethyl ketone

The resin obtained in the following synthesis example is a urethane acrylate resin (energy ray curable resin) having an unsaturated double bond, and corresponds to a comparative example.
(Comparative Synthesis Example 1)
200 parts of a polyester diol obtained from adipic acid having a number average molecular weight of 2000 and 3-methyl-1,5-pentanediol and 50.2 parts of isophorone diisocyanate were reacted at 80 ° C. for 4 hours under a nitrogen stream. A solution of terminal isocyanate prepolymer was obtained.
On the other hand, hydroquinone was added in an amount of 200 ppm with respect to the solid weight of the resin to be added below, and an oxygen atmosphere was set. Subsequently, 39.4 parts of hydroxyethyl acrylate was added thereto, and the terminal isocyanate prepolymer solution obtained previously was gradually added at 80 ° C. to carry out the reaction. The reaction solution was analyzed by infrared absorption spectrum. When the isocyanate absorption band disappeared, the reaction was completed, and a urethane acrylate resin (URA1) was obtained. The viscosity of the resin was 10,000 mPa · s / 25 ° C., and the weight average molecular weight was 6000.

2. Preparation of polyurethane resin particles (A) Synthesis examples of polyurethane resin particles are shown below. The synthesis was performed with reference to the method described in “Japanese Patent Application Laid-Open No. 2010-024319”.
The glass transition temperature was determined by DSC measurement, and the average particle size was determined by the integrated value 50% (D50) in the particle size distribution determined by laser diffraction / scattering method measurement. Details of each measurement condition are as follows.

<Glass transition temperature measurement conditions>
Measuring instrument: DSC8000 (manufactured by PerkinElmer)
Program: Temperature rising rate 10 ° C / min, temperature range -100 ° C to 100 ° C
Evaluation: The temperature at the midpoint of the temperature range where the glass transition occurs was defined as the glass transition temperature.

<Average particle diameter measurement conditions>
Measuring instrument: Microtrack MT3000II (manufactured by Microtrack Bell)
Measurement conditions: particles dispersed in ethyl acetate and measured at 25 ° C. Measurement range: 0.01 μm to 1000 μm
Evaluation: The integrated value 50% (D50) in the particle size distribution was taken as the average particle size.

(Synthesis Example 6)
A separable flask equipped with a 2 L stirrer was charged with 800 g of water, and 37 g of hydroxypropylmethylcellulose (Metroze 90SH-100, manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved therein to prepare a dispersion medium.
On the other hand, 187.5 g of polyester diol (PMPA, manufactured by Kuraray Co., Ltd.) obtained from adipic acid having a number average molecular weight of 6000 and 3-methyl-1,5-pentadiol as a polyol, one isocyanate of hexamethylene diisocyanate as a polyisocyanate component A resin particle material was prepared by mixing 112.5 g of a triisocyanate whose group was trimerized with an isocyanurate structure, 120 g of methyl ethyl ketone (MEK) as a diluent solvent, and 0.003 g of dibutyltin dilaurate as a catalyst. The molar ratio (NCO / OH) of the isocyanate component and the polyol component in the resin particle raw material was 9.8.
While stirring the previously prepared dispersion medium at 700 rpm, the resin particle raw material was added to prepare a suspension. Next, the suspension was heated to 60 ° C. while continuing stirring, reacted for 4 hours, and then cooled to room temperature. After cooling, it was separated into solid and liquid, thoroughly washed with water, and then dried at 50 ° C. for 20 hours to obtain resin particles.
The polyurethane-based resin particles (A-1) thus obtained had an average particle diameter of 7 μm and a glass transition temperature of −54 ° C.

(Synthesis Example 7)
In the preparation of the polyurethane resin particles (A-1) described in Synthesis Example 6, 27 g of hydroxypropylmethylcellulose, 160 g of PMPA having a number average molecular weight of 6000 as a polyol, and polycaprolactone triol (Placcel 320, number average molecular weight 2000, Daicel) Polyurethane in the same manner as in Synthesis Example 6 except that 80.0 g of Chemical Industry Co., Ltd.) was used and 60.0 g of diisocyanate in which one isocyanate group of hexamethylene diisocyanate was dimerized with a uretdione structure was used as polyisocyanate. Resin particle A-2 was obtained.
The molar ratio (NCO / OH) of the isocyanate component to the polyol component in the resin particle raw material was 1.8. Moreover, the average particle diameter of the obtained polyurethane-type resin particle (A-2) was 15 micrometers, and the glass transition temperature was -52 degreeC.

(Synthesis Example 8)
In the preparation of the polyurethane resin particles (A-1) described in Synthesis Example 6, the polyol was replaced with 208.0 g of polycaprolactone triol (Placcel 320, number average molecular weight 2000, manufactured by Daicel Chemical Industries, Ltd.), and uretdione as polyisocyanate. Polyurethane resin particles A-3 were obtained in the same manner as in Synthesis Example 6 except that the type polyisocyanate was replaced.
The molar ratio (NCO / OH) of the isocyanate component to the polyol component in the resin particle raw material was 1.8. Moreover, the average particle diameter of the obtained polyurethane-type resin particle (A-3) was 7 micrometers, and the glass transition temperature was -40 degreeC.

(Synthesis Example 9)
In the preparation of the polyurethane resin particles (A-1) described in Synthesis Example 6, the polyol was replaced with 240.0 g of polytetramethylene glycol (PTMG 2000, number average molecular weight 2000, manufactured by Mitsubishi Chemical Corporation), and hexamethylene diisocyanate Polyurethane resin particles A-4 were obtained in the same manner as in Synthesis Example 6 except that the amount of isocyanurate type polyisocyanate was changed to 60.0 g.
The molar ratio (NCO / OH) of the isocyanate component and the polyol component in the resin particle raw material was 1.3. The average particle diameter of the obtained polyurethane resin particles (A-4) was 7 μm, and the glass transition temperature was −78 ° C.

3. Preparation of coating agent composition for printing An example of preparing a coating agent composition for printing is shown below.
Example 1
20 parts of polyurethane resin solution PU1, 8 parts of polyurethane resin particles (A-1), 2 parts of polyethylene wax (manufactured by Mitsui Chemicals, 110P, melting point 109 ° C.), and mixed solvent (ethyl acetate / IPA = 50 / 50) 70 parts were mixed for 60 minutes using an air disper (rotation number 800 rpm) to obtain a coating composition S1 for printing.

(Examples 2 to 17)
Using the raw materials shown in Table 2-1 at the described blending ratios, printing agent compositions S2 to S17 were obtained in the same manner as in Example 1.
The raw materials described in Table 2-1 are as shown below.

<Resin particles (A)>
Polyurethane resin particles (a-1)
A-1 to A-4: Polyurethane resin particles (A-1) to (A-4) prepared in Synthesis Examples 6 to 9
SS-010T: acrylic particles manufactured by Negami Kogyo Co., Ltd., Tg-44 ° C., average particle diameter 10 μm)

<Thermoplastic binder resin (B)>
Polyurethane resin (b-1)
PU1 to PU5: Polyurethane resin solutions PU1 to PU5 prepared in Synthesis Examples 1 to 5 (solid content 30%)
Cellulosic resin (b-2)
DHX3-5: Nitrocellulose manufactured by Inabata Sangyo Co., Ltd. Solid content 30% IPA solution Vinyl chloride-vinyl acetate copolymer (b-3)
Solvain TA3: vinyl chloride-vinyl acetate copolymer manufactured by Nissin Chemical Co., Ltd., solid content 30% ethyl acetate solution, vinyl chloride / vinyl acetate / vinyl alcohol = 83/4/13, weight average molecular weight 25000
Ketone resin K-90: Arakawa Chemical Co., Ltd. ketone resin, solid content 30% MEK solution, Tg 90 ° C.
<Additives>
110P: polyethylene wax manufactured by Mitsui Chemicals, melting point 109 ° C

(Comparative Examples 1-17)
Using the raw materials shown in Table 2-2 at the respective blending ratios, printing agent compositions T1 to T17 for printing were obtained in the same manner as in Example 1. In addition, the raw material described in Table 2-2 is as showing below. Except as described below, it is as described above.
<Other resin particles>
Art Pearl C-600: Polyurethane fine particles manufactured by Negami Kogyo Co., Ltd., Tg-13 ° C., average particle size 10 μm
Art Pearl J-3PY: acrylic fine particles manufactured by Negami Kogyo Co., Ltd., Tg 34 ° C., average particle size 1.1 μm
Art Pearl AK-300TR: (Negami Kogyo's polyurethane fine particles, Tg-34 ° C., average particle size 22 μm
<Other binder components>
URA1: Urethane acrylate prepared in Comparative Synthesis Example 1

4). Printed matter An example of a method for producing a printed matter using the above coating composition for printing is shown below.
(Example 18)
<Preparation of printed material G1>
A small gravure printing machine equipped with a paper substrate (product name “Ryuou Coat Paper” manufactured by Daio Paper Co., Ltd., 65 g / m ² ) and a helio 175L (plate-type compressed) solid plate was prepared. Gravure ink (Eco Color F92 Black: manufactured by Toyo Ink Co., Ltd.) was diluted with a mixed solvent (MEK / n-propyl acetate / IPA = 50/30/20) so as to be 15 seconds with Zahn Cup # 3. The diluted gravure ink was supplied to the above-mentioned printing machine, and then 100 m was printed under conditions of a printing speed of 80 m / min and a drying temperature of 60 ° C. to obtain a printed matter.
Furthermore, a solution obtained by diluting the printing coating composition S1 with a mixed solvent (MEK / n-propyl acetate / IPA = 50/30/20) so as to be 15 seconds in Zahn cup # 3 is prepared, and corrosion 175 L ( (Print depth 40 μm) Using a small gravure printing machine equipped with a solid plate, printing was performed at a printing speed of 80 m / min and a drying temperature of 60 ° C. for 100 m on the printing surface of the printed matter obtained earlier, Print G1 was obtained.

(Examples 19 to 34)
<Preparation of printed materials G2 to G17>
By the same method as in Example 18, printed materials G2 to G17 (Examples) were obtained using the coating agent compositions for printing S2 to S17 described in Table 2-1.

(Examples 35-38)
<Preparation of printed materials G18 to G21>
Example 18 was the same as Example 18 except that the substrate was changed to a polyethylene terephthalate film (E5102, manufactured by Toyobo Co., Ltd., film thickness 30 μm), and the gravure ink was changed to JS581 Real Color 92T Black (manufactured by Toyo Ink Co., Ltd.). According to the method, printed matter G18-G21 (Example) was obtained using coating agent composition S1-S4 for printing of Table 2-1.

(Comparative Examples 18-34)
<Preparation of printed materials H1 to H17>
By the same method as in Example 18, printed materials H1 to H17 (comparative examples) were obtained using the coating composition for printing T1 to T17 described in Table 2-2.
In addition, the printed matter H3 to H6 is a printing machine equipped with an ultraviolet (UV) exposure machine, a printing speed of 30 m / min, one 160 W / cm high pressure mercury lamp, an irradiation distance of 10 cm, and an integrated light quantity of 300 mj / cm ² . Evaluation was performed after curing the printing layer.
Moreover, about the printed matter H7-H10, printing was performed on conditions with a printing speed of 20 m / min and a drying temperature of 100 ° C., and evaluation was performed after thermosetting at 80 ° C. for 60 minutes.

(Comparative Examples 35-38)
<Preparation of printed materials H18 to H21>
According to the same method as in Example 18, except that the base material was changed to a polyethylene terephthalate film (Toyobo, E5102, 30 μm) and the gravure ink was changed to JS581 Real Color 92T Black (manufactured by Toyo Ink Co.) in Example 18. The printed materials H18 to H21 (comparative examples) were obtained using the coating composition for printing T14 to T17 described in Table 2-2.

<Evaluation of various properties>
For the coating composition S1 to S17 and T1 to T17 for printing obtained in Examples 1 to 38 and Comparative Examples 1 to 38, and the printed materials G1 to G21 and H1 to H21, composition stability and resistance Blocking property, pencil hardness, friction resistance, and finger touch test were performed. Details of testing and evaluation methods for various properties are as follows.

<Composition stability>
The coating composition for printing S1 to S17 and T1 to T17 were stored in an oven at 50 ° C. for 1 week, and the stability over time was evaluated. For the measurement, Zahn Cup # 4 manufactured by Rouai Co., Ltd. was used. The evaluation results of each composition according to the following criteria are shown in Tables 3-1 to 3-2. If the evaluation result is “4” or “5”, there is no practical problem.
(Evaluation criteria)
5: No increase in viscosity over time (less than 2 seconds)
4: Thickening over 2 seconds to less than 5 seconds 3: Thickening over 5 seconds to less than 40 seconds 2: Almost no fluidity over time, significant thickening (thickening over 40 seconds)
1: Gelation over time

<Blocking resistance>
The printed materials G1 to G21 and H1 to H21 are stacked so that the printed surface and the non-printed surface are in contact with each other, applied with a load of 10 kgf / cm ² , and allowed to stand in an environment of 50 ° C.-80% RH for 24 hours. It was. After taking out the substrate, the state of transfer to the non-printing surface was evaluated in five stages according to the following criteria. The evaluation results are shown in Tables 3-1 to 3-2. If the evaluation result is “4” or “5”, there is no practical problem.
(Evaluation criteria)
5: 0% transfer to non-printed surface
4: Transfer amount less than 5% 3: Transfer amount from 5% to less than 30% 2: Transfer amount from 30% to less than 60% 1: Full adhesion

<Pencil hardness test>
About produced printed matter G1-G21 (Example) and printed matter H1-H21 (comparative example), based on JIS-K-5600, using a pencil hardness tester (Scratching Tester HEIDON-14 made by HEIDON), pencil The test was performed five times with a load of 500 g, while changing the hardness of the core of “B”, “HB”, and “F” in this order. The average core hardness in five tests was defined as the pencil hardness of the printed matter. The evaluation results are shown in Tables 3-1 and 3-2. Practical required physical properties are those having a pencil hardness of “HB” or higher.

<Abrasion resistance>
About printed matter G1-G21 (Example) and H1-H21 (comparative example), the test was done using the Gakushin type | mold friction-resistant tester (Load 200g, frequency | count 100 times, quality paper). The degree of film removal was observed with the naked eye, and the friction resistance was evaluated according to the following criteria. “Removal of coating” means peeling of the coating due to strong rubbing. The evaluation results are shown in Tables 3-1 and 3-2. If the evaluation result is “4” or “5”, there is no practical problem.
(Evaluation criteria)
5: Not removed throughout the coating.
4: Removed at a small portion of the film.
3: Taken in 30 to 60% of the coating.
2: Taken at 60 to 80% of coating.
1: The entire coating is removed.

<Finger touch test>
The finger touch test was done about printed matter G1-G21 (Example) and H1-H21 (comparative example). In addition, evaluation is performed under the condition of finger movement speed: about 20 mm / sec, finger-sample contact area: 1-2 cm ² , force of pushing the sample with the finger: about 3.0 × 103 Pa, and softness (softness) The wet and dry feeling (moist feeling) and the rough feeling (smoothness) were judged. The evaluation criteria are as follows. In any case, if the evaluation result is “4” or “5”, there is no practical problem.
(Evaluation criteria)
-Hardness (softness)
5: Elastic and very soft.
4: Elastic and soft.
3: Strong elasticity and slightly hard.
2: Strong elasticity and hard.
1: Hard.
・ Dry and wet feeling (moist feeling)
5: Very moist.
4: Moist.
3: Moist but slightly dry.
2: A dry feeling is felt.
1: A feeling of dryness is strong.
・ Rough feeling (smoothness)
5: Smooth and smooth.
4: Slip is slightly inferior, but smooth.
3: There is no slipping feeling and the smoothness is not felt so much.
2: There is a slight sense of crunch.
1: is looking.

From the various evaluation results shown in Tables 3-1 and 3-2, resin particles (A) having a glass transition temperature in the range of −80 ° C. to −35 ° C. and an average particle diameter in the range of 2 to 20 μm; The coating composition for printing containing the thermoplastic binder resin (B) and the organic solvent (C) can form a coating film by printing, and also has a good feeling of touch and friction resistance. It turns out that a coating film can be formed.

Claims (10)

  Resin particles (A) having a glass transition temperature in the range of −80 ° C. to −35 ° C. and an average particle diameter in the range of 2 to 20 μm, the thermoplastic binder resin (B), and the organic solvent (C) And a coating agent composition for printing.   The coating agent composition for printing according to claim 1, wherein the resin particles (A) are polyurethane resin particles (a-1).   The coating agent composition for printing of Claim 2 in which the said polyurethane-type resin particle (a-1) contains the structural unit derived from the polyester which consists of adipic acid and 3-methyl- 1,5-pentanediol.   The thermoplastic binder resin (B) is at least selected from the group consisting of a polyurethane resin (b-1), a cellulose resin (b-2), and a vinyl chloride-vinyl acetate copolymer (b-3). The coating agent composition for printing of any one of Claims 1-3 which is 1 type.   The polyurethane resin (b-1) includes at least one selected from the group consisting of a structural unit derived from a polyester polyol (b-1-1) and a structural unit derived from a polyether polyol (b-1-2). The coating agent composition for printing of Claim 4 containing.   The coating agent composition for printing of Claim 4 in which the said cellulose resin (b-2) contains a nitrocellulose resin.   The coating agent composition for printing according to any one of claims 1 to 6, wherein the organic solvent (C) does not contain an aromatic organic solvent.   The base material which has a printing ink layer in at least one part, and the coating layer formed using the coating agent composition for printing of any one of Claims 1-7 on the printing ink layer of the said base material And printed matter.   The printed matter according to claim 8, wherein the substrate is a paper substrate. The printed matter according to claim 8, wherein the substrate is a plastic substrate.