JP7110754B2 - Active energy ray-curable resin composition, coating agent using the same, and sheet - Google Patents

Description

The present invention relates to an active energy ray-curable resin composition. Active energy ray-curable resin composition having excellent chemical resistance, excellent workability, etc., and is particularly suitable for decorative molding applications, and a coating agent using the same , as well as sheets.

Plastic substrates such as polycarbonate and polymethyl methacrylate are widely used for home appliances, automotive products, liquid crystal display members, etc., because they are excellent in optical properties such as workability, impact resistance, and transparency.

However, since the surface of these plastic substrates is easily scratched, the surface of the plastic substrate is sometimes coated with a hard coating agent in order to impart scratch resistance. As the hard coating agent, an active energy ray-curable resin composition is often used because of its excellent adhesion to plastic substrates and high curing speed, which contributes to improved productivity.

In addition, the active energy ray-curable resin composition is sometimes used in decorative molding for imparting design properties.
As a method of decorative molding, conventionally, there is a method of kneading a pigment into a thermoplastic resin and molding it, or a method of spray coating a paint on the surface of a molded resin product to decorate. However, these techniques are difficult to apply to complex-shaped moldings.
Therefore, insert molding and in-mold molding using molds, and in recent years, three-dimensional molding such as TOM molding (three dimension overlay method (three-dimensional surface coating method)) that does not require a mold is used to achieve the above-mentioned decorative molding. By doing so, the application of decorative molding to molded products with complicated shapes is being studied.

In addition, in the active energy ray-curable resin composition used in the above-mentioned three-dimensional molding, etc., it is particularly important to have workability such that cracks do not occur even when molded into a complicated shape, conformability to molds, and elongation. degree is required.
Moreover, when the active energy ray-curable resin composition is used as the outermost surface material of a molded product, surface hardness and scratch resistance are required. In particular, molded articles that may come into contact with fingers require suppression of surface tackiness and chemical resistance to sunscreens, hand creams, etc., in addition to the properties described above.

Here, for example, Patent Document 1 below discloses a decorative molded sheet having a skin layer made of a reaction-cured product of a resin composition containing a polycarbonate-based polyurethane and a non-yellowing polyisocyanate. Patent Document 1 discloses that a molded product using the decorative molded sheet forms a complicated surface shape and has excellent scratch resistance.
Further, for example, Patent Document 2 below discloses a decorative sheet composition comprising a compound containing a furyl group, a polymerizable compound, and a polymerization initiator, and a method for producing a molded article. Patent Document 2 discloses that a decorative sheet using the above composition achieves both excellent hard coat properties and moldability at a high level, which are compatible with various molding processes.

JP 2014-128922 A JP 2017-193694 A

However, the resin composition disclosed in Patent Document 1 contains polyisocyanate as a heat curing agent, and in order to complete the curing of the coating film, it is necessary to apply heat or provide an aging period. Therefore, it is inferior in productivity.
In addition, although the composition disclosed in Patent Document 2 is excellent in hard coat properties and chemical resistance, it does not have elongation that can be applied to various molding methods, and there is a problem in this respect. remain.

The present invention has been made in view of such circumstances, and when cured, it has excellent adhesion to the substrate, elongation, elastic modulus and strength, has no surface tackiness, and has excellent chemical resistance. Provided are an active energy ray-curable resin composition, a coating agent using the same, and a sheet, which are excellent in processability and productivity and particularly suitable for use in decorative molding.

The present inventors have made intensive studies in order to solve the above problems. In the process of the research, the use of urethane (meth)acrylate as a main component of the active energy ray-curable resin composition was examined. Then, as the material of the urethane (meth)acrylate, the isocyanate used in the urethane reaction is an alicyclic structure-containing polyisocyanate, and the polyol used in the urethane reaction is a low molecular weight polyol having a number average molecular weight of 300 or less, and a number average polyol. A high-molecular-weight polyester-based polyol having a molecular weight of 500 or more was used in combination, and the urethane bond concentration of the urethane (meth)acrylate was set to a specific range. As a result, it was found that the above active energy ray-curable resin composition can form a cured coating film which is excellent in adhesion to substrates, elongation, elastic modulus and strength, and which is free from surface tackiness.

That is, the present invention provides an active energy ray containing a urethane (meth)acrylate (A) which is a reaction product of an alicyclic structure-containing polyisocyanate (a1), a polyol (a2), and a hydroxyl group-containing (meth)acrylate (a3). A curable resin composition,
The polyol (a2) contains a low molecular weight polyol (a2-1) having a number average molecular weight of 60 to 300 and a high molecular weight polyester polyol (a2-2) having a number average molecular weight of 500 to 20,000,
A first gist is an active energy ray-curable resin composition in which the urethane (meth)acrylate (A) has a urethane bond concentration of 3.5 mmol/g or more.

Moreover, this invention makes a 2nd summary the coating agent formed by containing the said active-energy-ray-curable resin composition. Furthermore, the third aspect of the present invention is a sheet comprising a cured product of the active energy ray-curable resin composition.

Thus, the active energy ray-curable resin composition of the present invention is a urethane (meth) which is a reaction product of an alicyclic structure-containing polyisocyanate (a1), a polyol (a2), and a hydroxyl group-containing (meth)acrylate (a3). ) containing acrylate (A). Then, as the polyol (a2), a low molecular weight polyol (a2-1) having a number average molecular weight of 60 to 300 and a high molecular weight polyester polyol (a2-2) having a number average molecular weight of 500 to 20,000 are used in combination. (Meth)acrylate (A) has a urethane bond concentration of 3.5 mmol/g or more. Therefore, a cured coating film formed from the active energy ray-curable resin composition of the present invention and a cured coating film formed from a coating agent containing the active energy ray-curable resin composition of the present invention are It has excellent adhesion to substrates, elongation, elastic modulus and strength, has no surface tackiness, has excellent chemical resistance, has excellent workability and productivity, and is particularly suitable for decorative molding.
Since the above effects are achieved, the active energy ray-curable resin composition of the present invention can be used as a coating agent for various substrates, as a material for molding sheets and their protective layers, and as a hard material for decorative films. It is useful as a coat material.

In particular, the ratio of the alicyclic structure-containing polyisocyanate (a1) to the total of the alicyclic structure-containing polyisocyanate (a1), the polyol (a2), and the hydroxyl group-containing (meth)acrylate (a3) is 30% by weight or more. Then, a cured coating film having a more excellent elastic modulus can be obtained.

Further, the alicyclic structure-containing polyisocyanate (a1) and the low molecular weight polyol (a2- When the total proportion of 1) is 40% by weight or more, the surface tackiness is further suppressed, and a cured coating film having an excellent elastic modulus can be obtained.

Furthermore, the ratio of the alicyclic structure-containing polyisocyanate (a1) to the total of the alicyclic structure-containing polyisocyanate (a1), the polyol (a2), and the hydroxyl group-containing (meth)acrylate (a3) is 30 to 60% by weight. %, the proportion of the low molecular weight polyol (a2-1) is 10 to 40% by weight, the proportion of the high molecular weight polyester polyol (a2-2) is 10 to 50% by weight, and the hydroxyl group-containing ( When the proportion of the meth)acrylate (a3) is 1 to 15% by weight, the surface tackiness is further suppressed, and a cured coating film excellent in elongation, elastic modulus and strength can be obtained.

In addition, when the low-molecular-weight polyol (a2-1) has a branched structure, association between urethane bonds is suppressed when a cured coating film is formed, and a suitable balance between crystallinity and flexibility is imparted. be able to.

Then, when the hydroxyl group-containing (meth)acrylate (a3) is a (meth)acrylate having one (meth)acryloyl group in the molecule, it imparts an appropriate crosslinked structure to the cured coating film and has elongation. can be given.

Next, an embodiment of the present invention will be described in detail. However, the present invention is not limited to this embodiment.

The active energy ray-curable resin composition (hereinafter sometimes abbreviated as "resin composition") of the present invention is obtained using a specific urethane (meth)acrylate (A). The content of the urethane (meth)acrylate (A) in the resin composition (excluding the solvent) is usually 50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight or more, More preferably, it is 95% by weight or more. In the present invention, the resin composition may be composed only of the urethane (meth)acrylate (A) excluding the solvent. Details of the urethane (meth)acrylate (A) and each component material appropriately contained in the active energy ray-curable resin composition are described below.

<<Urethane (meth)acrylate (A)>>
The urethane (meth)acrylate (A) used in the present invention is a reaction product obtained by reacting an alicyclic structure-containing polyisocyanate (a1), a polyol (a2), and a hydroxyl group-containing (meth)acrylate (a3). It is a thing. The polyol (a2) contains a low molecular weight polyol (a2-1) having a number average molecular weight of 60 to 300 and a high molecular weight polyester polyol (a2-2) having a number average molecular weight of 500 to 20,000.
That is, the urethane (meth)acrylate (A) used in the present invention has structural units derived from the alicyclic structure-containing polyisocyanate (a1), and a structure derived from the low molecular weight polyol (a2-1) having a number average molecular weight of 60 to 300. It is a compound having a unit, a structural unit derived from a high molecular weight polyester polyol (a2-2) having a number average molecular weight of 500 to 20,000, and a structural unit derived from a hydroxyl group-containing (meth)acrylate (a3).
From the viewpoint of the effects of the present invention, 50% by weight or more, particularly 80% by weight or more of the entire polyol (a2) is the low-molecular-weight polyol (a2-1) and the high-molecular-weight polyester-based polyol (a2-2). and more preferably all of the polyol (a2) consists of the low-molecular-weight polyol (a2-1) and the high-molecular-weight polyester-based polyol (a2-2).

The urethane bond concentration of the urethane (meth)acrylate (A) is 3.5 mmol/g or more. Preferably, the urethane bond concentration of the urethane (meth)acrylate (A) is 3.5 to 6 mmol/g, more preferably 4 to 5.5 mmol/g. The urethane bond concentration is a value obtained by calculating the ratio of urethane bonds [-NHC(=O)O-] in the urethane (meth)acrylate (A) from the composition of the urethane (meth)acrylate (A). be. Specifically, the number of isocyanate functional groups of the alicyclic structure-containing polyisocyanate (a1) is N, the molar mass of the alicyclic structure-containing polyisocyanate (a1) is M (g/mol), and the alicyclic structure-containing polyisocyanate (a1) , the polyol (a2), and the ratio of the alicyclic structure-containing polyisocyanate (a1) to the total of the hydroxyl group-containing (meth)acrylate (a3) is P (% by weight), the urethane bond concentration is expressed by the following formula: (1) can be obtained.
(N×1000/M)×(P/100) (1)
As described above, since the urethane bond concentration of the urethane (meth)acrylate (A) is high, it is possible to impart a high elastic modulus to a cured coating film formed from the active energy ray-curable resin composition of the present invention. can be done.

In the present invention, (meth)acryl means acryl or methacryl, (meth)acryloyl means acryloyl or methacryloyl, and (meth)acrylate means acrylate or methacrylate.

[Alicyclic structure-containing polyisocyanate (a1)]
Examples of the alicyclic structure-containing polyisocyanate (a1) include isophorone diisocyanate, norbornene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, hydrogenated diphenylmethane diisocyanate, and the like. is given.
These may be used individually by 1 type, and may be used in combination of 2 or more types.
Among them, the alicyclic structure-containing polyisocyanate (a1) is preferably a diisocyanate from the viewpoint of elongation of the cured coating film. From the same viewpoint, isophorone diisocyanate, 1,4-bis(isocyanatomethyl)cyclohexane, and 1,3-bis(isocyanatomethyl)cyclohexane are more preferred, and 1,3-bis(isocyanatomethyl) is particularly preferred. is cyclohexane.

In particular, with respect to the sum of the alicyclic structure-containing polyisocyanate (a1), the polyol (a2), and the hydroxyl group-containing (meth)acrylate (a3), which are constituent materials of the urethane (meth)acrylate (A), the alicyclic When the ratio of the structure-containing polyisocyanate (a1) is 30% by weight or more, a cured coating film having a more excellent elastic modulus can be obtained. The proportion of the alicyclic structure-containing polyisocyanate (a1) is preferably 30 to 60% by weight, more preferably 35 to 57% by weight, still more preferably 40 to 55% by weight.

[Polyol (a2)]
As the polyol (a2), as described above, a low molecular weight polyol (a2-1) having a number average molecular weight of 60 to 300 and a high molecular weight polyester polyol (a2-2) having a number average molecular weight of 500 to 20,000 ) are used in combination.

The number average molecular weight of the low molecular weight polyol (a2-1) is preferably 80-300, more preferably 100-200. The number average molecular weight of the high molecular weight polyester polyol (a2-2) is preferably 500 to 10,000, more preferably 600 to 3,000, still more preferably 700 to 2,200. By doing so, a higher elastic modulus and a higher elongation can be easily imparted, and the physical properties can be finely adjusted.

In addition, let number average molecular weight be the number average molecular weight calculated based on the hydroxyl value measured based on JISK1557 in this invention. Specifically, the hydroxyl value is measured and calculated by (56.1×1000×valence)/hydroxyl value [mgKOH/g] by the terminal group quantification method. In the above formula, the valence is the number of hydroxyl groups in one molecule.

The low molecular weight polyol ( The proportion of a2-1) is preferably 10 to 40% by weight, more preferably 12 to 30% by weight, still more preferably 14 to 25% by weight.
In addition, with respect to the total of the alicyclic structure-containing polyisocyanate (a1), the polyol (a2), and the hydroxyl group-containing (meth)acrylate (a3), which are the constituent materials of the urethane (meth)acrylate (A), the above high molecular weight The proportion of the polyester polyol (a2-2) is preferably 10 to 50 wt%, more preferably 15 to 45 wt%, still more preferably 20 to 40 wt%.
Furthermore, with respect to the total of the alicyclic structure-containing polyisocyanate (a1), the polyol (a2), and the hydroxyl group-containing (meth)acrylate (a3), which are constituent materials of the urethane (meth)acrylate (A), the alicyclic The total ratio of the structure-containing polyisocyanate (a1) and the low-molecular-weight polyol (a2-1) is preferably 40% by weight or more, more preferably 50 to 90% by weight, still more preferably 55 to 80% by weight. By setting it to such a range, the feeling of surface tack is suppressed, and a cured coating film excellent in elastic modulus can be obtained.

In particular, the ratio (a2-1/a2-2) between the low molecular weight polyol (a2-1) and the high molecular weight polyester polyol (a2-2) is 20/80 to 80/20 by weight. However, it is preferable because it is easy to impart a higher elastic modulus and a higher elongation and the physical properties can be finely adjusted. From the same point of view, the above ratio (weight ratio) is more preferably (a2-1/a2-2) = 22/78 to 70/30, particularly preferably (a2-1/a2-2) = 25 /75 to 60/40.

Specific examples of the low-molecular-weight polyol (a2-1) include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, dimethylolpropane, neopentyl glycol, 2,2-diethyl-1,3 -propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-tetramethylenediol, 1,3-tetramethylenediol, 2-methyl-1,3-trimethylenediol, 1,5 -pentamethylenediol, 1,6-hexamethylenediol, 3-methyl-1,5-pentamethylenediol, 2,4-diethyl-1,5-pentamethylenediol, pentaerythritol diacrylate, 1,9-nonanediol , 2-methyl-1,3-hexanediol, 2-methyl-1,8-octanediol and other aliphatic alcohols, 1,4-cyclohexanediol, cyclohexyldimethanol, tricyclodecanedimethanol and other alicyclic Examples include diols, bisphenols such as bisphenol A, and sugar alcohols such as xylitol and sorbitol, and these can be used singly or in combination of two or more.
Among these, diols having a branched structure are preferred, and diols having an aliphatic chain having a branched structure are particularly preferred, from the viewpoint of imparting appropriate crystallinity and flexibility to a cured coating film. From the viewpoint of yellowing of the cured coating film, more preferred are compounds having a structure that does not contain an aromatic ring or an unsaturated group, particularly preferred are aliphatic diols, and still more preferred is neopentyl glycol.

Examples of the high-molecular-weight polyester-based polyol (a2-2) include condensation polymers of polyhydric alcohols and polycarboxylic acids; ring-opening polymers of cyclic esters (lactones); polyhydric alcohols and polycarboxylic acids; A reactant with three kinds of components such as an acid and a cyclic ester can be mentioned.

Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylenediol, 1,3-tetramethylenediol, 2-methyl-1,3-tri methylenediol, 1,5-pentamethylenediol, neopentyl glycol, 1,6-hexamethylenediol, 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentamethylenediol, 2,4- Diethyl-1,5-pentamethylenediol, glycerin, trimethylolpropane, trimethylolethane, cyclohexanediols (1,4-cyclohexanediol, etc.), tricyclodecanedimethanol, bisphenols (bisphenol A, etc.), sugar alcohols (xylitol, sorbitol, etc.) and the like.

Examples of polyvalent carboxylic acids include aliphatic dicarboxylic acids such as malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid; alicyclic dicarboxylic acids such as -cyclohexanedicarboxylic acid;

Examples of the cyclic ester include propiolactone, β-methyl-δ-valerolactone, ε-caprolactone and the like.

As the polyol (a2) as a whole, it is preferable to use a bifunctional (having two hydroxyl groups) polyol from the viewpoint of imparting extensibility to a cured coating film. A polyol (having three hydroxyl groups) may be used in combination.

[Hydroxyl group-containing (meth)acrylate (a3)]
Specific examples of the hydroxyl group-containing (meth)acrylate (a3) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl ( Hydroxyalkyl (meth)acrylates having 1 to 16 (preferably 1 to 12) carbon atoms in the alkyl group such as meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 2-hydroxyethyl acryloyl phosphate, 2-(meth)acrylate Acryloyloxyethyl-2-hydroxypropyl phthalate, caprolactone-modified 2-hydroxyethyl (meth)acrylate, dipropylene glycol (meth)acrylate, fatty acid-modified glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono (Meth)acrylates, compounds having one (meth)acryloyl group such as 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate; glycerin di(meth)acrylate, 2-hydroxy-3-acryloyl- Compounds having two (meth)acryloyl groups such as oxypropyl methacrylate; pentaerythritol tri(meth)acrylate, caprolactone-modified pentaerythritol tri(meth)acrylate, ethylene oxide-modified pentaerythritol tri(meth)acrylate, dipentaerythritol penta ( Compounds having 3 or more (meth)acryloyl groups such as meth)acrylate, caprolactone-modified dipentaerythritol penta(meth)acrylate, ethylene oxide-modified dipentaerythritol penta(meth)acrylate, succinic acid-modified pentaerythritol tri(meth)acrylate, etc. etc.
These may be used individually by 1 type, and may be used in combination of 2 or more types.

Among these, a hydroxyl group-containing (meth) acrylate having one (meth) acryloyl group in the molecule is preferable because it can impart an appropriate crosslinked structure to the cured coating film and can impart extensibility, and more preferably , hydroxyalkyl (meth)acrylates, more preferably 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6 - hydroxyhexyl (meth) acrylate and caprolactone-modified 2-hydroxyethyl (meth) acrylate, particularly preferably 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate in terms of excellent reactivity and versatility acrylate, 4-hydroxybutyl (meth)acrylate, and caprolactone-modified 2-hydroxyethyl (meth)acrylate.

Then, the hydroxyl group-containing The proportion of (meth)acrylate (a3) is preferably 1 to 15 wt%, more preferably 2 to 13 wt%, still more preferably 2 to 10 wt%.

[Preparation of urethane (meth)acrylate (A)]
The urethane (meth)acrylate (A) used in the present invention includes, for example, the alicyclic structure-containing polyisocyanate (a1), low molecular weight polyol (a2-1), high molecular weight polyester polyol (a2-2), hydroxyl group-containing (Meth)acrylate (a3) can be produced by charging a reactor all at once or separately and reacting with a low-molecular-weight polyol (a2-1) and a high-molecular-weight polyester-based polyol (a2-2). , The reaction product obtained by pre-reacting with the alicyclic structure-containing polyisocyanate (a1) is reacted with the hydroxyl group-containing (meth)acrylate (a3) to improve the stability of the reaction and the reduction of by-products. useful from the point of view.
In particular, an alicyclic structure-containing polyisocyanate (a1) and a low-molecular-weight polyol (a2-1) are added to an organic solvent for reaction, and then a high-molecular-weight polyester-based polyol (a2-2) is further added for reaction. Then, the reaction product obtained as a result is reacted with the hydroxyl group-containing (meth)acrylate (a3) to produce the desired urethane (meth)acrylate (A). can be manufactured.

Then, in order to obtain a urethane (meth)acrylate (A) in good yield, an alicyclic structure-containing polyisocyanate (a1), a low molecular weight polyol (a2-1), a high molecular weight polyester polyol (a2-2), a hydroxyl group-containing The molar ratio of (meth)acrylate (a3) is preferably as follows.

Known reaction means can be used for the reaction of the alicyclic structure-containing polyisocyanate (a1), the low-molecular-weight polyol (a2-1), and the high-molecular-weight polyester-based polyol (a2-2). At that time, for example, the isocyanate group in the alicyclic structure-containing polyisocyanate (a1) and the hydroxyl group in the polyol (the hydroxyl group in the low molecular weight polyol (a2-1) and the hydroxyl group in the high molecular weight polyester polyol (a2-2) (total) is generally about 2:1 to 20:19 in terms of molar ratio of isocyanate groups:hydroxyl groups, to obtain a terminal isocyanate group-containing urethane (meth)acrylate with residual isocyanate groups. Then, the terminal isocyanate group can undergo an addition reaction with the hydroxyl group-containing (meth)acrylate (a3).

A reaction product obtained by pre-reacting the alicyclic structure-containing polyisocyanate (a1), the low molecular weight polyol (a2-1), and the high molecular weight polyester polyol (a2-2), and a hydroxyl group-containing (meth) Known reaction means can also be used for the addition reaction with the acrylate (a3).

The reaction molar ratio between the reaction product and the hydroxyl group-containing (meth)acrylate (a3) is, for example, two isocyanate groups in the alicyclic structure-containing polyisocyanate (a1) and hydroxyl groups in the hydroxyl group-containing (meth)acrylate (a3). is one, the reaction product: the hydroxyl group-containing (meth)acrylate (a3) is about 1:2, the alicyclic structure-containing polyisocyanate (a1) has three isocyanate groups, and the hydroxyl group-containing ( When the meth)acrylate (a3) has one hydroxyl group, the ratio of the reaction product to the hydroxyl group-containing (meth)acrylate (a3) is about 1:3.

In the addition reaction between the reaction product and the hydroxyl group-containing (meth)acrylate (a3), the residual isocyanate group content in the reaction system is preferably 0.3% by weight or less, more preferably 0.1% by weight or less. By terminating the reaction at a point in time, unreacted components can be reduced, and urethane (meth)acrylate (A) can be obtained with good reproducibility.

Regarding the reaction conditions, for example, the reaction temperature is preferably set in the range of about 30 to 80° C. in order to obtain the urethane (meth)acrylate (A) in good yield, but the reaction heat can be controlled. Therefore, it is suitable to carry out the reaction at 60 to 70° C., and the reaction time is usually 2 to 10 hours, preferably 3 to 8 hours.

Reaction of the above alicyclic structure-containing polyisocyanate (a1), low molecular weight polyol (a2-1), and high molecular weight polyester polyol (a2-2), further reaction product and hydroxyl group-containing (meth)acrylate (a3) ), it is also preferable to use a catalyst for the purpose of promoting the reaction. Examples of the catalyst include dibutyltin dilaurate, dibutyltin diacetate, trimethyltin hydroxide, tetra-n-butyltin, bisacetyl Organometallic compounds such as zinc acetonate, zirconium tris(acetylacetonate) ethylacetoacetate, zirconium tetraacetylacetonate, tin octoate, zinc hexanoate, zinc octenoate, zinc stearate, zirconium 2-ethylhexanoate, naphthene metal salts such as cobalt acid, stannous chloride, stannic chloride, potassium acetate, triethylamine, triethylenediamine, benzyldiethylamine, 1,4-diazabicyclo[2,2,2]octane, 1,8-diazabicyclo[5, Amine catalysts such as 4,0]-7-undecene, N,N,N',N'-tetramethyl-1,3-butanediamine, N-methylmorpholine, N-ethylmorpholine, bismuth nitrate, bismuth bromide , bismuth iodide, bismuth sulfide, etc., organic bismuth compounds such as dibutylbismuth dilaurate, dioctylbismuth dilaurate, bismuth 2-ethylhexanoate, bismuth naphthenate, bismuth isodecanoate, bismuth neodecanoate, lauric acid Organic acid bismuth salts such as bismuth salts, bismuth maleates, bismuth stearates, bismuth oleates, bismuth linoleates, bismuth acetates, bismuth ribs neodecanoate, bismuth disalicylate, and bismuth digallate and bismuth-based catalysts such as dibutyltin dilaurate and 1,8-diazabicyclo[5,4,0]-7-undecene are preferred.
These may be used individually by 1 type, and can also be used in combination of 2 or more types.

The blending amount of the above catalyst is usually 5 to 1,000 ppm, preferably 10 to 500 ppm, more preferably 20 to 200 ppm, based on the total sum of the reaction components.

Moreover, in the above reaction, it is preferable to further use a polymerization inhibitor. As the polymerization inhibitor, known general ones that are used as polymerization inhibitors can be used. 5-di-t-butylhydroquinone, methylhydroquinone, mono-t-butylhydroquinone and other quinones, 4-methoxyphenol, 2,6-di-tert-butylcresol and other aromatics, pt-butylcatechol etc. can be mentioned. Among them, aromatics are preferred, and 4-methoxyphenol and 2,6-di-tert-butylcresol are particularly preferred.
These may be used individually by 1 type, and can also be used in combination of 2 or more types.

As mentioned above, it is preferable to use an organic solvent in the above reaction. Examples of the organic solvent include ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone and cyclohexanone; cellosolves such as ethyl cellosolve; aromatics such as toluene and xylene; etc. can be given. These organic solvents may be used alone or in combination of two or more.
In addition, the content of the organic solvent in the active energy ray-curable resin composition of the present invention is usually 1 to 90% by weight, preferably 10 to 80% by weight, more preferably 20 to 70% by weight, still more preferably 30% by weight. ~60% by weight. That is, if the content of the organic solvent is too small, the viscosity may be significantly increased and the handling property may be impaired. Because it is possible.

The number of ethylenically unsaturated groups contained in the urethane (meth)acrylate (A) is preferably 1-10, more preferably 1-6, and particularly preferably 1-3.

The weight average molecular weight of the urethane (meth)acrylate (A) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, particularly preferably 10,000 to 40,000, and more preferably 10,000 to 40,000. preferably 15,000 to 30,000. If the weight-average molecular weight of the urethane (meth)acrylate (A) is too small, the concentration of ethylenically unsaturated groups in the cured coating film becomes relatively large, and the cured coating film cannot obtain extensibility. If the weight average molecular weight of the urethane (meth)acrylate (A) is too large, the viscosity tends to increase and the reaction control tends to be difficult, and the ethylenically unsaturated group concentration in the cured coating film Since it becomes relatively small and the crosslink density becomes low, although the stretchability of the cured coating film is obtained, the elastic modulus tends to be low.

The weight-average molecular weight is the weight-average molecular weight in terms of standard polystyrene molecular weight. and two ACQUITY APC XT 45 in series.

In addition, the viscosity of the urethane (meth)acrylate (A) is adjusted by the content of the organic solvent described above, and is preferably 10 to 100,000 mPa·s at 20°C. It is more preferably 100 to 50,000 mPa·s, still more preferably 1,000 to 25,000 mPa·s. If the viscosity is too low, the coating properties tend to deteriorate, and if the viscosity is too high, the handling tends to become difficult and the coating properties tend to deteriorate.
In addition, the said viscosity is measured using a Brookfield viscometer.

《Other materials》
The active energy ray-curable resin composition of the present invention preferably further contains a photopolymerization initiator in order to impart curability.

The photopolymerization initiator is not particularly limited as long as it generates radicals by the action of light. Examples include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and benzyldimethyl. ketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxy-cyclohexyl-phenyl-ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2- Hydroxy-2-methyl-1-propan-1-one, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl ) acetophenones such as butanone, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone oligomer; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. benzoins; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone , 2,4,6-trimethylbenzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenyloxy)ethyl]benzenemethanaminium bromide, (4-benzoylbenzyl)trimethyl Benzophenones such as ammonium chloride; Thioxanthones such as hydroxy)-3,4-dimethyl-9H-thioxanthon-9-one mesochloride; 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4 ,4-trimethyl-pentylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; and the like. In addition, these photoinitiators may be used individually by 1 type, and can also use 2 or more types together.

Further, as an auxiliary agent for the photopolymerization initiator, triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (Michler's ketone), 4,4'-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, 4- Ethyl dimethylaminobenzoate, (n-butoxy)ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4- It is also possible to use diisopropylthioxanthone or the like in combination. These auxiliaries may be used singly or in combination of two or more.

The content of the photopolymerization initiator is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, relative to 100 parts by weight of the specific urethane (meth)acrylate (A). parts by weight, more preferably 1 to 7.5 parts by weight. If the content is too low, curing will be poor and the coating film will tend to be difficult to form.

Furthermore, in addition to the specific urethane (meth)acrylate (A) and the photopolymerization initiator, the active energy ray-curable resin composition of the present invention contains an antioxidant, a flame retardant, an antistatic agent, and a filler. , a leveling agent, a stabilizer, a reinforcing agent, a delustering agent, and the like. Furthermore, as a cross-linking agent, compounds having the action of inducing cross-linking by heat, specifically epoxy compounds, azilysine compounds, melamine compounds, isocyanate compounds, chelate compounds and the like can be used.

<<Active energy ray-curable resin composition>>
The active energy ray-curable resin composition of the present invention is produced by adding various additives such as a photopolymerization initiator in a predetermined blending amount to the specific urethane (meth)acrylate (A) and mixing them. can do.

The above-mentioned active energy ray-curable resin composition can be prepared by heating each of the above ingredients to room temperature (25° C.±10° C.) or in a temperature range of room temperature to 60° C. and mixing. Preferably, each component excluding the photopolymerization initiator is preliminarily mixed (0.5 to 30 hours) at room temperature or in a heated state in the above temperature range, and then the photopolymerization initiator is mixed to obtain the above active energy. It is to prepare a radiation-curable resin composition.

The active energy ray-curable resin composition thus obtained preferably has a viscosity of 10 to 100,000 mPa s, more preferably 100 to 50,000 mPa s at 20° C. It is preferably 1,000 to 25,000 mPa·s. If the viscosity is too low, the coating properties tend to deteriorate, and if the viscosity is too high, the handling tends to become difficult and the coating properties tend to deteriorate.
In addition, the said viscosity is measured using a Brookfield viscometer.

《Coating agents, sheets》
The active energy ray-curable resin composition of the present invention is used, for example, as a coating agent.

Further, the active energy ray-curable resin composition can also be used as a sheet. A sheet can be produced by this.

In the present invention, the term "sheet" conceptually includes sheets and films.

Substrates to be coated with the active energy ray-curable resin composition of the present invention include polyolefin resins, polyester resins, polycarbonate resins, acrylic resins, acrylonitrile-butadiene-styrene copolymers (ABS), and polystyrene. Plastic substrates such as system resins and their molded products (films, sheets, cups, etc.), composite substrates thereof, or composite substrates of the above materials mixed with glass fibers and inorganic substances, metals (aluminum, copper, (iron, SUS, zinc, magnesium, alloys thereof, etc.), and substrates such as glass having a primer layer provided thereon.

Examples of the method for applying the active energy ray-curable resin composition of the present invention include wet coating methods such as spraying, showering, dipping, rolling, spinning, and screen printing. What is necessary is just to apply to a base material.

Examples of the active energy ray used for curing the active energy ray-curable resin composition coated on the substrate include light rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, and infrared rays, X rays, γ rays, and the like. In addition to electromagnetic waves, electron beams, proton beams, neutron beams, etc. can be used, but curing by ultraviolet irradiation is advantageous in terms of curing speed, availability of irradiation equipment, price, and the like. When electron beam irradiation is performed, curing can be performed without using the above-mentioned photopolymerization initiator.

When curing the active energy ray-curable resin composition of the present invention by ultraviolet irradiation, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical A lamp, an electrodeless discharge lamp, an LED, or the like may be used to irradiate ultraviolet rays at a dose of usually 30 to 3,000 mJ/cm ² (preferably 100 to 1,500 mJ/cm ² ).
After the ultraviolet irradiation, heating may be performed as necessary to complete curing. The heating conditions at that time include, for example, a temperature of 120 to 200°C.

The coating film thickness (film thickness after curing) is usually 0.5 to 100 μm, preferably 0.5 to 100 μm, in consideration of light transmission so that the photopolymerization initiator uniformly reacts as an ultraviolet curable coating film. is 0.7 to 30 μm, more preferably 1 to 10 μm.

After forming a coating film using an active energy ray-curable resin composition, if an organic solvent remains in the resin composition when curing it, the organic solvent is removed by drying and then cured. is preferred. The drying conditions are preferably 40 to 120° C. for 1 to 20 minutes, more preferably 50 to 100° C. for 2 to 10 minutes.

INDUSTRIAL APPLICABILITY The active energy ray-curable resin composition of the present invention has high workability such that cracks do not occur even when molded into a complicated shape, conformability to molds, and high elongation, and also has high adhesion to substrates. Furthermore, since it has no surface tackiness and excellent chemical resistance (resistance to sunscreens, hand creams, etc.), it is excellent as a material for forming molded articles that may come into contact with fingers. It is especially suitable for decorative molding applications.
Due to these characteristics, for example, hard coating agents applied to the surface of plastic parts, etc., mobile phones such as smartphones, interior and exterior parts for automobiles, sign poles, hairdressing equipment, amusement equipment, etc. It can be used as a forming material for

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.
In addition, "parts" and "%" in the examples mean weight standards.
The weight average molecular weight, number average molecular weight and viscosity were measured according to the methods described above.

[Example 1]
In a flask equipped with an internal thermometer, a stirrer and a condenser, 250 g (1.29 mol) of 1,3-bis(isocyanatomethyl)cyclohexane (corresponding to (a1) of the present invention), neopentyl glycol ( (a2-1)) {molecular weight: 104} 120.7 g (1.16 mol) and 500 g of ethyl acetate as a dilution solvent were charged and heated at 50°C. After the neopentyl glycol (corresponding to (a2-1) of the present invention) was dissolved, 0.1 g of dibutyltin dilaurate was added as a reaction catalyst and reacted at 70°C. When the residual isocyanate group is 1.2% or less, bifunctional polyester polyol (corresponding to (a2-2) of the present invention) {composition: adipic acid, isophthalic acid, 3-methyl-1,5-penta 114 g (0.06 mol) of methylene diol, a hydroxyl value of 63 mg KOH/g and a number average molecular weight of 1,780} were added and reacted at 70°C. When the residual isocyanate groups became 0.6% or less, it was cooled to 60° C., and 15.0 g (0.13 mol) of 2-hydroxyethyl acrylate (corresponding to (a3) of the present invention) and 2 as a polymerization inhibitor ,6-di-tert-butyl cresol 0.4 g was further charged and reacted at 60° C. When the residual isocyanate groups became 0.1% or less, the reaction was terminated, and the urethane acrylate compound (A-1). (weight average molecular weight of A-1: 23,950, solution viscosity: 13,300 mPa·s/20° C.).
4 parts of a photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by IGM Resins, "Omnilad 184")) was further mixed with 100 parts of the urethane acrylate compound (A-1) in the above solution. , to obtain an active energy ray-curable resin composition.

[Example 2]
In a flask equipped with an internal thermometer, a stirrer, and a condenser tube, 218 g (1.12 mol) of 1,3-bis(isocyanatomethyl)cyclohexane (corresponding to (a1) of the present invention), neopentyl glycol ( (a2-1) of (a2-1)) {molecular weight: 104} 87.5 g (0.84 mol) and 500 g of ethyl acetate as a dilution solvent were charged and heated at 50°C. After the neopentyl glycol (corresponding to (a2-1) of the present invention) was dissolved, 0.1 g of dibutyltin dilaurate was added as a reaction catalyst and reacted at 70°C. When the residual isocyanate group is 2.9% or less, a bifunctional polyester polyol (corresponding to (a2-2) of the present invention) {composition: adipic acid, isophthalic acid, 1,6-hexamethylenediol, hydroxyl group 173 g (0.19 mol) having a molecular weight of 121 mg KOH/g and a number average molecular weight of 927} was added and reacted at 70°C. When the residual isocyanate groups became 0.8% or less, it was cooled to 60° C., and 21.7 g (0.19 mol) of 2-hydroxyethyl acrylate (corresponding to (a3) of the present invention) and 2 as a polymerization inhibitor. ,6-di-tert-butyl cresol 0.4 g was further charged and reacted at 60° C. When the residual isocyanate groups became 0.1% or less, the reaction was terminated, and the urethane acrylate compound (A-2). (weight average molecular weight of A-2: 19,000, solution viscosity: 8,000 mPa·s/20° C.).
4 parts of a photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by IGM Resins, "Omnilad 184")) was further mixed with 100 parts of the urethane acrylate compound (A-2) in the above solution. , to obtain an active energy ray-curable resin composition.

[Example 3]
In a flask equipped with an internal thermometer, a stirrer, and a condenser, 203 g (1.04 mol) of 1,3-bis(isocyanatomethyl)cyclohexane (corresponding to (a1) of the present invention), neopentyl glycol ( (a2-1)) {molecular weight: 104} 87 g (0.84 mol) and 500 g of ethyl acetate as a dilution solvent were charged and heated at 50°C. After the neopentyl glycol (corresponding to (a2-1) of the present invention) was dissolved, 0.1 g of dibutyltin dilaurate was added as a reaction catalyst and reacted at 70°C. When the residual isocyanate groups are 2.2% or less, a bifunctional polyester polyol (corresponding to (a2-2) of the present invention) {composition: adipic acid, isophthalic acid, 3-methyl-1,5-penta 185 g (0.10 mol) of methylene diol, a hydroxyl value of 63 mg KOH/g and a number average molecular weight of 1,780} were added and reacted at 70°C. When the residual isocyanate groups became 0.9% or less, it was cooled to 60° C., and 24.6 g (0.21 mol) of 2-hydroxyethyl acrylate (corresponding to (a3) of the present invention) and 2 as a polymerization inhibitor ,6-di-tert-butyl cresol 0.4 g was further charged and reacted at 60° C. When the residual isocyanate groups became 0.1% or less, the reaction was terminated, and the urethane acrylate compound (A-3). (weight average molecular weight of A-3: 15,700, solution viscosity: 5,100 mPa·s/20° C.).
4 parts of a photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by IGM Resins, "Omnilad 184")) was further mixed with 100 parts of the urethane acrylate compound (A-3) in the above solution. , to obtain an active energy ray-curable resin composition.

[Example 4]
In a flask equipped with an internal thermometer, a stirrer, and a condenser, 216 g (1.11 mol) of 1,3-bis(isocyanatomethyl)cyclohexane (corresponding to (a1) of the present invention), neopentyl glycol ( (a2-1)) {molecular weight: 104} 96.7 g (0.93 mol) and 500 g of ethyl acetate as a dilution solvent were charged and heated at 50°C. After the neopentyl glycol (corresponding to (a2-1) of the present invention) was dissolved, 0.1 g of dibutyltin dilaurate was added as a reaction catalyst and reacted at 70°C. When the residual isocyanate group is 1.9% or less, bifunctional polyester polyol (corresponding to (a2-2) of the present invention) {composition: adipic acid, isophthalic acid, 3-methyl-1,5-penta 165 g (0.09 mol) of methylene diol, a hydroxyl value of 63 mg KOH/g and a number average molecular weight of 1,780} were added and reacted at 70°C. When the residual isocyanate groups became 0.8% or less, it was cooled to 60° C., and 21.9 g (0.19 mol) of 2-hydroxyethyl acrylate (corresponding to (a3) of the present invention) and 2 as a polymerization inhibitor ,6-di-tert-butyl cresol 0.4 g was further charged and reacted at 60° C. When the residual isocyanate groups became 0.1% or less, the reaction was terminated, and the urethane acrylate compound (A-4). (weight average molecular weight of A-4: 17,700, solution viscosity: 6,300 mPa·s/20° C.).
4 parts of a photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by IGM Resins, "Omnilad 184")) was further mixed with 100 parts of the urethane acrylate compound (A-4) in the above solution. , to obtain an active energy ray-curable resin composition.

[Example 5]
In a flask equipped with an internal thermometer, a stirrer, and a condenser, 236 g (1.21 mol) of 1,3-bis(isocyanatomethyl)cyclohexane (corresponding to (a1) of the present invention), neopentyl glycol ( (a2-1)) {molecular weight: 104} 111 g (1.06 mol) and 500 g of butyl acetate as a dilution solvent were charged and heated at 50°C. After the neopentyl glycol (corresponding to (a2-1) of the present invention) was dissolved, 0.1 g of dibutyltin dilaurate was added as a reaction catalyst and reacted at 70°C. When the residual isocyanate group is 1.5% or less, bifunctional polyester polyol (corresponding to (a2-2) of the present invention) {composition: adipic acid, isophthalic acid, 3-methyl-1,5-penta 136 g (0.08 mol) of methylene diol, a hydroxyl value of 63 mg KOH/g and a number average molecular weight of 1,780} were added and reacted at 70°C. When the residual isocyanate groups became 0.7% or less, it was cooled to 60° C., and 17.6 g (0.15 mol) of 2-hydroxyethyl acrylate (corresponding to (a3) of the present invention) and 2 as a polymerization inhibitor ,6-di-tert-butyl cresol 0.4 g was further charged and reacted at 60° C. When the residual isocyanate groups became 0.1% or less, the reaction was terminated, and the urethane acrylate compound (A-5). (weight average molecular weight of A-5: 22,400, solution viscosity: 20,900 mPa·s/20° C.).
4 parts of a photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by IGM Resins, "Omnilad 184")) was further mixed with 100 parts of the urethane acrylate compound (A-5) in the above solution. , to obtain an active energy ray-curable resin composition.

[Example 6]
Into a flask equipped with an internal thermometer, a stirrer and a condenser, 233 g (1.20 mol) of 1,3-bis(isocyanatomethyl)cyclohexane (corresponding to (a1) of the present invention), neopentyl glycol ( (a2-1)) {molecular weight: 104} 93.6 g (0.90 mol) and 500 g of ethyl acetate as a dilution solvent were charged and heated at 50°C. After the neopentyl glycol (corresponding to (a2-1) of the present invention) was dissolved, 0.1 g of dibutyltin dilaurate was added as a reaction catalyst and reacted at 70°C. When the residual isocyanate group is 3.1% or less, bifunctional polyester polyol (corresponding to (a2-2) of the present invention) {composition: adipic acid, isophthalic acid, 1,6-hexamethylenediol, hydroxyl group 139 g (0.15 mol) having a molecular weight of 121 mg KOH/g and a number average molecular weight of 927} was added and reacted at 70°C. When the residual isocyanate groups became 1.3% or less, it was cooled to 60° C., and 34.8 g (0.30 mol) of 2-hydroxyethyl acrylate (corresponding to (a3) of the present invention) and 2 as a polymerization inhibitor ,6-di-tert-butyl cresol 0.4 g was further charged and reacted at 60° C. When the residual isocyanate groups became 0.1% or less, the reaction was terminated, and the urethane acrylate compound (A-6). (weight average molecular weight of A-6: 10,940, solution viscosity: 2,200 mPa·s/20° C.).
4 parts of a photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by IGM Resins, "Omnilad 184")) was further mixed with 100 parts of the urethane acrylate compound (A-6) in the above solution. , to obtain an active energy ray-curable resin composition.

[Comparative Example 1]
181 g (0.93 mol) of 1,3-bis(isocyanatomethyl)cyclohexane (corresponding to (a1) of the present invention), neopentyl glycol ( (a2-1)) {molecular weight: 104} 48.7 g (0.47 mol) and 300 g of butyl acetate as a dilution solvent were added and heated at 50°C. After the neopentyl glycol (corresponding to (a2-1) of the present invention) was dissolved, 0.1 g of dibutyltin dilaurate was added as a reaction catalyst and reacted at 70°C. When the residual isocyanate groups are 7.4% or less, a bifunctional polyester polyol (corresponding to (a2-2) of the present invention) {composition: adipic acid, isophthalic acid, 3-methyl-1,5-penta 415 g (0.23 mol) of methylene diol, a hydroxyl value of 63 mg KOH/g and a number average molecular weight of 1,780} were added and reacted at 70°C. When the residual isocyanate groups became 2.1% or less, it was cooled to 60° C., and 55.1 g (0.47 mol) of 2-hydroxyethyl acrylate (corresponding to (a3) of the present invention) and 2 as a polymerization inhibitor ,6-di-tert-butyl cresol 0.4 g was further charged and reacted at 60° C. When the residual isocyanate groups became 0.1% or less, the reaction was terminated, and a urethane acrylate compound (A′-1 ) was obtained (weight average molecular weight of A′-1: 13,200, solution viscosity: 7,000 mPa·s/20° C.).
4 parts of a photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by IGM Resins, "Omnilad 184")) are mixed with 100 parts of the urethane acrylate compound (A'-1) in the above solution. to obtain an active energy ray-curable resin composition.

[Comparative Example 2]
In a flask equipped with an internal thermometer, a stirrer, and a condenser, 227 g (1.17 mol) of 1,3-bis(isocyanatomethyl)cyclohexane (corresponding to (a1) of the present invention), neopentyl glycol ( (a2-1) of (a2-1)) {molecular weight: 104} 81.2 g (0.78 mol) and 300 g of ethyl acetate as a dilution solvent were charged and heated at 50°C. After the neopentyl glycol (corresponding to (a2-1) of the present invention) was dissolved, 0.1 g of dibutyltin dilaurate was added as a reaction catalyst and reacted at 70°C. When the residual isocyanate groups are 5.4% or less, a bifunctional polyester polyol (corresponding to (a2-2) of the present invention) {composition: adipic acid, isophthalic acid, 3-methyl-1,5-penta 346 g (0.19 mol) of methylene diol, a hydroxyl value of 63 mg KOH/g and a number average molecular weight of 1,780} were added and reacted at 70°C. When the residual isocyanate groups became 1.7% or less, it was cooled to 60° C., and 45.9 g (0.40 mol) of 2-hydroxyethyl acrylate (corresponding to (a3) of the present invention) and 2 as a polymerization inhibitor ,6-di-tert-butyl cresol 0.4 g was further charged and reacted at 60° C. When the residual isocyanate groups became 0.1% or less, the reaction was terminated, and a urethane acrylate compound (A′-2 ) was obtained (weight average molecular weight of A′-2: 13,300, solution viscosity: 9,000 mPa·s/20° C.).
4 parts of a photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by IGM Resins, "Omnilad 184")) are mixed with 100 parts of the urethane acrylate compound (A'-2) in the above solution. to obtain an active energy ray-curable resin composition.

[Comparative Example 3]
Into a flask equipped with an internal thermometer, a stirrer and a condenser, 162 g (0.84 mol) of 1,3-bis(isocyanatomethyl)cyclohexane (corresponding to (a1) of the present invention), a bifunctional polyester polyol ( Corresponding to (a2-2) of the present invention) {Composition: adipic acid, isophthalic acid, 3-methyl-1,5-pentamethylenediol, hydroxyl value 63 mg KOH/g, number average molecular weight 1,780} 739 g (0.42) mol) was charged, and 0.1 g of dibutyltin dilaurate was added as a reaction catalyst and reacted at 60°C. When the residual isocyanate groups became 3.9% or less, 98.4 g (0.85 mol) of 2-hydroxyethyl acrylate (corresponding to (a3) of the present invention), 2,6-di- 0.4 g of tert-butyl cresol was further charged and reacted at 60° C. When the residual isocyanate groups became 0.1% or less, the reaction was terminated to obtain a urethane acrylate compound (A′-3) ( A′-3 weight average molecular weight: 10,000, viscosity: 50,000 mPa·s/60° C.).
4 parts of a photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by IGM Resins, "Omnilad 184")) are mixed with 100 parts of the urethane acrylate compound (A'-3) in the above solution. to obtain an active energy ray-curable resin composition.

[Comparative Example 4]
Into a flask equipped with an internal thermometer, a stirrer and a condenser, 418 g (2.15 mol) of 1,3-bis(isocyanatomethyl)cyclohexane (corresponding to (a1) of the present invention), neopentyl glycol ( (a2-1)) {molecular weight: 104} 179 g (1.72 mol) and 300 g of ethyl acetate as a dilution solvent were charged and heated at 70°C. After the neopentyl glycol (corresponding to (a2-1) of the present invention) was dissolved, 0.1 g of dibutyltin dilaurate was added as a reaction catalyst and reacted at 70°C. When the residual isocyanate groups became 4.0% or less, it was cooled to 60° C., and 102 g (0.88 mol) of 2-hydroxyethyl acrylate (corresponding to (a3) of the present invention), 2,6 as a polymerization inhibitor, - 0.4 g of di-tert-butyl cresol was further charged and reacted at 60 ° C. When the residual isocyanate group became 0.1% or less, the reaction was terminated, and the urethane acrylate compound (A'-4) A 30% solution of ethyl acetate was obtained (weight average molecular weight of A'-4: 3,900, solution viscosity: 10,000 mPa·s/20°C).
4 parts of a photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by IGM Resins, "Omnilad 184")) are mixed with 100 parts of the urethane acrylate compound (A'-4) in the above solution. to obtain an active energy ray-curable resin composition.

Using the active energy ray-curable resin composition thus obtained, a sample for evaluation was prepared as follows, and the sample was evaluated for elongation, elastic modulus, strength, surface tack evaluation, and chemical resistance. , was evaluated as follows. The results are shown in Table 1 below. In addition, in Table 1 below, the material composition (%) of the urethane acrylate compounds (A-1 to A-6, A'-1 to A'-4) that are the constituent components of the active energy ray-curable resin composition (Use ratio of each material corresponding to each of a1, a2-1, a2-2, and a3 of the present invention), and from the composition of the urethane acrylate compound, the urethane bond [-NHC (= The value (urethane bond concentration (mmol/g)) calculated according to the above formula (1) for the proportion of O)O-] is also shown.

[Preparation of sample for evaluation]
The active energy ray-curable resin composition was applied onto a release polyethylene terephthalate (PET) film with an applicator, dried in a dryer at 60°C for 30 minutes, and dried with a single high-pressure mercury lamp (80 W) to a thickness of 18 cm. Two passes of ultraviolet irradiation (cumulative irradiation amount: 800 mJ/cm ² ) were carried out from a height of 3.4 m/min at a conveyor speed to obtain a cured coating film (thickness: 100 μm). Then, this cured coating film was punched out with a dumbbell to prepare a strip-shaped sample having a width of 15 mm and a length of 75 mm, and then the cured coating film was peeled off from the PET film to obtain a sample piece for evaluation.

<Elongation>
The sample was subjected to a tensile test according to JIS K 7127 using a tensile tester "AG-X" (manufactured by Shimadzu Corporation) at a temperature of 23°C and a humidity of 50%. The tensile speed was 10 mm/min, and the elongation at the breaking point of the coating film was measured and evaluated according to the following criteria.
A: 200% or more.
○: 100% or more and less than 200%.
x: Less than 100%.

<Elastic modulus>
The sample was subjected to a tensile test according to JIS K 7127 using a tensile tester "AG-X" (manufactured by Shimadzu Corporation) at a temperature of 23°C and a humidity of 50%. The tensile speed was 10 mm/min, and the elastic modulus was measured in the range of 1 to 2% of the displacement of extensional deformation of the coating film, and evaluated according to the following criteria.
A: 20 (N/mm ² ) or more.
◯: 10 (N/mm ² ) or more and less than 20 (N/mm ² ).
×: Less than 10 (N/mm ² ).

<Strength>
The sample was subjected to a tensile test according to JIS K 7127 using a tensile tester "AG-X" (manufactured by Shimadzu Corporation) at a temperature of 23°C and a humidity of 50%. The tensile speed was 10 mm/min, and the strength at the breaking point of the coating film was measured and evaluated according to the following criteria.
A: 15 (N/mm ² ) or more.
○: 5 (N/mm ² ) or more and less than 15 (N/mm ² ).
×: Less than 5 (N/mm ² ).

<Surface tack evaluation>
The presence or absence of tack on the surface of the sample was evaluated by finger touch according to the following criteria.
A: No tack is felt at all.
◯: Slight tackiness is felt when a finger is strongly pressed.
x: A tack is felt when a finger is pressed.

<Chemical resistance (i)>
A waste cloth (“Kimwipe” manufactured by Nippon Paper Crecia Co., Ltd.) impregnated with ethanol was pressed against the surface of the sample with a weight of 500 g, and the sample was reciprocated 10 times in this state. After that, the condition of the sample surface was visually evaluated according to the following criteria.
Good: No change on the sample surface.
Δ: The surface of the sample is slightly opaque or scratched.
x: The surface of the sample is cloudy.

<Chemical resistance (ii)>
A sunscreen (“Neutrogena SPF45” manufactured by Johnson & Johnson) was applied to the surface of the sample at 0.02 g/cm ² , left at 40° C. for 1 hour, wiped off, and the condition of the sample surface was visually evaluated.
Good: No change on the sample surface.
Δ: The surface of the coating film is slightly opaque or scratched.
x: The coating film surface is cloudy.

From the above results, in all the examples, the elongation, elastic modulus and strength were all high, and furthermore, high evaluations were obtained in terms of surface tack evaluation and chemical resistance.

In contrast, in the active energy ray-curable resin compositions of Comparative Examples 1 to 3, the urethane bond concentration of the urethane acrylate compound is low, and the elastic modulus of the cured body of the resin composition is affected. The result was inferior in surface tack evaluation and chemical resistance to sunscreen. In addition, the cured coating film composed of the active energy ray-curable resin composition of Comparative Example 4 was inferior in elongation and chemical resistance to ethanol.

INDUSTRIAL APPLICABILITY The active energy ray-curable resin composition of the present invention has high workability such that cracks do not occur even when molded into a complicated shape, conformability to molds, and high elongation, and also has high adhesion to substrates. Furthermore, since it has no surface tackiness and excellent chemical resistance (resistance to sunscreens, hand creams, etc.), it is excellent as a material for forming molded articles that may come into contact with fingers. It is especially suitable for decorative molding applications.
Due to these characteristics, for example, hard coating agents applied to the surface of plastic parts, etc., mobile phones such as smartphones, interior and exterior parts for automobiles, sign poles, hairdressing equipment, amusement equipment, etc. It can be used as a forming material for In addition, it can be used for other applications that take advantage of the above characteristics.

Claims (8)

An active energy ray-curable resin composition containing a urethane (meth)acrylate (A) that is a reaction product of an alicyclic structure-containing polyisocyanate (a1), a polyol (a2), and a hydroxyl group-containing (meth)acrylate (a3) There is
The polyol (a2) contains a low molecular weight polyol (a2-1) having a number average molecular weight of 60 to 300 and a high molecular weight polyester polyol (a2-2) having a number average molecular weight of 500 to 20,000,
The hydroxyl group-containing (meth) ) the proportion of acrylate (a3) is 1 to 15% by weight,
An active energy ray-curable resin composition, wherein the urethane (meth)acrylate (A) has a urethane bond concentration of 3.5 mmol/g or more. The ratio of the alicyclic structure-containing polyisocyanate (a1) to the total of the alicyclic structure-containing polyisocyanate (a1), the polyol (a2), and the hydroxyl group-containing (meth)acrylate (a3) is 30% by weight or more. The active energy ray-curable resin composition according to claim 1, characterized by: The alicyclic structure-containing polyisocyanate (a1) and the low molecular weight polyol (a2-1) are The active energy ray-curable resin composition according to claim 1 or 2, wherein the total ratio of is 40% by weight or more. The ratio of the alicyclic structure-containing polyisocyanate (a1) to the total of the alicyclic structure-containing polyisocyanate (a1), the polyol (a2), and the hydroxyl group-containing (meth)acrylate (a3) is 30 to 60% by weight. There, the proportion of the low molecular weight polyol (a2-1) is 10 to 40% by weight, the proportion of the high molecular weight polyester polyol (a2-2) is 10 to 50% by weight, and the hydroxyl group-containing (meth) 4. The active energy ray-curable resin composition according to any one of claims 1 to 3, wherein the proportion of acrylate (a3) is 1 to 15% by weight. 5. The active energy ray-curable resin composition according to any one of claims 1 to 4, wherein the low molecular weight polyol (a2-1) has a branched structure. The activation energy according to any one of claims 1 to 5, wherein the hydroxyl group-containing (meth)acrylate (a3) is a (meth)acrylate having one (meth)acryloyl group in the molecule. A ray-curing resin composition. A coating agent comprising the active energy ray-curable resin composition according to any one of claims 1 to 6. A sheet comprising a cured body of the active energy ray-curable resin composition according to any one of claims 1 to 6.