JP2013253231A - Curable urethane polymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the adhesion of a resulting coating film to a substrate while securing low tackiness only by performing simple drying.SOLUTION: A curable coating agent contains a urethane-acryl polymer composition, which contains a urethane polymer (A) obtained by reacting a polyvalent isocyanate compound with a diol compound, and a polymerizable monomer (B) including a multifunctional (meth)acrylic monomer having a plurality of double bonds at a ratio of 20/80 or more and 80/20 or less in terms of (A)/(B) (weight ratio), and further includes 0.01-3 pts.wt. of an ultraviolet curing agent (C) relative to 100 pts.wt. of (B).

Description

  The present invention relates to a coating agent and a laminate comprising a curable urethane polymer composition.

  The ultraviolet curable resin is composed of polymerizable monomers and oligomers such as (meth) acrylic compounds and urethane acrylic compounds, and can be cured by irradiating ultraviolet rays after adding an ultraviolet curing agent (Patent Literature). 1).

  This UV curable resin may be diluted with a solvent so that it can be easily applied when applied to a substrate, and there are also those designed to be diluted with water from an environmental point of view. .

JP 2002-200722 A

  By the way, as the ultraviolet curing agent, one diluted with a solvent or water needs to be dried once and then cured. At this time, in a state where it is only dried, there may be a case where tack is present on the coated surface. In this case, for example, when the film is coated, wound and stored, there is a possibility that rewinding may be difficult.

  Furthermore, when the ultraviolet curable resin is applied to a substrate, the resulting film may not have sufficient adhesion. In this case, it is necessary to apply the primer to the substrate in advance.

  In addition, when the object to be coated with the ultraviolet curable resin is porous such as wood, since the penetration when the ultraviolet curable resin is applied is large, the function to be imparted to the surface cannot be sufficiently obtained, It is necessary to form a penetration preventing layer such as a sealant.

  Therefore, an object of the present invention is to show low tackiness even in a state after drying, and to improve the adhesion of the obtained film to a substrate.

  The present invention relates to a polymerizable monomer comprising a urethane polymer (A) obtained by reacting a polyvalent isocyanate compound and a diol compound, and a polyfunctional (meth) acrylic monomer having a plurality of double bonds. (B) is contained in a ratio of 20/80 or more and 80/20 or less as (A) / (B) (weight ratio), and (B) the ultraviolet curing agent (C) is added in an amount of 0. The said subject is solved by using the curable coating agent characterized by containing the urethane-acrylic polymer composition containing 01-3 weight part.

  Since this invention contains a urethane polymer (A), it is possible to suppress stickiness (tack) in a dry state after coating, and a polyfunctional (meth) acrylic monomer having a plurality of double bonds Since it contains a polymerizable monomer (B) consisting of a body, crosslinking of the component (B) proceeds during curing, and a tough film is formed and cured in a state of being in close contact with the surface of the substrate. It becomes possible to improve adhesion.

The present invention will be described in detail below.
The curable coating agent according to the present invention includes a urethane polymer (hereinafter referred to as “component (A)”), a polymerizable monomer (hereinafter referred to as “component (B)”), and an ultraviolet curing agent ( Hereinafter, it is a coating agent containing a urethane-acrylic polymer composition containing “(C) component”.

[(A) component]
The urethane prepolymer as the component (A) is a polymer obtained by urethanizing a polyvalent isocyanate compound and a diol compound.

  The polyvalent isocyanate compound refers to a compound having at least two isocyanate groups as functional groups. Specific examples include tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, or a mixture thereof. can give.

  The diol compound means a compound having at least two hydroxyl groups as functional groups, and generally known diols are used. Examples of the diol include polyester polyol, polycarbonate polyol, polyether polyol, carboxyl group-containing diol, and other diols.

  Specific examples of the carboxyl group-containing diol include dimethylol alkanoic acids such as dimethylolpropionic acid and dimethylolbutanoic acid.

  Specific examples of the other diols include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl- 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, trimethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, cyclohexane dimethanol, methylpentanediol adipate, etc. Silicone modified dimers such as relatively low molecular weight diols, polymer diols such as polyester diols, polyester ether diols and polycarbonate diols, and alcohol-modified silicone oils. Lumpur, and the like. These diol compounds may be used alone or in combination of two or more.

  By the way, when it contains the ultraviolet curing agent mentioned later and makes it disperse | distribute to water, when a carboxyl group containing diol is used among said diol compounds, the characteristic as a dispersing agent will be provided to (A) component itself obtained. And can be dispersed in an aqueous medium without using other dispersants.

  When the component (A) is an aqueous dispersion, the mixing ratio of the polyvalent isocyanate and the diol compound is an equivalent ratio, and the polyvalent isocyanate compound / diol compound is preferably 1.2 / 1.0 or more, 1.4 / 1.0 or more is preferable. When the ratio is smaller than 1.2 / 1.0, the viscosity of the urethane prepolymer is increased, and the dispersibility in water is reduced to cause aggregation and coarse particles may be generated. On the other hand, the upper limit of the mixing ratio is preferably 2.0 / 1.0, and preferably 1.9 / 1.0. If the ratio is larger than 2.0 / 1.0, the unreacted polyvalent isocyanate becomes excessive, and the dispersion state may deteriorate due to aggregation during foaming or foaming.

  For the reaction temperature and reaction time of the urethanization reaction, production conditions similar to those for ordinary urethane polymers can be selected. Specifically, the reaction temperature is preferably 50 to 120 ° C, and preferably 70 to 100 ° C. The reaction time is preferably 0.5 to 15 hours, and preferably 3 to 5 hours.

  When a carboxyl group-containing diol is used as the diol compound, the obtained component (A) contains a carboxyl group. At this time, when at least a part is neutralized with the basic compound, the resulting aqueous dispersion is further stabilized and, as described later, when dispersed in an aqueous medium, the dispersion can be performed without using a dispersant. This is also preferable. The basic compound is not particularly limited as long as it can neutralize the carboxyl group, and examples thereof include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, trialkylamines such as trimethylamine and triethylamine, and the like. It is done. Among these basic compounds, trialkylamine is preferable from the viewpoint of water resistance when used as at least part of the basic compound to be used.

  As the diol compound, in addition to the above carboxyl group-containing diol, polyester di (poly) ol is preferable because it has less stickiness (tackiness), particularly when it is formed into a coating film.

  The obtained component (A) can be dispersed in an aqueous medium which is water or a mixture of water and an organic solvent such as methanol or ethanol having hydrophilicity, whereby an aqueous dispersion can be obtained. When the obtained component (A) contains a carboxyl group that is at least partially neutralized, the component (A) itself can serve as a dispersant. It becomes possible to disperse in the aqueous medium without using it. In addition, when the obtained component (A) does not contain a carboxyl group, it can be dispersed in the aqueous medium by using a commonly used dispersant.

[Component (B)]
The component (B) is a polymerizable monomer containing a polyfunctional (meth) acrylic monomer having a plurality of double bonds. The component (B) may contain a monofunctional (meth) acrylic monomer having one double bond and other monofunctional vinyl monomers. Moreover, when the said (B) component has a functional group which can couple | bond with a urethane polymer (A), (A) component and (B) component can be compounded more closely. For this reason, from the viewpoint other than the number of double bonds, the component (B) is a polymerizable monomer having a functional group capable of binding to the urethane polymer (A) (hereinafter referred to as “urethane bondable polymerizable monomer”). It may be referred to as “body”.).

  As said (B) component used for the curable coating agent concerning this invention, a polyfunctional (meth) acrylic-type monomer is contained as an essential component as above-mentioned, and it is monofunctional (meth) as needed. An acrylic monomer may be contained. Examples of the urethane-bondable polymerizable monomer include (meth) acrylic monomers containing a hydroxyl group that can be bonded to an isocyanate group contained in a urethane polymer constituent unit. In this specification, “(meth) acryl” means “acryl or methacryl”.

  Specific examples of the polyfunctional (meth) acrylic monomer include 1,6-hexanediol di (meth) acrylate and 1,9-nonanediol di (meth) acrylate as bifunctional monomers. A polymerizable monomer having no functional group capable of binding to the urethane polymer (A) such as (hereinafter sometimes referred to as “urethane non-bonding polymerizable monomer”), and the like. Examples of the above monomers include non-urethane-bondable polymerizable monomers such as trimethylolpropane tri (meth) acrylate and dipentaerythritolpropane hexa (meth) acrylate, and trisacrylic acid = hydroxyethyllysine tri (methylene). And urethane bondable polymerizable monomers such as.

  Next, examples of the monofunctional (meth) acrylic monomers include (meth) acrylic acid ester compounds such as (meth) acrylic acid alkyl esters, (meth) acrylic acid alkoxyalkyl esters, and other (meth) Examples include acrylic monomers.

  Specific examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. And non-urethane polymerizable monomers such as cyclohexyl (meth) acrylate, benzyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, and the like.

  Specific examples of the other monofunctional (meth) acrylic monomers include urethane-binding polymerizable monomers such as hydroxyethyl (meth) acrylate and hydroxyisopropyl (meth) acrylate, and (meth) acrylic acid. Examples thereof include urethane non-bonding polymerizable monomers such as 2-methoxyethyl, 2-ethoxyethyl (meth) acrylate, and 2-butoxyethyl (meth) acrylate.

  In addition, each said (meth) acrylic-type monomer may be used independently, and 2 or more types may be mixed and used for it. In addition, the components (A) and (B) used are not limited to the compounds listed above, and can be used as long as the effects of the present invention are not adversely affected. For example, examples of the polymerizable monomer other than the component (B) include styrene and its derivatives, and other vinyl monomers.

  Examples of the styrene and derivatives thereof include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene and the like.

  Examples of the other polymerizable monomers include vinyl group-containing monomers such as vinyl halide compounds and polyfunctional unsaturated monomers.

[Mixing of component (B) to component (A)]
As a method of mixing the component (B) with the component (A), a method of mixing the component (B) with the component (A) after the formation reaction of the urethane polymer as the component (A), Examples thereof include a method of obtaining a component (A) by subjecting a polyvalent isocyanate compound and a diol compound to a urethane reaction in a (meth) acrylic monomer which is a constituent component of the component B). In particular, when the latter method is employed, the resulting curable urethane polymer composition is preferable because the component (A) and the component (B) can be more closely combined. In this case, when at least a part of the component (B) includes a urethane-bondable polymerizable monomer such as the hydroxyl group-containing (meth) acrylic monomer, it can react with the polyvalent isocyanate. In this case, when the polymerizable functional group is present in the component (A) and ultraviolet curing is performed, the component (A) and the component (B) can be combined more closely, which is preferable.

  By the way, the urethane polymer composition obtained may be an aqueous dispersion. By using an aqueous dispersion, liquid handling is possible without using an organic solvent, and the working environment and workability are excellent.

  As a method for preparing an aqueous dispersion, the above-mentioned aqueous medium and, if necessary, a dispersant are added to the mixture of the component (A) and the component (B) to cause phase inversion, and the aqueous dispersion of the component (A) , (B) component mixing method and the like.

  As a specific example of the former method, a urethane polymerization step for obtaining a urethane polymer solution by reacting a polyvalent isocyanate and a diol was performed, and then a mixing step for mixing a polyfunctional (meth) acrylic monomer was performed. Then, by adding water to the obtained urethane polymer solution to invert the phase to obtain an aqueous dispersion, a method for obtaining an aqueous dispersion or a polyfunctional (meth) acrylic polyhydric isocyanate and diol After performing a urethane polymerization step to obtain a urethane polymer solution by reacting in the presence of a system monomer, water is added to the obtained urethane polymer solution to perform phase inversion to obtain an aqueous dispersion, A method for obtaining an aqueous dispersion can be mentioned. Of these methods, the latter method is preferable because the component (A) and the component (B) can be more closely combined.

  When preparing an aqueous dispersion of the urethane-acrylic polymer composition constituting the curable coating agent according to the present invention using any of the mixing methods described above, the component (A) in the aqueous dispersion and ( The mixing ratio with the component (B) is preferably (A) / (B) = 20/80 or more, more preferably 30/70 or more, in terms of the solid content weight ratio. If it is smaller than 20/80, the dispersibility in water tends to be insufficient. On the other hand, the upper limit of the mixing ratio is preferably 80/20, and preferably 70/30. If it is larger than 80/20, the adhesion to the substrate may be lowered.

  The content ratio of the polyfunctional (meth) acrylic monomer in the polymerizable monomer (B) is preferably 30% by weight or more, and preferably 50% by weight or more. If it is less than 30% by weight, the surface hardness (pencil hardness) may be insufficient. In addition, the upper limit of a content rate is 100 weight%.

  Further, the content of the monofunctional (meth) acrylic monomer in the polymerizable monomer (B) is preferably 70% by weight or less, and preferably 50% by weight or less. If it exceeds 70% by weight, the surface hardness (pencil hardness) may be insufficient. On the other hand, the lower limit of the content ratio does not need to be set and may be 0% by weight.

[Component (C)]
The ultraviolet curing agent as the component (C) refers to an agent that initiates radical polymerization by irradiating ultraviolet rays.

  Examples of the ultraviolet curing agent include 1-hydroxy-cyclohexyl-phenyl ketone and 2-hydroxy-2-methyl-1-phenyl-propan-1-one.

  The amount of the ultraviolet curing agent used is preferably 0.01 to 3 parts by weight with respect to 100 parts by weight (solid content) of the component (B). Moreover, what is necessary is just to select the wavelength and intensity | strength of an ultraviolet-ray suitably according to the kind of the said ultraviolet curing agent.

[Dispersant]
As described above, as a dispersant used for obtaining an aqueous dispersion of the urethane-acrylic polymer composition constituting the curable coating agent according to the present invention, a carboxyl group-containing diol is obtained as a part of the raw material diol. In addition to the self-dispersing method using the urethane polymer as the component (A), various known dispersants can be used as long as the effects of the present invention are not adversely affected. In addition, if necessary, a colorant such as a pigment, a wax, an antifoaming agent, a plasticizer, a film forming auxiliary agent, and the like are added to the aqueous polymer dispersion as long as the effects of the present invention are not impaired. can do.

[Use of urethane-acrylic polymer composition]
The aqueous dispersion of the urethane-acrylic polymer composition obtained by the above method is used as one component of the curable coating agent.

  The curable coating agent is applied onto a substrate and dried to form a coating film. During this drying or after drying, the component (B) is polymerized by curing by irradiation with energy rays such as ultraviolet rays, and the composition is cured to obtain a laminate having a cured layer. Can do.

  As the substrate, for example, films, sheets, or molded articles made of various resins such as polyester, polyolefin, and polyamide can be used.

  The laminate thus obtained has a feature that the adhesion to the substrate is good despite the low stickiness of the surface (tackiness), for example, a protective adhesive film, It can be used as a masking adhesive film, a decorative film, and the like. Moreover, since these films have low tackiness, they can be easily rewound even if they are wound and stored.

In addition, by further laminating and curing a layer made of the curable coating agent or the ultraviolet curable composition of the present invention on the coated surface of the above laminate, better water resistance and surface hardness can be obtained. Particularly preferred.
In addition, as an ultraviolet curable composition used here, what added about 0.3-2 weight part of said (C) component per 100 weight part of the above-mentioned polyfunctional (meth) acrylic-type monomer is used preferably. .

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example, this invention is not limited by a following example, unless the summary is exceeded. First, the evaluation method and the raw materials used will be described.

<Raw materials>
[Polyisocyanate compound]
IPDI: isophorone diisocyanate ... manufactured by Evonik Degussa
H12MDI: 4,4′-dicyclohexylmethane diisocyanate: Sumitomo Bayer Urethane Co., Ltd .: Desmodur W (trade name).

[Diol compound]
1.6-hexanediol: Ube Industries, Ltd .: UH200 (trade name), hereinafter referred to as “UH200”.
Polypropylene glycol: manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: D200 (trade name), hereinafter referred to as “D200”.
Dimethylolpropionic acid: Mallinckrodt Chemical Inc. “DMPA” manufactured by the company.

[Neutralizer]
Triethylamine: Wako Pure Chemical Industries, Ltd., hereinafter referred to as “TEA”.

[(Meth) acrylic monomer]
Trimethylolpropane triacrylate: Osaka Organic Chemical Co., Ltd., hereinafter referred to as “TMP3A”.
Dipentaerythritol propane hexaacrylate: manufactured by Daicel Cytec Co., Ltd., hereinafter referred to as “DPHA”.
Dipropylene glycol diacrylate: manufactured by Daicel Cytec Co., Ltd., hereinafter referred to as “DPGDA”.
Trisacrylic acid = hydroxyethyl lysine tri (methylene): manufactured by Osaka Organic Chemical Co., Ltd., hereinafter referred to as “V # 300”.

[Polymerization catalyst]
Dibutyltin dilaurate: manufactured by Aldrich, hereinafter referred to as “DBTDL”.
[UV curing agent]
1-hydroxy-cyclohexyl-phenyl ketone: manufactured by BASF: Irgacure 184 (trade name), hereinafter referred to as “Irgacure 184”.
[Others: Urethane-acrylic emulsion]
-SU-100 (trade name) ... manufactured by Chuo Rika Kogyo Co., Ltd .: Urethane-acrylic emulsion (obtained from (meth) acrylic monomer not containing polyfunctional (meth) acrylic monomer and urethane polymer) Urethane-acrylic polymer composite emulsion)

<Evaluation method>
[Finger touch after drying]
After the first layer was dried, the coated surface was touched with a finger, and whether or not there was a tack was confirmed according to the following criteria.
○: No tack.
X: There is tack.

[Cross-cut peel test]
A total of 100 cuts were made on the coated surface of the obtained laminate in a vertical and horizontal direction with a cutter, and then a cellophane tape was applied, followed by peeling. At this time, the number of eyes in which the coated surface was not peeled out of 100 eyes was counted.

[Fingerprint adhesion]
A finger was applied to the coated surface of the obtained laminate, and whether or not a fingerprint was formed was visually confirmed according to the following criteria.
○: Almost no fingerprint marks can be confirmed.
X: The trace of a fingerprint can be confirmed clearly.

[Pencil hardness]
The surface hardness of the obtained laminate was evaluated by measuring the pencil hardness according to JIS K5600-5-4.

[water resistant]
The water resistance of the obtained laminate was evaluated according to the following criteria based on the state of the coated surface (whitening and peeling) after the laminate was immersed in warm water at 50 ° C. for 3 hours.
◎: Neither whitening nor peeling ○: Partially whitened only at the edge, but no peeling △: Almost the entire surface was whitened and no peeling ×: The coating layer was peeled off from the PET film of the substrate

(Production of UV-curable polymerizable monomer-containing urethane polymer (hereinafter referred to as “urethane polymer / polymerizable monomer mixture”))
(Production of urethane polymer / polymerizable monomer mixture 1)
Each component of the polyol shown in Table 1 and each component of the polymerizable monomer shown in Table 1 were added to a four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, and the internal temperature was 50. The polyisocyanate in the amount shown in Table 1 was added, and the mixture was heated to 90 ° C. and reacted at this temperature for 5 hours to obtain a urethane prepolymer solution.
The obtained urethane prepolymer solution was cooled to 50 ° C., and the neutralizing agent (TEA) in the amount shown in Table 1 was added to neutralize the carboxyl groups in the urethane prepolymer solution, thereby producing a urethane polymer / polymerizable monomer. A body mixture 1 was obtained.

(Production of urethane polymer / polymerizable monomer mixture 2-6)
Each component of the polyol shown in Table 1 and each component of the polymerizable monomer shown in Table 1 were added to a four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, and the internal temperature was 50. The polyisocyanate in the amount shown in Table 1 was added, and the mixture was heated to 90 ° C. and reacted at this temperature for 5 hours to obtain a urethane prepolymer solution.
The obtained urethane prepolymer solution was cooled to 50 ° C., and the neutralizing agent in the amount shown in Table 1 was added to neutralize the carboxyl groups in the urethane prepolymer solution.
Next, ion exchange water (phase inversion water) in the amount shown in Table 1 was dropped into this urethane prepolymer solution over 10 minutes, and a urethane polymer / polymerizable monomer mixed liquid which was a milky white aqueous dispersion. 2-6 were obtained.

(Manufacture of coating liquids 1-6)
2 wt% of the ultraviolet curing agent Irgacure 184 is added to 100 parts by weight of the total amount of the polymer and the polymerizable monomer in the urethane polymer / polymerizable monomer mixed liquids 1 to 6 obtained above, As shown in Table 2, UV curable compositions (coating solutions) 1 to 6 were obtained.

(Coating liquids 7 and 8)
As shown in Table 2, predetermined polyfunctional vinyl monomers, a diluting solvent and an ultraviolet curing agent were mixed to obtain UV curable compositions (coating liquids) 7 and 8.

(Create laminate)
Example 1
Coating film 1 is applied to a PET film (Toray Industries, Inc .: Lumirror, thickness 50 μm) so that the film thickness after curing is 1 μm, and UV-cured using a 120 W / cm ozone-less metal halide lamp. Got. About this, the cross-cut peeling test and the fingerprint adhesion evaluation were performed. The results are shown in Table 3.

(Examples 2-9)
A coating solution of the first layer shown in Table 3 was applied to the PET film so that the film thickness after curing was 1 μm, and then dried under conditions of 100 ° C. × 1 minute, and tack evaluation was performed. Subsequently, it was ultraviolet-cured using a 120 W / cm ozone-less metal halide lamp to obtain a laminate.
Next, in the examples in which the second layer is described in Table 3, the coating liquid for the second layer shown in Table 3 is similarly applied on the laminate obtained by curing after coating the first layer. The film was applied to a thickness of 1 μm, then dried at 100 ° C. for 1 minute, and then UV-cured using a 120 W / cm ozone-less metal halide lamp to obtain a laminate.
Using the obtained laminate, the cross-cut peel test and the fingerprint adhesion evaluation were performed. The results are summarized in Table 3.

(Comparative Examples 1 and 4)
Using the coating liquids 7 and 8 shown in Table 2, coating and curing were performed in the same manner as in Example 1 to obtain a laminate. About this, each evaluation similar to Example 1 was performed. The results are shown in Table 3.

(Comparative Examples 2 and 3)
In the same manner as in Example 1, the film thickness after curing the aqueous urethane- (meth) acrylic polymer composite emulsion (SU-100) containing no polyfunctional (meth) acrylic monomer on the PET film is 1 μm. It was coated as the first layer, and then dried at 100 ° C. for 1 minute to obtain a laminate.
Next, on the laminate obtained by drying the first layer, the coating solution of the second layer shown in Table 3 was applied to 1 μm, and then dried under conditions of 100 ° C. × 1 minute, Tack evaluation was performed. Subsequently, it was ultraviolet-cured using a 120 W / cm ozone-less metal halide lamp to obtain a laminate.
Using the obtained laminate, the cross-cut peel test and the fingerprint adhesion evaluation were performed. The results are shown in Table 3.

なお、実施例１及び比較例１は、塗工後、直ちに硬化したので、乾燥工程を行っていない。

In addition, since Example 1 and Comparative Example 1 were cured immediately after coating, the drying process was not performed.

(result)
In Example 1, the adhesion evaluation by the cross-cut peel test was good and the fingerprint adhesion was also good.
In Examples 2 to 5, Polymers 2 to 5 were used as a primer for improving the adhesion between the second-layer ultraviolet curable resin and the PET film. Compared with the case of using the aqueous urethane acrylic emulsions of Comparative Examples 2 and 3, adhesion and fingerprint adhesion are greatly improved.
Example 7 and Comparative Example 4 are systems containing the same polyfunctional vinyl monomer (DPHA), but when combined with polyurethane as in the present invention, the adhesion is excellent and the fingerprint adhesion is also good. Become.
In Example 9, since “V # 300” having a hydroxyl group capable of reacting with an isocyanate group in urethane is used as the polymerizable monomer, the urethane polymer has a vinyl group at the terminal, and the urethane polymer ( Pencil hardness and water resistance are further improved because A) and the polymerizable monomer (B) are chemically bonded.

Claims (9)

  A urethane polymer (A) obtained by reacting a polyvalent isocyanate compound and a diol compound, and a polymerizable monomer (B) containing a polyfunctional (meth) acrylic monomer having a plurality of double bonds; (A) / (B) (weight ratio) in a ratio of 20/80 or more and 80/20 or less, and (B) 0.01 to 3 weight of the ultraviolet curing agent (C) per 100 parts by weight. A curable coating agent comprising a urethane-acrylic polymer composition containing a part.   The urethane polymer (A) is a urethane polymer in which a carboxyl group-containing diol is used as a raw material diol compound, and at least a part of the carboxyl group is neutralized with a basic compound. The curable coating agent described in 1.   The curable coating agent according to claim 1 or 2, further comprising a monofunctional (meth) acrylic monomer as the polymerizable monomer (B).   The curability according to any one of claims 1 to 3, wherein the polymerizable monomer (B) includes a polymerizable monomer having a functional group capable of binding to the urethane polymer (A). Coating agent.   The curable coating agent according to claim 4, wherein the polymerizable monomer (B) having a functional group capable of binding to the urethane polymer (A) is a hydroxyl group-containing (meth) acrylic monomer. .   The curable coating agent according to any one of claims 1 to 5, wherein the urethane- (meth) acrylic polymer composition is dispersed in an aqueous medium.   A laminate obtained by applying, drying and curing the curable coating agent according to any one of claims 1 to 6 on a substrate.   After applying, drying and curing the curable coating agent according to any one of claims 1 to 6 on a substrate, a layer made of the curable coating agent or the ultraviolet curable composition is laminated and cured. A multilayer laminate.   The laminate according to claim 7, wherein the substrate is a resin film.