TW201425465A - Active energy ray-curable resin composition, coating agent composition, and laminate - Google Patents

Abstract

An active energy ray-curable resin composition which is characterized by containing (A) a urethane (meth)acrylate compound and (B) a fine particulate synthetic resin filler, a coating agent composition which uses the active energy ray-curable resin composition, and a laminate are provided as an active energy ray-curable resin composition which forms a coating layer that has moist and soft finger tactile, while having excellent workability during a coating process and excellent productivity during a curing process, a coating agent composition which uses the active energy ray-curable resin composition, and a laminate.

Description

Active energy ray curable resin composition, coating composition, and laminate

The present invention relates to an active energy ray-curable resin composition, a coating agent composition, and a laminate, and more particularly to an active energy ray-curable resin composition, which is known as a cured coating film. It is a soft touch and a soft touch, and can form a hardened coating film which has an excellent high-grade appearance, and a coating composition which is formed by using it, and more preferably, has a substrate and A laminate of coating layers composed of the aforementioned coating composition.

In the past, the coating agent for the interior parts such as the plastic panel in the automobile has been made of a polyurethane-based coating agent containing organic fine particles in order to provide a feeling of high-grade and moist hand touch.

In general, a polyurethane coating agent is a thermosetting coating agent obtained by reacting a polyol component and an isocyanate component, and since the polyol component and the isocyanate component have high reactivity, they are usually carried out in two liquids. When it is applied to the substrate, the two are used in combination, so that the workability and productivity are inferior.

Therefore, various thermosetting polyurethane coating agents which have improved workability have been developed. For example, in Japanese Patent Laid-Open No. 1, a water-based coating material containing the following components is disclosed: The first urethane resin obtained by the reaction of the polycarbonate-based polyol and the polyisocyanate, and the second urethane resin obtained by the reaction of the polyether-based polyol and the polyisocyanate are contained in one molecule. Two or more cross-linking agents of carbodimide, with Urethane Beads, and surface modifiers of organic bismuth compounds; Patent Document 2 discloses a hardenable composition for a coating comprising a hardener composition (X) containing a specific polyisocyanate and an aliphatic polycarbonate diol (Y) as essential components, and a hardener composition ( X) The mixed molar ratio NCO/OH of the NCO group and the OH group contained in the aliphatic polycarbonate diol (Y) is 0.8 to 2.0.

[Previous Technical Literature]

[Japanese Patent Literature]

[Japanese Patent Document 1] Japanese Patent Laid-Open Publication No. 2007-319836

[Japanese Patent Document 2] Japanese Patent Laid-Open Publication No. 2010-13529

However, in the technique disclosed in the above Japanese Patent Document 1, in order to control the reactivity in the aqueous coating liquid, an aqueous dispersion solution of carbodiimide is used as a crosslinking agent to extend the operation time of the coating material. However, in order to harden the coating layer, it is necessary to take a few days in a humidity-conditioning environment in addition to the drying conditions at 80 ° C for 30 minutes. Therefore, although the solution stability (workability) is somewhat improved, it is insufficient. Satisfy productivity.

Moreover, in the solvent disclosed in the above-mentioned Japanese Patent Publication No. 2, it is estimated that the durability of various coating layers is improved as compared with the conventional coating liquid, but it is considered that the stability of the coating liquid obtained by mixing the isocyanate with the polyol has not yet been obtained. It is enough that the problem of workability remains.

In view of the above, it is an object of the present invention to provide a liquid-based curable resin composition which is excellent in workability, but which has a moist soft hand touch when formed into a coating layer, and is coated. An active energy ray-curable resin composition excellent in productivity during workability or hardening, and a coating agent composition using the same.

The inventors of the present invention have deliberately studied the results of the problem and found that the resin component is blended with the particles. In the coating agent composition obtained by the synthetic resin filler, an active energy ray-curable urethane (meth) acrylate is used as a resin component instead of the conventional thermosetting urethane resin. An active energy ray-curable resin composition excellent in workability at the time of coating or productivity at the time of hardening, and a coating film (coating layer) obtained after hardening has a moist soft hand touch, and the present invention is completed. .

In other words, the present invention relates to an active energy ray-curable resin composition comprising a urethane (meth)acrylate compound (A) and a particulate synthetic resin filler (B).

Further, in the present invention, a coating agent composition comprising the active energy ray-curable resin composition is further provided, and a coating layer comprising a substrate and a coating composition comprising the coating composition is further provided. Laminate.

When the active energy ray-curable resin composition of the present invention is used as a coating agent, it is an active energy ray-curable resin composition excellent in workability at the time of coating or productivity at the time of curing, and is It is especially useful as a coating agent if it has the effect of having a moist soft touch feeling after the coating layer obtained after hardening.

The invention is described in detail below.

The active energy ray-curable resin composition of the present invention contains a urethane (meth) acrylate compound (A) and a particulate synthetic resin filler (B).

Further, in the present invention, the (meth)acrylic group means an acrylic group or a methacryl group; the (meth)acryloyl group means an acryl group or a methacryl group; and the (meth)acrylate means an acrylic group. Ester or methacrylate.

[Carbamate (meth) acrylate compound (A)]

The content of the ethylenically unsaturated group of the urethane (meth)acrylate compound (A) used in the present invention is preferably 2 to 10, particularly preferably 2 to 6. When the number of the ethylenically unsaturated groups is too large, the crosslinking density after curing becomes too large, and the coating film becomes too hard, and it tends to be difficult to obtain a wet soft touch. If the amount is too small, a sufficient crosslinking density cannot be obtained. The surface of the hardened coating film is sticky, or the durability of various coatings is lowered.

The weight average molecular weight of the urethane (meth) acrylate type compound (A) used in the present invention is preferably from 1,000 to 50,000, more preferably from 1,500 to 40,000, particularly preferably from 2,000 to 35,000.

When the weight average molecular weight is too small, the relative crosslinking density becomes too large, so that the surface of the cured coating film becomes too hard, and it is difficult to obtain a soft soft touch feeling. If the weight is too large, the viscosity of the curable resin composition becomes too high. In addition, there is a tendency that a sufficient crosslink density cannot be obtained, the surface of the hardened coating film is sticky, or various durability is easily lowered.

Further, the weight average molecular weight described above is a weight average molecular weight obtained by converting the molecular weight of the standard polystyrene, and is used in high-speed liquid chromatography (Waters 2695 (main body) and "Waters 2414" manufactured by Waters Corporation, Japan. "))) 3 columns connected in series: Shodex GPC KF-806L (molecular weight exclusion limit: 2 × 10 ⁷ , separation range: 100 ~ 2 × 10 ⁷ , theoretical number of plates: 10,000 plates / root, filler material: The styrene-divinylbenzene copolymer and the filler particle diameter: 10 μm) were measured.

The viscosity of the urethane (meth) acrylate compound (A) at 60 ° C is preferably from 1,000 to 100,000 mPa. s, especially good for 1,500~50,000mPa. s. When the viscosity is outside the above range, the coating property tends to be lowered.

Furthermore, the viscosity measurement method uses an E-type viscometer.

The urethane (meth) acrylate type compound (A) used in the present invention may, for example, be a hydroxyl group-containing (meth) acrylate compound (a1) or a polyvalent isocyanate compound (a2). A urethane (meth) acrylate compound (A1) obtained by reacting a polyol compound (a3), or a hydroxyl group-containing (meth) acrylate compound (a1) and a polyvalent isocyanate compound ( A2) The urethane (meth) acrylate type compound (A2) obtained by the reaction may be used alone or in combination of two or more kinds.

In particular, in view of suppressing the stickiness of the coating film when the cured coating film is formed, and from the viewpoint of obtaining a crosslinking density sufficient to impart durability to the cured coating film, it is preferable to synthesize it at a lower molecular weight. The urethane (meth) acrylate type compound (A2) is preferred, and from the viewpoint of imparting flexibility to the cured coating film, a urethane obtained by reacting the polyol compound (a3) is preferable ( The methyl acrylate compound (A1) is preferred.

It is conceivable to appropriately select such physical properties as the intended hard coat film.

<Aminoformate (meth) acrylate type compound (A1)>

The urethane (meth) acrylate type compound (A1), as described above, is a hydroxyl group-containing (meth) acrylate type compound (a1), a polyvalent isocyanate type compound (a2), and a polyol type compound ( A3) The reaction is obtained. A compound containing a hydroxyl group-containing (meth)acrylate compound (a1), a polyvalent isocyanate compound (a2), and a polyol compound (in order to obtain a urethane (meth)acrylate compound (A1) ( A3) will be described in the following order.

<Hydroxy group-containing (meth) acrylate type compound (a1)>

The hydroxyl group-containing (meth)acrylate compound (a1) may, for example, be 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate or 2-hydroxyl (meth)acrylate. Butyl methacrylate, 4-hydroxybutyl (meth) acrylate, hydroxyalkyl (meth) acrylate such as 6-hydroxyhexyl (meth) acrylate, 2-hydroxyethyl acrylate, 2-(methyl) Propylene methoxyethyl 2-hydroxypropyl phthalate, caprolactone modified 2-hydroxyethyl (meth) acrylate, dipropylene glycol (meth) acrylate, fatty acid modification (methyl ) Glycidyl acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxy-3-(methyl) propylene methoxy propyl (meth) acrylate a (meth) acrylate compound containing one ethylenically unsaturated group such as an ester; two ethylenes such as glycerol di(meth)acrylate or 2-hydroxy-3-propenyloxypropyl methacrylate Unsaturated (meth) acrylate compound; pentaerythritol tri (meth) acrylate, caprolactone modified pentaerythritol tri (meth) acrylate, oxyethylene modified pentaerythritol tri (methyl) Acrylate, dipentaerythritol penta (meth) acrylate, hexyl A (meth) acrylate-based compound containing three or more ethylenically unsaturated groups, such as a lactone-modified dipentaerythritol penta (meth) acrylate or an oxyethylene-modified dipentaerythritol penta (meth) acrylate.

Among these, a hydroxy (meth) acrylate type compound having one ethylenically unsaturated group is preferable because it can alleviate the hardening shrinkage at the time of formation of a coating film; more preferably (meth)acrylic acid 2- Hydroxyethyl ester, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, etc. (hydroxy) hydroxyalkyl acrylate, caprolactone modified 2-hydroxyethyl (meth) acrylate; particularly excellent in reactivity and versatility, 2-hydroxyethyl (meth) acrylate, (A 2-hydroxypropyl acrylate, caprolactone modified 2-hydroxyethyl (meth) acrylate.

Further, these may be used alone or in combination of two or more.

<Poly Isocyanate Compound (a2)>

The polyisocyanate compound (a2) may, for example, be methylphenyl diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylene diisocyanate or the like. An aromatic polyisocyanate such as methylxylene diisocyanate, phenyl diisocyanate or naphthalene diisocyanate; hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, diazonic acid diisocyanate, lysine Aliphatic polyisocyanate such as triisocyanate; hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis(isocyanatomethyl) An alicyclic polyisocyanate such as cyclohexane; or a ternary compound or a polyvalent compound of the polyisocyanate, an allophanate type polyisocyanate, a biuret type polyisocyanate, or a water-dispersible polyisocyanate ( For example, "AQUANATE 100", "AQUANATE 110", "AQUANATE 200", "AQUANATE 210", etc., manufactured by Nippon Polyurethane Industry Co., Ltd.) Wait.

Among these, in particular, from the viewpoint of less yellowing, aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and isocyanuric acid diisocyanate, and hydrogenated diphenyl groups are preferable. Methane diisocyanate, hydrogenated xylene diisocyanate, isophorone diisocyanate, An alicyclic diisocyanate such as norbornene diisocyanate or 1,3-bis(isocyanooxymethyl)cyclohexane, more preferably isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate or hydrogenated Xylene diisocyanate and hexamethylene diisocyanate are more preferably isophorone diisocyanate or hexamethylene diisocyanate which are excellent in reactivity and versatility.

<Polyol compound (a3)>

The polyol-based compound (a3) may be a compound containing two or more hydroxyl groups, and examples thereof include an aliphatic polyhydric alcohol, an alicyclic polyhydric alcohol, a polyether polyhydric alcohol, a polyester polyhydric alcohol, and a poly A carbonate-based polyol, a polyolefin-based polyol, a polybutadiene-based polyol, a polyisoprene-based polyol, a (meth)acrylic polyol, a polyoxyalkylene-based polyol, or the like.

The weight average molecular weight of the polyol compound (a3) is preferably from 60 to 20,000, more preferably from 100 to 15,000, still more preferably from 150 to 8,000. When the weight average molecular weight of the polyol-based compound (a3) is too large, sufficient crosslinking density cannot be obtained at the time of curing, the surface of the cured coating film is sticky, or various durability tends to be lowered, and a curable resin composition is obtained. It becomes a tendency for high viscosity to become difficult to handle. In addition, when the weight average molecular weight of the polyol compound (a3) is too small, the flexibility of the coating film after curing is lowered, and it is difficult to obtain a moist soft hand touch.

Further, the polyol compound (a3) preferably contains a polyol compound (a3-1) having a weight average molecular weight of 500 and a weight average molecular weight of 500 to 20,000 from the viewpoint of alkali resistance and ethanol resistance. Alcohol compound (a3-2).

The weight average molecular weight of the polyol compound (a3-1) is less than 500, preferably 60 to 450, more preferably 60 to 400, still more preferably 100 to 300. When the weight average molecular weight of the polyol compound (a3-1) is too large, as a blending composition, the degree of hydrogen bonding-bonded bridge (PSEUDO CROSSLINKING) which is characteristic of the urethane bond is lowered, and the hardening is caused. The durability of the coating film such as chemical resistance is lowered.

The weight average molecular weight of the polyol compound (a3-2) is from 500 to 20,000, preferably from 2,000 to 15,000, more preferably from 3,000 to 8,000. If the weight average of the polyol compound (a3-2) When the amount is too small, the molecular weight of the urethane (meth) acrylate-based compound (A) is relatively small. Therefore, when the composition is blended, the elasticity of the cured coating film tends to decrease; if it is too large, A coating film composed of a resin solution which is blended as an active energy ray-curable composition tends to be sticky. In addition, since the weight average molecular weight of the polyol compound (a3-2) is large, the reactivity at the time of synthesis becomes insufficient, so the reaction time becomes extremely long, and the practicality as a synthesis condition is not preferable.

Further, in the weight average molecular weight of the polyol compound, the difference between the polyol compound (a3-1) and the polyol compound (a3-2) is preferably 400 or more, more preferably 800 or more, and still more preferably 1,200 or more, particularly preferably 2,000 or more. If the difference is too small, the balance between the chemical resistance and the elasticity of the cured coating film is poor, and the mechanical properties tend to be difficult.

The blend ratio (mol ratio) of the polyol compound (a3-1) to the polyol compound (a3-2) is preferably (a3-1): (a3-2) = 30: 70 to 95: 5 More preferably (a3-1): (a3-2)=40:60~90:10, and more preferably (a3-1): (a3-2)=50:50~85:15.

When the blending ratio of the polyol compound (a3-1) is too large, the viscosity tends to increase excessively. When the amount is too small, alkali resistance or ethanol resistance tends to be lowered.

Examples of the polyol compound (a3-1) having a weight average molecular weight of less than 500 include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, and dimethylolpropane. Neopentyl glycol, 1,2-hexanediol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-tetramethylene Glycol, 1,3-tetramethylene glycol, 2-methyl-1,3-trimethylene glycol, 1,5-pentamethylene glycol, 1,6-hexamethylene Alcohol, 3-methyl-1,5-pentamethylene glycol, 2,4-diethyl-1,5-pentamethylene glycol, 1,9-nonanediol, 2-methyl- An aliphatic alcohol such as 1,8-octanediol, ditrimethylolpropane, dipentaerythritol or tripentaerythritol; a cyclohexanediol such as 1,4-cyclohexanediol or cyclohexyldimethanol; and bisphenol A phenol such as A, a sugar alcohol such as tricyclodecane dimethanol, xylitol or sorbitol, and the like may be used alone or in combination of two or more. Among them, in particular, since the crystallinity of neopentyl glycol, 1,2-hexanediol, and tricyclodecane dimethanol is low, it is preferably used.

In addition, examples of the polyol compound (a3-2) having a weight average molecular weight of 500 to 20,000 include aliphatic polyols, alicyclic polyols, polyether polyols, polyester polyols, and polycarbons. An acid ester type polyol, a polyolefin type polyol, a polybutadiene type polyol, a (meth)acrylic type polyol, a polyoxyalkylene type polyol, or the like.

The aliphatic polyol may, for example, be ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, dimethylolpropane, neopentyl glycol or 2,2-diethyl- 1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-tetramethylene glycol, 1,3-tetramethylene glycol, 2-methyl-1 , 3-trimethylene glycol, 1,5-pentamethylene glycol, 1,6-hexamethylene glycol, 3-methyl-1,5-pentamethylene glycol, 2,4 -Diethyl-1,5-pentamethylene glycol, pentaerythritol diacrylate, 1,9-nonanediol, 2-methyl-1,8-octanediol, etc. a sugar alcohol such as xylitol or sorbitol, an aliphatic alcohol containing three or more hydroxyl groups such as glycerin, trimethylolpropane or trimethylolethane, etc., or one of them may be used. Use two or more types.

Examples of the alicyclic polyol include cyclohexanediols such as 1,4-cyclohexanediol and cyclohexyldiethanol, hydrogenated bisphenols such as hydrogenated bisphenol A, and tricyclodecane dimethanol. These may be used alone or in combination of two or more.

Examples of the polyether-based polyol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polytetramethylene glycol, polypentamethylene glycol, and polyhexamethylene glycol. A polyether polyol having an alkyl structure, or a random or block copolymer of the polyalkylene glycol.

Examples of the polyester-based polyol include a condensation polymer of a polyhydric alcohol and a polyvalent carboxylic acid; a ring-opening polymer of a cyclic ester (lactone); and three kinds of a polyhydric alcohol, a polyvalent carboxylic acid, and a cyclic ester. The reactants obtained from the ingredients, and the like.

Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylene glycol, and 1,3-tetramethylene glycol. , 2-methyl-1,3-trimethylene glycol, 1,5-pentamethylene glycol, neopentyl glycol, 1,6-hexamethylene glycol, 3-methyl-1, 5-pentamethylene glycol, 2,4-diethyl-1,5-pentamethylene glycol, glycerol, trimethylolpropane, trimethylolethane, cyclohexanediol Examples (such as 1,4-cyclohexanediol), bisphenols (such as bisphenol A), and sugar alcohols (such as xylitol or sorbitol).

Examples of the polyvalent carboxylic acid include malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, sebacic acid, and dodecanedioic acid. Alicyclic dicarboxylic acid; alicyclic dicarboxylic acid such as 1,4-cyclohexanedicarboxylic acid; terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalene dicarboxylic acid, An aromatic dicarboxylic acid such as phenyldicarboxylic acid or benzotricarboxylic acid is added.

Examples of the cyclic ester include propiolactone, β-methyl-8-valerolactone, and ε-caprolactone.

Examples of the polycarbonate-based polyol include a reaction product of a polyhydric alcohol and phosgene; a ring-opening polymer of a cyclic carbonate (such as an alkylene carbonate).

The polyhydric alcohol may, for example, be a polyol exemplified in the description of the polyester-based polyol, and examples of the alkylene carbonate may include ethyl methyl carbonate, trimethyl carbonate, and tetramethylene carbonate. , hexamethylene carbonate and the like.

Further, the polycarbonate-based polyol may have a carbonate bond and a terminal having a hydroxyl group in the molecule, and may have both a carbonate bond and an ester bond.

The polyolefin-based polyol may, for example, be a homopolymer or a copolymer having ethylene, propylene, butylene or the like as a saturated hydrocarbon skeleton and having a hydroxyl group at a molecular terminal thereof.

The polybutadiene-based polyol may, for example, have a copolymer of butadiene as a hydrocarbon skeleton and a molecular terminal having a hydroxyl group.

The polybutadiene-based polyol may also be a hydrogenated polybutadiene polyol obtained by hydrogenating all or a part of the ethylenically unsaturated group contained in the structure.

The polyisoprene-based polyol may, for example, be a copolymer having isoprene as a hydrocarbon skeleton and a molecular terminal having a hydroxyl group.

The polyisoprene-based polyol may also be a hydrogenated polyisoprene polyol which is hydrogenated all or a part of the ethylenically unsaturated group contained in the structure.

The (meth)acrylic polyol may, for example, be a (meth) acrylate polymer or a copolymer having at least two hydroxyl groups in the molecule, and examples of the (meth) acrylate include: Methyl)methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, (methyl) An alkyl (meth)acrylate such as 2-ethylhexyl acrylate, decyl (meth) acrylate, dodecyl (meth)acrylate or octadecyl (meth)acrylate.

The polyoxyalkylene-based polyol may, for example, be dimethylpolydecane polyol or methylphenyl polyoxyalkylene polyol.

Among these, from the viewpoint of suppressing stickiness when the film is cured, it is preferable to use an aliphatic polyol or an alicyclic polyol, and from the viewpoint of imparting flexibility, it is preferred to use a polyester polyol or a polyether. Polyol or polycarbonate polyol.

The method for producing the urethane (meth)acrylate compound (A1) is usually a hydroxyl group-containing (meth)acrylate compound (a1), a polyvalent isocyanate compound (a2), or a polyol system. The compound (a3) may be added to the reactor once or separately, and the polyol compound (a3) and the polyisocyanate compound (a2) may be previously obtained in view of stability of the reaction or reduction of by-products. It is useful to carry out a reaction to obtain a reactant, and to react the hydroxyl group-containing (meth) acrylate type compound (a1) with it.

A known reaction method can be used for the reaction of the polyol compound (a3) with the polyvalent isocyanate compound (a2). In this case, for example, the molar ratio of the hydroxyl group in the isocyanate group:polyol compound (a3) in the polyisocyanate compound (a2) is 2n:(2n-2) (n is an integer of 2 or more) To the extent that the terminal isocyanate group-containing urethane (meth) acrylate compound having an isocyanate group remaining is obtained, an addition reaction with the hydroxyl group-containing (meth) acrylate compound (a1) is possible.

The polyol compound (a3) is reacted with the polyvalent isocyanate compound (a2) in advance. The reaction product obtained is reacted with a hydroxyl group-containing (meth) acrylate-based compound (a1), and a known reaction method can also be used.

Reaction molar ratio of the reaction product to the hydroxyl group-containing (meth) acrylate compound (a1), for example, when the polyisocyanate compound (a2) has two isocyanate groups and a hydroxyl group-containing (meth) acrylate system When the hydroxyl group of the compound (a1) is one, the reaction product: the hydroxyl group-containing (meth)acrylate compound (a1) is about 1:2; and the polyisocyanate compound (a2) has three isocyanate groups. When the hydroxyl group-containing (meth) acrylate-based compound (a1) has one hydroxyl group, the reaction product: hydroxyl group-containing (meth) acrylate-based compound (a1) is about 1:3.

In the addition reaction of the reaction product with the hydroxyl group-containing (meth) acrylate-based compound (a1), when the residual isocyanate group content of the reaction system is 0.5% by weight or less, the reaction is terminated, whereby the amine A can be obtained. Acid ester (meth) acrylate compound (A1).

The reaction between the polyol compound (a3) and the polyvalent isocyanate compound (a2) is further carried out in the reaction between the reaction product and the hydroxyl group-containing (meth) acrylate compound (a1) for the purpose of promoting the reaction. The medium is also preferable. Examples of the catalyst include organometallic compounds such as dibutyltin dilaurate, trimethyltin hydroxide, and tetra-n-butyltin, zinc octenoate, tin octenate, and cobalt naphthenate. a metal salt such as tin (II) chloride or tin (IV) chloride, triethylamine, benzyldiethylamine, 1,4-diazabicyclo[2,2,2]octane, 1,8-di Azabicyclo[5,4,0]undecene, N,N,N,'N'-tetramethyl-1,3-butanediamine, N-ethyl An amine-based catalyst such as porphyrin, cerium nitrate, cerium bromide, cerium iodide, cerium sulfide, etc., other organic cerium compounds such as dibutyl hydrazine dilaurate, dioctyl bismuth dilaurate or 2-ethylhexanoic acid Barium salt, barium naphthenate salt, barium isononium salt, barium neodecanoate salt, barium laurate salt, barium maleate salt, barium stearate salt, barium oleate salt, linolenic acid barium salt, acetic acid Anthraquinone-based catalysts such as barium salts, barium neodymium citrate, barium sulphate salts, bismuth subgallate salts, and the like, among which dibutyltin dilaurate, 1 The 8-diazabicyclo[5,4,0]undecene is ideal.

Further, it is also preferable to use a zirconium-based catalyst and a liquid zinc-based catalyst.

Further, in the reaction between the polyol compound (a3) and the polyvalent isocyanate compound (a2), in the reaction of the reaction product with the hydroxyl group-containing (meth) acrylate compound (a1), An organic solvent having no functional group reactive with isocyanate groups, such as an ester such as ethyl acetate or butyl acetate; a ketone such as methyl ethyl ketone or fenyl isobutyl ketone; or an aromatic compound such as toluene or xylene; Etc. Organic solvents.

Further, the reaction temperature is usually from 30 to 90 ° C, preferably from 40 to 80 ° C, and the reaction time is usually from 2 to 10 hours, preferably from 3 to 8 hours.

The urethane (meth)acrylate compound (A1) is preferably one having 2 to 10 ethylenically unsaturated groups from the viewpoint of imparting durability to the cured coating film, and particularly preferably having 2 to 10 6 ethylenically unsaturated bases. When the number of the ethylenically unsaturated groups is too large, the crosslinking density after hardening becomes too large, and the coating film becomes too hard, and it is difficult to obtain a wet soft touch feeling. When the amount is too small, it is difficult to obtain a sufficient crosslinking density, so that it is hardened. The surface of the coating film is sticky, or the durability is lowered.

The weight average molecular weight of the urethane (meth) acrylate type compound (A1) is preferably from 1,000 to 50,000, more preferably from 2,000 to 40,000. When the weight average molecular weight is too small, the cured coating film tends to become brittle, and if it is too large, the viscosity tends to be high and it is not easy to handle.

In addition, as the polyol compound (a3) constituting the urethane (meth)acrylate compound (A1), a polyol compound (a3-1) having a weight average molecular weight of less than 500 and a weight average molecular weight of 500 are used. In the case of the polyol compound (a3-2) of 20,000, the weight average molecular weight of the urethane (meth) acrylate compound (A1) is preferably from 2,500 to 50,000, more preferably from 2,500 to 40,000. Good for 3,500~30,000.

When the weight average molecular weight is too small, the amount of the unsaturated group in the compounding ratio is relatively increased. Therefore, when the film is cured, the difference in hardness from the particulate synthetic resin filler (B) is remarkable, and the external component cannot be released. The stress tends to be easily wounded. If the viscosity is too large, the viscosity of the curable resin composition tends to be too high, and if sufficient crosslink density is not obtained, the surface of the cured coating film becomes sticky, or various durability is easily lowered. tendency.

Further, the weight average molecular weight described above was measured in the same manner as described above.

The viscosity of the urethane (meth) acrylate compound (A1) at 60 ° C is preferably from 1,000 to 100,000 mPa. s, more preferably 1,500~50,000mPa. s. If the viscosity is outside the above range, the coating property tends to be lowered.

Further, in the measurement method of the viscosity, an E-type viscometer was used in the same manner as described above.

<Aminoformate (meth) acrylate type compound (A2)>

The urethane (meth) acrylate type compound (A2) in the present invention is obtained by reacting a hydroxyl group-containing (meth) acrylate type compound (a1) and a polyvalent isocyanate compound (a2).

The content of the ethylenically unsaturated group of the urethane (meth)acrylate compound (A2) used in the present invention is preferably 2 to 10, more preferably 2 to 6. When the number of the ethylenically unsaturated groups is too large, the crosslinking density after curing becomes too large, and the coating film becomes too hard, and it tends to be difficult to obtain a soft soft touch feeling. If too small, it is difficult to obtain a sufficient crosslinking density, so that it is hardened. The surface of the coating film is sticky, or the durability is lowered.

Further, in order to adjust the number of ethylenically unsaturated groups, it is preferred to suitably use a hydroxyl group-containing (meth)acrylate compound (a1) and a polyvalent isocyanate compound (a2), for example, as a hydroxyl group ( When the methyl group-containing compound (a1) has three ethylenically unsaturated groups, and the polyisocyanate compound (a2) is a diisocyanate compound, the urethane (meth)acrylate compound is used. The number of ethylenic unsaturated groups in (A2) was six.

The method for producing the urethane (meth) acrylate-based compound (A2) may be produced according to the method for producing the urethane (meth) acrylate-based compound (A1).

In addition, the reaction molar ratio of the polyisocyanate compound (a2) to the hydroxyl group-containing (meth)acrylate compound (a1) is, for example, two isocyanate groups of the polyisocyanate compound (a2), and a hydroxyl group. When the hydroxyl group of the (meth) acrylate type compound (a1) is one, the polyvalent isocyanate type compound (a2): the hydroxyl group-containing (meth) acrylate type compound (a1) is about 1:2, When the polyisocyanate compound (a2) has three isocyanate groups and the hydroxyl group-containing (meth)acrylate compound (a1) has one hydroxyl group, the polyisocyanate compound (a2): hydroxyl group-containing The (meth) acrylate compound (a1) is about 1:3.

In the addition reaction of the polyisocyanate compound (a2) and the hydroxyl group-containing (meth) acrylate compound (a1), the reaction is terminated when the residual isocyanate group content of the reaction system is 0.5% by weight or less. Thus, a urethane (meth) acrylate type compound (A2) can be obtained.

The weight average molecular weight of the obtained urethane (meth) acrylate type compound (A2) is preferably from 1,000 to 20,000, more preferably from 1,000 to 10,000. When the weight average molecular weight is too small, the softness of the cured coating film is lowered, and the tendency to obtain a soft soft touch is hardly obtained. When the weight is too large, sufficient crosslinking density cannot be obtained at the time of hardening, the surface of the cured coating film is sticky, or durability is easy. Reduce the tendency.

Further, the weight average molecular weight described above was measured in the same manner as described above.

The viscosity of the urethane (meth) acrylate compound (A2) at 60 ° C is preferably from 1,000 to 30,000 mPa. s, more preferably 1,000 to 20,000 mPa. s. If the viscosity is outside the above range, the coating property tends to be lowered.

Further, in the measurement method of the viscosity, an E-type viscometer was used in the same manner as described above.

[Particle-like synthetic resin filler (B)]

The particulate synthetic resin filler (B) in the present invention may, for example, contain a nitrogen atom such as a nylon filler, a polyurethane filler, a polyurea filler, a polyamidoximine filler, or a polypropylene decylamine filler. a synthetic resin filler; a polyolefin resin filler such as a polyethylene filler or a polypropylene filler; a poly(meth)acrylic acid filler, a polybutyl (meth)acrylic acid filler, or a polystyrene filler, which is composed of a single polymerization component ( a (meth)acrylic synthetic resin filler containing a (meth)acrylic group-containing synthetic resin filler composed of two or more kinds of polymerized components; a polyphenylene sulfide filler; a synthetic resin filler containing a sulfur atom such as an ether hydrazine filler; a synthetic resin filler containing a fluorine atom such as a polytetrafluoroethylene filler; and an epoxy resin-containing synthetic resin filler composed of an epoxy resin; A polycarbonate resin filler; a composite synthetic resin filler of the foregoing filler; a core-shell multilayer filler.

Among these, a synthetic resin filler containing a nitrogen atom and a polyolefin resin filler are preferable. The synthetic resin filler containing a nitrogen atom preferably has an affinity with the urethane (meth)acrylate compound (A), excellent particle aggregation stability, and sedimentation stability, or is easy to impart a hard coat. The viewpoint of the soft touch or elasticity of the film wet is a polyurethane filler, and the polyolefin resin filler is preferably a polyethylene filler. Further, in order to impart a wet touch feeling to the cured coating film, it is preferred to use the polyurethane filler and the polyethylene filler in combination.

The nylon filler may, for example, be manufactured by Toray Industries, Inc. (product name; "SP-10", "SP-500", "TR-1", "TR-2", "842-P48", "842- P70", "842-P80"), etc.

As the polyurethane filler, for example, Urethane Beads (trade name; "ART PEARL C series", "ART PEARL P series", "ART" manufactured by Kokusai Industrial Co., Ltd. PEARL JB Series, ART PEARL U Series, ART PEARL CE Series, ART PEARL AK Series, ART PEARL HI Series, ART PEARL MM Series, ART PEARL FF Series, ART PEARL TK series, "ART PEARL C-TH series", "ART PEARL RW~Z series", "ART PEARL RU~V series", "ART PEARL BP series").

In particular, it is preferable that a transparent white coating film is preferably used as a transparent fine particle for a cured coating film, and a fine white surface is preferably white. Specific examples of the filler include: ART PEARL C-400T, ART PEARL C-600T, ART PEARL C-800T, ART PEARL P-400T, ART PEARL P-600T, ART PEARL P-800T, ART PEARL JB- 400T, ART PEARL JB-600T, ART PEARL JB-800T, ART PEARL U-600T, ART PEARL CE-400T, ART PEARL CE-800T, ART PEARL AK-300TR, ART PEARL AK-400TR, ART PEARL AK-800TR, ART PEARL HI-400T, ART PEARL MM-120T, ART PEARL FF-421T, ART PEARL FF-411T, ART PEARL FF-413T, ART PEARL TK-600T, ART PEARL C-600TH, ART PEARL RZ-600T, ART PEARL RY-600T, ART PEARL RT-600T, ART PEARL RX-600T, ART PEARL RW-600T, ART PEARL RZ-600T, ART PEARL RV-600T, ART PEARL RU- 600T, ART PEARL RV-600T, ART PEARL BP-600T.

The polyamidoximine resin filler may, for example, be manufactured by Toray Industries, Inc. (trade name; "Toraypearl PAI").

The polyethylene filler is preferably a solvent-dispersed polyethylene filler, and examples thereof include polyethylene wax and modified polyethylene wax manufactured by Xingyang Chemical Co., Ltd. (trade name; "Micro. Flat UN-8", "Micro .Flat PEX-101", "Micro.Flat B-501"), polyethylene wax made by BYK Chemical Japan, and modified polyethylene wax (trade name; "CERAFLOUR928", "CERAFLOUR950", "CERAFLOUR988", "CERAFLOUR990", "CERAFLOUR991", "CERAFLOUR995", "CERACOL39", "CERAFAK111", "CERAMAT250", "CERAMAT258", "MINERPOL221").

The polypropylene filler is preferably a solvent dispersion, and examples thereof include a polypropylene wax manufactured by BYK Chemical Co., Ltd., and a modified polypropylene wax (trade name "CERAFLOUR970").

The synthetic resin filler containing a (meth)acrylic group may, for example, be an acrylic bead (trade name; "ART PEARL GR series", "ART PEARL SE series", "ART PEARL G series", "ART PEARL GS Series", "ART PEARL J Series", "ART PEARL MF Series", "ART PEARL BE Series"), etc. Among them, in particular, it is preferable that the transparent hard white film is preferably used as the transparent fine particles of the hard coat film, and the white crystal coating film is preferably white. Specific examples of the filler include: ART PEARL GR-300T, ART PEARL GR-400T, ART PEARL GR-600T, ART PEARL GR-800T, ART PEARL SE-020T, ART PEARL SE-010T, ART PEARL SE- 006T, ART PEARL G-400T, ART PEARL G-800T, ART PEARL GS-310T, ART PEARL GS-350T, ART PEARL GS-850TC, ART PEARL J-4P, ART PEARL J-5P, ART PEARL J-7P, ART PEARL J-4PY, ART PEARL J-6PF, ART PEARL J-7PY, ART PEARL MF-0063, ART PEARL BE-006T.

The synthetic resin filler containing the sulfur atom may, for example, be a polyphenylene sulfide resin particle (trade name; "Toraypearl PPS") manufactured by Toray Industries, Ltd., or a polyether resin (trade name; "Toraypearl PES"). Wait.

The synthetic resin filler containing a fluorine atom may, for example, be a polyethylene or a polytetrafluoroethylene mixed wax (trade name; "Micro. Flat PF-8") manufactured by Hyosung Chemical Co., Ltd., manufactured by BYK Chemical Japan Co., Ltd. PTFE wax (trade name; "CERAFLOUR980", "CERAFLOUR981"), polyethylene-polytetrafluoroethylene mixed wax (trade name; "CERAFLOUR997"), PTFE modified polyethylene wax (trade name; CERAFLOUR998", "CERACOL607"), PTFE particles made by Kitamura (trade name; "KTL-8N", "KTL-8F", "KTL-9S", "KTL-10N", "KTL-20N" )Wait.

The epoxy resin-containing synthetic resin filler may, for example, be manufactured by Toray Industries, Inc. (trade name; "Toraypearl EP").

The polycarbonate resin filler may, for example, be manufactured by Hyosung Chemical Co., Ltd. (trade name; "Micro. Flat MA-07N").

The average particle diameter of the particulate synthetic resin filler (B) in the present invention is preferably from 1 to 30 μm, more preferably from 2 to 20 μm, still more preferably from 4 to 15 μm.

When the average particle diameter is too small, the gloss of the cured coating film becomes high, and the appearance tends to be less likely to feel a high-grade feeling. When the size is too large, the wear contact point is increased to reduce the abrasion resistance, and the unevenness of the hardened surface is increased. It is not smooth, so it is not easy to obtain a moist soft touch feeling.

Further, since the particulate synthetic resin filler (B) has a substantially spherical shape, the particle diameter can be determined from the basic shape of the ball, and the number average particle diameter, the average length particle diameter, and the area are generally flat. The average particle diameter, the volume average particle diameter, and the like, but the average particle diameter of the present invention means a volume average particle diameter which is generally used, and the volume average particle diameter is laser diffraction. The scattering type particle size distribution meter performs the measurement.

The true specific gravity of the particulate synthetic resin filler (B) is preferably from 0.8 to 2.3, more preferably from 0.8 to 2, still more preferably from 0.8 to 1.5.

When the true specific gravity is too large, particles are precipitated in the drying step after coating, and the surface unevenness tends not to be exhibited. When the content is too small, the mixing of the urethane (meth)acrylate compound (A) is likely to become difficult. The tendency.

The method for producing the particulate synthetic resin filler (B) may, for example, be a method in which a monomer is polymerized by suspension polymerization, emulsion polymerization, seed polymerization or the like to directly form a particulate synthetic resin, or may be borrowed. A conventional synthetic resin produced by various methods is mechanically pulverized to form a particulate form.

Among these, in particular, the shape of the fine particles is particularly preferably a polymerization method from the viewpoint of obtaining a spherical shape excellent in fluidity or dispersibility.

The glass transition temperature (Tg) of the particulate synthetic resin filler (B) in the present invention is preferably -140 to 40 ° C, more preferably -135 to 20 ° C, still more preferably -130 to 0 ° C.

When the glass transition temperature is too low, the tackiness of the surface of the coating film tends to be too large. When the glass transition temperature is too high, there is a tendency that the rubber film-like wet soft touch is hard to be obtained on the surface of the coating film.

The glass transition temperature can be measured by using a temperature-modulated DSC (DSC2920, manufactured by T.A. Instruments). The measurement conditions were such that a sample of about 1 to 5 mg was sealed in a dedicated aluminum pan, and the temperature was raised to 3 ° C / min in the range of -100 ° C to 100 ° C.

The content (solid content) of the particulate synthetic resin filler (B) in the present invention is preferably 25 to 400 parts by weight based on 100 parts by weight of the urethane (meth)acrylate compound (A). More preferably, it is 30 to 350 parts by weight, and more preferably 35 to 250 parts by weight. When the content of the particulate synthetic resin filler (B) is too large, the abrasion resistance of the cured coating film tends to be extremely lowered, and the surface of the coating film tends to be easily wounded, and if it is too small, the tendency to obtain a moist soft hand touch is difficult. .

In addition, the content (solid content) of the polyurethane filler is preferably 25 to 400 parts by weight, more preferably 30 parts by weight based on 100 parts by weight of the urethane (meth)acrylate compound (A). ~300 parts by weight, more preferably 35 to 250 parts by weight. When the content of the polyurethane filler is too large, the abrasion resistance of the cured coating film tends to be extremely lowered, and the surface of the coating film tends to be easily wounded. When the content is too small, it tends to be difficult to obtain a soft and soft hand touch.

Further, as a ratio (weight ratio of the solid content) when the polyurethane filler and the polyethylene filler are used in combination, the polyethylene filler is preferably 0.1 to 70 by weight based on 100 parts by weight of the polyurethane filler. More preferably, it is 0.5 to 50 parts by weight, and more preferably 1 to 30 parts by weight.

If the content ratio of the polyethylene filler to the polyurethane filler is too small, the soft touch of the coating film is lowered, and the gloss is increased, so that the high-grade feeling tends to be impaired, and the damage resistance of the hardened coating film is easily lowered. The tendency.

In the case where the particulate synthetic resin filler (B) is a dispersion of a solvent or the like, the weight of the solid content is defined.

The active energy ray-curable resin composition of the present invention contains the urethane (meth)acrylate compound (A) and the particulate synthetic resin filler (B) as essential components, and more It is preferable to form a mesh structure by crosslinking with active energy ray to adjust the balance between hardness and flexibility in the coating film, or to improve durability such as water resistance and heat resistance. The ethylenically unsaturated monomer (C) is blended.

[Ethylene unsaturated monomer (C)]

The ethylenically unsaturated monomer (C) is an ethylenically unsaturated monomer (aminoformate (meth)acrylate type compound (A) having one or more ethylenically unsaturated groups in one molecule. In addition, it may be, for example, a monofunctional monomer, a bifunctional monomer, or a trifunctional or higher monomer.

The monofunctional monomer may be a monomer containing one ethylenically unsaturated group, and examples thereof include styrene, vinyl toluene, chlorostyrene, α-methylstyrene, and (meth)acrylic acid. Ester, ethyl (meth)acrylate, acrylonitrile, vinyl acetate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, Phenyloxyethyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, (meth)acrylic acid 3-chloro-2-hydroxypropyl ester, glycerol mono(meth)acrylate, glycidyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, (methyl) Isodecyl acrylate, tricyclodecyl (meth) acrylate, dicyclopentenyl (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate , (meth)acrylic acid octyl ester, (meth)acrylic acid decyl ester, (meth)acrylic acid decyl ester, (meth)acrylic acid isodecyl ester, (meth)acrylic acid lauryl ester, (meth)acrylic acid hard Lipid ester, benzyl (meth)acrylate Phenoxyethylene modified (meth) acrylate, nonylphenol oxypropylene modified (meth) acrylate, 2-(methyl) propylene oxy-2-hydroxypropyl phthalate, etc. Semi-ester (meth) acrylate of phthalic acid derivatives, tetrahydrofurfuryl (meth) acrylate, carbitol (meth) acrylate, benzyl (meth) acrylate, caprolactone modified (A 2-hydroxyethyl acrylate, butoxyethyl (meth) acrylate, allyl (meth) acrylate, propylene fluorenyl Porphyrin, 2-hydroxyethyl acrylamide, N-methylol (meth) acrylamide, N-vinyl pyrrolidone, 2-vinyl pyridine, 2-(methyl) propylene methoxyethyl acid phosphate Ester monoester and the like.

Further, in addition to the above-mentioned monofunctional monomer, for example, Michael's adduct of acrylic acid or 2-propenyloxyethyl dicarboxylic acid monoester may be mentioned; as a wheat-additive of acrylic acid, for example, For example: acrylic acid dimer, methacrylic acid dimer, acrylic acid terpolymer, methacrylic acid terpolymer, acrylic acid tetramer, methacrylic acid tetramer, and the like. Further, examples of the carboxylic acid having a specific substituent, that is, 2-propenyloxyethyl dicarboxylic acid monoester, may be, for example, 2-propenyloxyethylsuccinic acid monoester or 2-methylpropene oxime. Oxyethyl succinate monoester, 2-propenyl methoxyethyl phthalate monoester, 2-methyl propylene oxiranyl phthalate monoester, 2-propenyl oxiranyl hexahydroortho Monoester of phthalic acid, 2-methylpropenyl oxiranyl hexahydrophthalic acid monoester, and the like. Further, for example, an oligoester acrylate can also be mentioned.

The bifunctional monomer may be a monomer containing two ethylenically unsaturated groups, and examples thereof include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and tetra. Ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylic acid Ester, butanediol di(meth) propylene Acid ester, neopentyl glycol di(meth) acrylate, ethylene oxide modified bisphenol A type di(meth) acrylate, propylene oxide modified bisphenol A type di(meth) acrylate, 1,6-hexanediol di(meth)acrylate, 1,6-hexanediol oxyethylene modified di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, Di(meth)acrylate, pentaerythritol di(meth)acrylate, ethylene glycol diglycidyl di(meth)acrylate, diethylene glycol diglycidyl di(meth)acrylate , diglycidyl phthalate di(meth) acrylate, hydroxytrimethyl acetic acid modified neopentyl glycol di(meth) acrylate, isocyanuric acid ethylene oxide modified diacrylate , 2-(meth)acryloxyethyl acid phosphate diester, and the like.

The monomer having three or more functional groups may be a monomer containing three or more ethylenically unsaturated groups, and examples thereof include trimethylolpropane tri(meth)acrylate and pentaerythritol tri(meth)acrylate. , pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris (meth) propylene methoxy ethoxy trimethylol propane, glycerol poly Glycidyl ether poly(meth) acrylate, isocyanuric acid ethylene oxide modified triacrylate, oxyethylene modified dipentaerythritol penta (meth) acrylate, ethylene oxide modified dipentaerythritol Methyl) acrylate, oxyethylene modified pentaerythritol tri(meth) acrylate, ethylene oxide modified pentaerythritol tetra(meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, Lactone modified dipentaerythritol hexa(meth) acrylate, caprolactone modified pentaerythritol tri(meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, succinic acid modified pentaerythritol tris (a) Base) acrylate and the like.

These ethylenically unsaturated monomers (C) may be used alone or in combination of two or more. Further, the ethylenically unsaturated monomer (C) may be blended separately from the urethane (meth) acrylate compound (A) or the particulate synthetic resin filler (B). The raw material for the production of the urethane (meth) acrylate-based compound (A) remains in the system at the time of production.

In the ethylenically unsaturated monomer (C), a monofunctional monomer and a bifunctional monomer are preferred, and from the viewpoint of no aromatic ring, yellowing of the coating film, and high versatility, it is more preferable. Cyclohexyl (meth)acrylate, isodecyl (meth)acrylate, dicyclopentenyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, diethylene glycol di(meth)acrylate , tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6- Hexanediol di(meth)acrylate.

Further, it is also preferable to use a hydroxyl group-containing ethylenically unsaturated monomer. As a specific example, from the viewpoint of no aromatic ring and yellowing of the coating film, 2-hydroxyethyl (meth)acrylate is preferable. 2-hydroxypropyl acrylate, 2-hydroxybutyl (meth) acrylate, caprolactone modified 2-hydroxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol Acrylates are preferred, especially 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, caprolactone modified (methyl) 2-Hydroxyethyl acrylate is particularly desirable from the standpoint of versatility.

In the present invention, the content of the ethylenically unsaturated monomer (C) is preferably from 0 to 500 parts by weight, more preferably from 100 parts by weight to the urethane (meth)acrylate compound (A). It is 5 to 350 parts by weight, and more preferably 10 to 150 parts by weight. When the content of the ethylenically unsaturated monomer (C) is too large, in the case of a monofunctional monomer, the coating film after curing tends to be sticky, and in the case of a monomer having two or more functional groups, after curing The coating film becomes too hard, and it is difficult to obtain a moist soft touch feeling.

[Photopolymerization initiator (D)]

In addition to the urethane (meth)acrylate compound (A) and the fine particulate synthetic resin filler (B), in order to efficiently perform curing by active energy rays, the present invention preferably contains Photopolymerization initiator (D).

The photopolymerization initiator (D) may, for example, be diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzoin dimethyl ketal, or 4- (2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2- Oxo (4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4- Acetophenones such as phenylphenyl)butanone and 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone oligomer; benzoin, benzoin Benzoin such as methyl ether, benzoin ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl phthalate, 4-phenyl diphenyl ketone , 4-benzylidene-4'-methyl-diphenyl sulfide, 3,3',4,4'-tetrakis(t-butylperoxycarbonyl)diphenyl ketone, 2,4,6 -trimethyldiphenyl ketone, 4-benzylidene-N,N-dimethyl-N-[2-(1-o-oxy-2-propenyloxy)ethyl]benzene bromide Diphenylketones such as (Methanaminium), (4-benzylidenebenzyl)trimethylammonium chloride; 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-di Ethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-(3-dimethylamino-2-hydroxy)-3,4-dimethyl Thiophenone 2,4,6-trimethylbenzimidyl-diphenylphosphine oxide, bis(2,6-dimethoxybenzamide), such as -9-thioxanthone-9-one mesochloride a fluorenylphosphine oxide such as -2,4,4-trimethylpentylphosphine oxide or bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide; In addition, these photopolymerization initiators (D) may be used alone or in combination of two or more.

Further, as such an auxiliary agent, triethanolamine, triisopropanolamine, 4,4'-dimethylaminodiphenyl ketone (milaxone), 4,4'-diethylamino group may also be used in combination. Phenyl ketone, 2-dimethylaminoethyl benzoic acid, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid (n-butoxy)ethyl ester, 4-dimethylamino benzene Isoamyl formate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and the like.

Among these, benzoin dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoin isopropyl ether, 4-(2-hydroxyethoxy)-phenyl (2-hydroxy-2-) Propyl)ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one is preferred.

The content of the photopolymerization initiator (D) is 100 parts by weight based on the urethane (meth)acrylate compound (A) (in the case where the ethylenically unsaturated monomer (C) is contained) It is preferably 0.1 to 40 parts by weight, more preferably 1 to 20 parts by weight, particularly preferably 2 to 20 parts by weight.

When the content of the photopolymerization initiator (D) is too small, the curing tends to be poor. When the amount is too large, the stability of the solution such as precipitation may be lowered as a coating agent, or the problem of embrittlement or coloring may occur. tendency.

Thus, the urethane (meth)acrylate-based compound (A) and the particulate synthetic resin filler (B) of the present invention can be obtained, and it is preferable to further contain an ethylenically unsaturated monomer (C), which is photopolymerized. The active energy ray-curable resin composition of the starting agent (D) may further contain a coating agent (E), a surface conditioner, a polymerization inhibitor or the like as needed.

As the coating agent (E), if it is a solution which wets and disperses the fine particles to a solvent, etc. The particle may be imparted with a function of moisture permeability, and a known ordinary leveling agent may be used. For example, an anthrone modified resin, a fluorine modified resin, an alkyl modified resin or the like may be used.

The commercially available product of the coating agent (E) may, for example, be a Megafac series manufactured by DIC Corporation (MCF350-5, F472, F476, F445, F444, F443, F178, F470, F475, F479, F477, F482, F486, TF1025, F478, F178K, etc.; X22-3710, X22-162C, X22-3701E, X22160AS, X22170DX, X224015, X22176DX, X22-176F, X224272, KF8001, X22-2000, etc. manufactured by Shin-Etsu Chemical Co., Ltd.; The company's FM4421, FM0425, FMDA26, FS1265, etc.; BY16-750, BY16880, BY16848, SF8427, SF8421, SH3746, SH8400, SF3771, SH3749, SH3748, SH8410, etc. made by Toray Road Corning Co., Ltd.; Momentive. Performance. Materials. Japan's TSF series (TSF4460, TSF4440, TSF4445, TSF4450, TSF4446, TSF4453, TSF4452, TSF4730, TSF4770, etc.), FGF502, SILWET series (SILWETL77, SILWETL2780, SILWETL7608, SILWETL7001, SILWETL7002, SILWETL7087, SILWETL7200, SILWETL7210, SILWETL7220, SILWETL7230, SILWETL7500, SILWETL7510, SILWETL7600, SILWETL7602, SILWETL7604, SILWETL7604, SILWETL7605, SILWETL7607, SILWETL7622, SILWETL7644, SILWETL7650, SILWETL7657, SILWETL8500, SILWETL8600, SILWETL8610, SILWETL8620, SILWETL720, etc.; Fergent series made by NEOS (FTX218, 250, 245M) , 209F, 222F, 245F, 208G, 218G, 240G, 206D, 240D, etc.) or KB series; BYK 333, 300, etc. made by BYK Chemical Japan Co., Ltd.; KL600 manufactured by Kyoeisha Chemical Co., Ltd., etc.

The surface conditioning agent may, for example, be an alkyd resin or a cellulose acetate butyrate.

The alkyd resin or cellulose acetate butyrate has a function of imparting film forming property at the time of coating, or Solution viscosity adjustment.

Examples of the polymerization inhibitor include p-benzyl hydrazine, naphthoquinone, formazan, 2,5-diphenyl-p-benzyl bromide, hydroquinone, 2,5-di-t-butylhydroquinone, and methylhydroquinone. Hydroquinone monomethyl ether, mono-tert-butylhydroquinone, p-tert-butylcatechol, and the like.

Further, in the active energy ray-curable resin composition of the present invention, an oil, an antioxidant, a flame retardant, an antistatic agent, a stabilizer, a reinforcing agent, a grinding agent, an inorganic fine particle, a polymer compound (acrylic resin) may be blended. , polyester resin, epoxy resin, etc.).

Further, it is also preferred that the active energy ray-curable resin composition of the present invention is blended with an organic solvent (F) to adjust the viscosity. Examples of the organic solvent (F) include alcohols such as methanol, ethanol, propanol, n-butanol, and isobutanol, and ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone, and cyclohexanone. Classes, ethyl acesulfame, etc., races, aromatics such as toluene and xylene, glycol ethers such as propylene glycol monomethyl ether, acetates such as methyl acetate, ethyl acetate and butyl acetate, diacetone Alcohol, etc. These organic solvents may be used singly or in combination of two or more.

The active energy ray-curable resin composition of the present invention can be applied to a substrate by using the organic solvent (F), usually diluted to 3 to 60% by weight.

Further, when the active energy ray-curable resin composition of the present invention is produced, the urethane (meth)acrylate compound (A), the particulate synthetic resin filler (B), and the ethylenic acid to be used may be used. The method of mixing the unsaturated monomer (C), the photopolymerization initiator (D), and the coating agent (E) is not particularly limited and may be mixed by various methods.

The active energy ray-curable resin composition of the present invention can be effectively used as a curable resin composition for forming a coating film having a soft hand touch feeling for various substrates, and an active energy ray curable resin. After the composition is applied to the substrate (when the composition is diluted with an organic solvent, it is further dried), it is hardened by irradiation with an active energy ray. The coating method is not particularly limited, and examples thereof include spray coating, shower coating, dip coating, flow coating, and gravure Wet coating method such as coating, roll coating, spin coating, dispenser coating, ink jet coating, screen printing coating, and the like.

As the active energy ray, light rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, and infrared rays, electromagnetic waves such as X-rays and gamma rays, and other electron beams, proton beams, neutron beams, and the like can be used, and the curing speed and the irradiation device can be used. It is advantageous to be hardened by ultraviolet irradiation, such as easy availability and price. Further, in the case of performing electron beam irradiation, it can be cured without using a photopolymerization initiator (D).

As a method of hardening 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 lamp, an electrodeless discharge lamp, an LED, etc., which emit light in a wavelength region of 150 to 450 nm, are used. It can be irradiated at around 30~3,000mJ/cm ² .

After the ultraviolet ray is irradiated, heating may be performed in order to completely harden it.

The coating film thickness (film thickness after curing) is usually preferably from 1 to 50 μm, more preferably from 2 to 40 μm, still more preferably from 5 to 30 μm.

The base material to which the active energy ray-curable resin composition of the present invention is applied may, for example, be a polyolefin resin, a polyester resin, a polycarbonate polyol resin, or an acrylonitrile butadiene styrene copolymer. (ABS), polystyrene resin, polyamide resin, or other molded articles (film, sheet, cup, etc.), metal substrate (metal vapor deposited layer, metal plate (copper, stainless steel (SUS304, SUSBA, etc.) , aluminum, zinc, magnesium, etc.), glass, etc., their composite substrates.

The active energy ray-curable resin composition containing the urethane (meth)acrylate compound (A) and the particulate synthetic resin filler (B) of the present invention has a soft touch and soft touch. It has a moist hand touch and a hardened coating film having an excellent high-grade appearance in the appearance of the cured coating film. Further, the active energy ray-curable resin composition of the present invention is very useful as a coating agent (coating in the non-optical field), and workability (solution storage stability) or productivity (manufacturing speed) at the time of coating. It is also very useful for those who have excellent results.

The coating agent composition preferably contains the urethane (meth)acrylate compound (A) in an amount of 2 to 60% by weight, more preferably 3 to 40% by weight, based on the entire coating composition. More preferably 5 to 30% by weight. Further, the coating agent composition may or may not contain an organic solvent.

When the content of the urethane (meth) acrylate-based compound (A) is too small, it tends to be difficult to obtain a moist soft hand touch, and if it is too large, the abrasion resistance of the cured coating film tends to be extremely lowered.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the scope of the present invention is not limited to the following examples. In the examples, "parts" and "%" mean the basis of weight.

Prior to the examples and comparative examples, the following were produced as the urethane (meth)acrylate compound (A).

<Production Example 1: Aminoformate (meth)acrylate compound (A1-1)>

Into a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 13.2 g (0.06 mol) of isophorone diisocyanate and 82.1 g of a bifunctional polyester polyol (hydroxyl price: 54 mgKOH/g) were placed. 0.04 moles, 0.02 g of hydrogenated methyl ether as a polymerization inhibitor, and 0.02 g of dibutyltin dilaurate as a reaction catalyst, the reaction was allowed to proceed at 60 ° C for 3 hours, and 4.7 g of 2-hydroxyethyl acrylate (0.04) was placed. The reaction was carried out at 60 ° C for 3 hours, and when the residual isocyanate group became 0.3% or less, the reaction was terminated to obtain a bifunctional urethane acrylate (A1-1) (weight average molecular weight (Mw): 16,500).

<Production Example 2: Aminoformate (meth)acrylate compound (A1-2)>

Into a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 16.1 g (0.07 mol) of isophorone diisocyanate and 75.2 g of a bifunctional polyester polyol (hydroxyl price: 54 mgKOH/g) were placed. 0.04 moles, 0.02 g of hydrogenated methyl ether as a polymerization inhibitor, and 0.02 g of dibutyltin dilaurate as a reaction catalyst, the reaction was allowed to proceed at 60 ° C for 3 hours, and 8.6 g of 2-hydroxyethyl acrylate (0.07) was placed. The reaction was carried out at 60 ° C for 3 hours, and the reaction was terminated when the residual isocyanate group became 0.3% or less to obtain a bifunctional urethane acrylate (A1-2) (weight average molecular weight (Mw): 9,500).

<Production Example 3: Aminoformate (meth)acrylate compound (A1-3)>

In a 4-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 16.1 g (0.08 mol) of hydrogenated xylene diisocyanate and 73.7 g of a bifunctional polyester polyol (hydroxyl price: 63.9 mgKOH/g) were placed. (0.04 mol), 0.02 g of hydrogenated methyl ether as a polymerization inhibitor, and 0.02 g of dibutyltin dilaurate as a reaction catalyst, the reaction was allowed to proceed at 60 ° C for 3 hours, and 9.2 g of 2-hydroxyethyl acrylate was placed. 0.09 mol), the reaction was allowed to proceed at 60 ° C for 3 hours, and the reaction was terminated when the residual isocyanate group became 0.3% or less to obtain a bifunctional urethane acrylate (A1-3) (weight average molecular weight (Mw): 10,400) .

<Production Example 4: urethane (meth) acrylate compound (A1-4)>

In a 4-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 30.0 g (0.13 mol) of hydrogenated xylene diisocyanate and a bifunctional polycarbonate polyol (hydroxyl price 139.4 mgKOH/g) 54.2 were placed. g (0.07 mol), 0.02 g of hydrogenated methyl ether as a polymerization inhibitor, and 0.02 g of dibutyltin dilaurate as a reaction catalyst, the reaction was allowed to proceed at 60 ° C for 3 hours, and 2-hydroxyethyl acrylate was added in an amount of 15.9 g. (0.14 mol), the reaction was allowed to proceed at 60 ° C for 3 hours, and the reaction was terminated when the residual isocyanate group became 0.3% or less to obtain a bifunctional urethane acrylate (A1-4) (weight average molecular weight (Mw): 5,000) ).

<Production Example 5: urethane (meth) acrylate compound (A1-5)>

A four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, filled with an isocyanate compound (reactant of (a2) and (a3)) ("DURANATE E402" hexamethylene diisocyanate manufactured by Asahi Kasei Chemicals Co., Ltd.) Addition type (adduct type), 0.056 mol) 78 g, adding 2-hydroxyethyl acrylate 22 g (a1) (0.17 mol), and 0.02 g of hydrogenated methyl ether as a polymerization inhibitor, as a reaction catalyst 0.02 g of dibutyl tin laurate, and the reaction was allowed to stand for 3 hours after the internal temperature was 70 ° C, and the reaction was terminated when the residual isocyanate group became 0.3% or less to obtain a urethane (meth) acrylate. Compound (A1-5) (weight average molecular weight (Mw): 3,700).

<Production Example 6: Aminoformate (meth)acrylate compound (A2-1)>

A four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, filled with an isocyanate compound (a2) (isocyanate compound composed of a trimer of "CORONATE HX" hexamethylene diisocyanate manufactured by Nippon Polyurethane Industry Co., Ltd.) , 0.070 mol, 42.2 g, added polycaprolactone-modified hydroxy acrylate compound (a1) ("SC1010A" manufactured by MIWON Co., Ltd., 48.5 g (0.21 mol), and hydrogenated methyl ether as a polymerization inhibitor 0.2 g, 0.02 g of dibutyl tin laurate as a reaction catalyst, and after the internal temperature was 70 ° C, the reaction was allowed to proceed for 3 hours, and further added 9.3 g of SC1010A, and kept at 70 ° C for 1 hour to leave residual isocyanate groups. When the ratio was 0.3% or less, the reaction was terminated to obtain a urethane (meth)acrylate compound (A2-1) (weight average molecular weight (Mw): 3,500).

Further, in the urethane (meth) acrylate type compound (A2-1), as the ethylenically unsaturated monomer (C-1), a polycaprolactone-modified hydroxy group-containing acrylate compound is contained. "SC1010A" is 9.3%.

<Production Example 7: Carbamate (meth) acrylate compound (A2-2)>

a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas-filled inlet, and filled with an isocyanate compound (a2) (isocyanate compound composed of a trimer of "CORONATE HX" hexamethylene diisocyanate manufactured by Nippon Polyurethane Industry Co., Ltd., 60.4 g of 0.10 mol, adding 39.6 g of 2-hydroxypropyl acrylate (a1) (0.30 mol), 0.2 g of hydroquinone methyl ether as a polymerization inhibitor, and dibutyl tin dilaurate as a reaction catalyst After 0.02 g, the internal temperature was 70 ° C, the reaction was allowed to proceed for 3 hours, and the temperature was 70 ° C for 1 hour. When the residual isocyanate group became 0.3% or less, the reaction was terminated to obtain a urethane (meth) acrylate compound. (A2-2) (weight average molecular weight (Mw): 2,200).

<Production Example 8: Aminoformate (meth)acrylate compound (A2-3)>

The four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet was filled with an isocyanate compound (a2) (biuret modified type of "Desmodur N3200" hexamethylene diisocyanate manufactured by Bayer MaterialScience Co., Ltd. 34.2 g of 0.06 mol, and a polycaprolactone-modified hydroxy acrylate compound (a1) (65.8 g (0.19 mol) of "M100D" manufactured by MIWON Co., Ltd., and 0.2 g of hydrogenated methyl ether as a polymerization inhibitor, 0.02 g of dibutyl tin laurate as a reaction catalyst, the internal temperature was 70 ° C, and the reaction was allowed to proceed for 3 hours in the residual isocyanate. When the acid ester group became 0.3% or less, the reaction was terminated, and a urethane (meth)acrylate compound (A2-3) (weight average molecular weight (Mw): 3,600) was obtained.

The following is prepared as a particulate synthetic resin filler (B).

(B-1): Polyurethane microparticles (average particle diameter 6.2 μm: glass transition temperature - 52 ° C)

(B-2): Polyurethane microparticles (average particle diameter 16.7 μm: glass transition temperature - 34 ° C)

(B-3): Polyurethane fine particles (average particle diameter: 6.5 μm: glass transition temperature - 34 ° C)

(B-4): Polyurethane fine particles (average particle diameter 13.5 μm: glass transition temperature - 13 ° C)

(B-5): Polyethylene wax (particle size 5~10μm)

In addition, the following non-synthetic resin filler is prepared as a filler for a comparative example of the particulate synthetic resin filler (B).

(B'-1: for comparative use): fumed silica (particle size 50 nm)

The following was prepared as a photopolymerization initiator (D).

(D-1): 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF JAPAN, Irgacure 184)

Prepare the following as a leveling agent (E).

(E-1): Polyether modified polydimethyl siloxane (BYK-UV3510, manufactured by BYK Chemical Co., Ltd.)

[Example 1]

100 parts of the bifunctional urethane (meth) acrylate type compound (A1-1) obtained in the above Production Example 1, 65.9 parts of the fine synthetic resin filler (B-1), and a particulate synthetic resin filler ( B-5) 0.5 parts (solid content), 6.8 parts of photopolymerization initiator (D-1), and 2.7 parts of coating agent (E-1), blended with ethyl acetate to make the solid content 50% An active energy ray curable resin composition was obtained.

[Embodiment 2]

100 parts of a bifunctional urethane (meth) acrylate type compound (A1-2) obtained in the above Production Example 2, 67.0 parts of a fine synthetic resin filler (B-3), and a particulate synthetic resin filler (B-5) 2.6 parts (solid content), photopolymerization initiator (D-1) 6.9 parts, and coating agent (E-1) 2.7 parts, blended with ethyl acetate to make the solid content 50 %, an active energy ray curable resin composition was obtained.

[Example 3]

100 parts of the bifunctional urethane (meth) acrylate type compound (A1-3) obtained in the above Production Example 3, 65.9 parts of the fine synthetic resin filler (B-1), and a particulate synthetic resin filler ( B-5) 0.5 parts (solid content), 6.8 parts of photopolymerization initiator (D-1), and 2.7 parts of coating agent (E-1), blended with ethyl acetate to make the solid content 50% An active energy ray curable resin composition was obtained.

[Example 4]

100 parts of the bifunctional urethane (meth) acrylate type compound (A1-4) obtained in the above Production Example 4, 65.9 parts of the fine synthetic resin filler (B-1), and a particulate synthetic resin filler ( B-5) 0.5 parts (solid content), 6.8 parts of photopolymerization initiator (D-1), and 2.7 parts of coating agent (E-1), blended with ethyl acetate to make the solid content 50% An active energy ray curable resin composition was obtained.

[Example 5]

100 parts of the urethane (meth)acrylate compound (A1-5) obtained in the above Production Example 5, 67.2 parts of the fine synthetic resin filler (B-2), and a particulate synthetic resin filler (B- 5) 3.3 parts (amount of solid content), 6.9 parts of a photopolymerization initiator (D-1), and 2.2 parts of a leveling agent (E-1), which were blended with ethyl acetate so that the solid content became a concentration of 50%. Active energy ray curable resin composition.

[Embodiment 6]

100 parts of the urethane (meth) acrylate type compound (A1-5) obtained in the above Production Example 5, 67.2 parts of the fine synthetic resin filler (B-3), and a particulate synthetic resin filler (B- 5) 3.3 parts (amount of solid content), 6.9 parts of a photopolymerization initiator (D-1), and 2.2 parts of a leveling agent (E-1), which were blended with ethyl acetate so that the solid content became a concentration of 50%. Active energy ray curable resin composition Things.

[Embodiment 7]

100 parts of the urethane (meth) acrylate type compound (A2-1) obtained in the above Production Example 6, 67.2 parts of the fine synthetic resin filler (B-1), and a particulate synthetic resin filler (B- 5) 3.3 parts (amount of solid content), 6.9 parts of a photopolymerization initiator (D-1), and 2.2 parts of a leveling agent (E-1), which were blended with ethyl acetate so that the solid content became a concentration of 50%. Active energy ray curable resin composition.

[Embodiment 8]

100 parts of the urethane (meth)acrylate compound (A2-1) obtained in the above Production Example 6, 67.2 parts of the fine synthetic resin filler (B-2), and a particulate synthetic resin filler (B- 5) 3.3 parts (amount of solid content), 6.9 parts of a photopolymerization initiator (D-1), and 2.2 parts of a leveling agent (E-1), which were blended with ethyl acetate so that the solid content became a concentration of 50%. Active energy ray curable resin composition.

[Embodiment 9]

100 parts of the urethane (meth) acrylate type compound (A2-1) obtained in the above Production Example 6, 67.2 parts of the fine synthetic resin filler (B-1), and a photopolymerization initiator (D-1) 6.9 parts and 2.8 parts of a leveling agent (E-1) were blended with ethyl acetate so that the solid content became a concentration of 50%, and an active energy ray-curable resin composition was obtained.

[Embodiment 10]

100 parts of the urethane (meth)acrylate compound (A2-2) obtained in the above Production Example 7, 65.9 parts of the fine synthetic resin filler (B-1), and a particulate synthetic resin filler (B- 5) 0.5 parts (amount of solid content), 6.8 parts of a photopolymerization initiator (D-1), and 2.7 parts of a leveling agent (E-1), which were blended with ethyl acetate so that the solid content became a concentration of 50%. Active energy ray curable resin composition.

[Example 11]

100 parts of the urethane (meth) acrylate type compound (A2-3) obtained in the above Production Example 8, 65.9 parts of the fine synthetic resin filler (B-1), and a particulate synthetic resin filler (B- 5) 0.5 parts (amount of solid content), 6.8 parts of a photopolymerization initiator (D-1), and 2.7 parts of a leveling agent (E-1), which were blended with ethyl acetate so that the solid content became a concentration of 50%. Active energy ray curable resin composition.

[Comparative Example 1]

In Example 5, except for the synthetic resin filler (B-2), (B-5), and the coating agent (E-1) which are not blended with the fine particles, the photopolymerization initiator (D-1) is used. The active energy ray-curable resin composition was obtained in the same manner as in the Example except that the blending amount was changed to 4 parts.

[Comparative Example 2]

In Example 7, except for the synthetic resin fillers (B-1), (B-5), and the leveling agent (E-1) which are not blended with the fine particles, the photopolymerization initiator (D-1) is used. The active energy ray-curable resin composition was obtained in the same manner as in Example 7 except that the blending amount was changed to 4 parts.

[Comparative Example 3]

In Example 3, except that the particulate synthetic resin fillers (B-1) and (B-5) were changed to (B'-1) 6.2 parts, and the photopolymerization initiator (D-1) was blended. The active energy ray-curable resin composition was obtained in the same manner as in Example 3 except that the amount of the coating agent (E-1) was changed to 1.8 parts.

The active energy ray-curable resin composition obtained in the above Examples 1 to 11 and Comparative Examples 1 to 3 was applied to a polycarbonate substrate (manufactured by Nippon Testpanel Co., Ltd.) with an applicator to make the cured coating film 10 μm thick. After drying at 90 ° C for 3 minutes, a high-pressure mercury lamp 80 W, 1 lamp was used, and two pulses of ultraviolet irradiation (additional irradiation amount 800 mJ/cm ² ) were performed from a height of 18 cm at a conveyor speed of 3.4 m/min to obtain a hard coating. membrane.

Using the above-mentioned cured coating film, the soft hand feeling of the cured coating film, the substrate adhesion, and the surface hardness were evaluated as follows.

<soft hand (hand touch)>

The surface of the hardened coating film was touched by hand to evaluate the soft touch. The evaluation criteria are as follows. The evaluation results are shown in Table 1 below.

(evaluation benchmark)

◎: good soft touch (smooth and moist)

○: Still good soft touch (smooth)

×: Can not feel soft touch (rough, or not rough but no soft touch, or the surface of the coating is sticky)

<Substrate adhesion>

Using the above-mentioned cured coating film, a checkerboard tape method was carried out in accordance with JIS K 5400 (1990 edition), and the substrate adhesion was evaluated. The evaluation results are shown in Table 1 below.

(evaluation benchmark)

○: The film is still completely adhered to the substrate after the tape test (100/100)

×: The film was peeled off from the substrate after the tape test (less than 100/100)

<surface hardness>

A 500 g load was applied to the hardened coating film, and at the same time, the nail end portion of the human nail was used to move in the longitudinal direction of the nail ground portion, and a nail scratch test was performed to evaluate the practical physical properties of the surface of the coating film. The evaluation results are shown in Table 1 below.

(evaluation benchmark)

○: No damage caused by rubbing with a nail.

×: There is a negative injury by scratching with a nail.

* In the table, (-) indicates that it is not blended.

Further, A2-1* indicates that C-19.3% by weight is contained.

Moreover, in order to evaluate the abrasion resistance of the cured coating film, the cured coating films of the above-described Examples 5 and 7 and Comparative Example 1 were used, and the evaluation of the abrasion resistance of the cured coating film was carried out as follows.

<Abrasion resistance>

The active energy ray-curable resin composition obtained in the above-mentioned Examples and Comparative Examples was applied to an easy-to-peel PET (manufactured by Toyobo Co., Ltd.; trade name "COSMOSHINE A4300", film thickness: 125 μm) by an applicator to form a cured coating film. The film was made to have a thickness of 10 μm and dried at 90° C. for 3 minutes, and then subjected to two-time pulsed ultraviolet irradiation (accumulated irradiation amount: 800 mJ/cm ² ) at a conveyor speed of 3.4 m/min from a height of 18 cm using a high-pressure mercury lamp of 80 W and a lamp. A 100 mm rectangular coating film was obtained to form a film.

The coating film-forming film obtained was subjected to abrasion resistance evaluation using a Taber abrasion tester (manufactured by TESTER SANGYO Co., Ltd.; AB-101 TABERTYPE ABRASION TESTER) under the conditions of 60 rpm, 250 g load, 500 rotation, and wear wheel CS10F. The evaluation coating film was fixed to the sample set SUS plate with a double-sided tape. The evaluation results are shown in Table 2 below.

(evaluation benchmark)

The portion of the coating film defect (base film exposed) in the wear wheel (12.5 mm width) of the coating film after the evaluation was measured by a gauge and accumulated to have the largest value with respect to the width of the wear wheel (12.5 mm width). The comparison was performed by calculating the ratio (accumulated defect portion/wearing wheel mark (12.5 mm)).

○: The defect rate is less than 30%

△: The defect rate is 30% or more and less than 50%.

×: The defect rate is 50% or more

From the evaluation results of the above Tables 1 and 2, the activity of Examples 1 to 11 in which the urethane (meth) acrylate compound (A) was blended with the particulate synthetic resin filler (B) was obtained. Energy ray hard The cured resin composition can obtain a cured coating film having a soft hand property and excellent in abrasion resistance, adhesion, and hardness. On the other hand, the activity of the comparative example containing no particulate fine synthetic resin filler (B) The hardened coating film obtained by the energy ray curable resin composition is excellent in adhesion and hardness, but is inferior in soft hand feeling and abrasion resistance.

In addition, as the polyol compound (a3) which is one of the components for obtaining the urethane (meth)acrylate compound (A1), a polyol compound having a weight average molecular weight of less than 500 (a3) is mentioned. An example of the polyol compound (a3-2) having a weight average molecular weight of 500 to 20,000 is described below.

Prior to this example, the following was produced as the urethane (meth)acrylate compound (A1).

<Production Example 9: urethane (meth) acrylate type compound (A1-6)>

In a 4-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 42.9 g of ethyl acetate, 32.3 g of hydrogenated xylene diisocyanate (a2), and neopentyl glycol (a3-1) (weight average) Molecular weight (Mw) 104) 11.6 g, bifunctional polyester polyol (a3-2) (hydroxyl group 63 mgKOH/g, weight average molecular weight (Mw) 5,000) 49.6 g, hydrogenation methyl ether as a polymerization inhibitor 0.02 g 0.02 g of dibutyltin diacetate as a reaction catalyst was allowed to react at 60 ° C for 2 hours, and 6.50 g of 2-hydroxyethyl acrylate (a1) was placed, and the reaction was allowed to proceed at 60 ° C for 3 hours, and the residual isocyanate group became 0.3%. The reaction was terminated at the following point to obtain an ethyl acetate solution (A1-6) of a urethane (meth) acrylate type compound (weight average molecular weight (Mw); 14,000) (solid content concentration: 70%, viscosity (20 ° C) ) 11,000mPa.s).

<Production Example 10: urethane (meth) acrylate compound (A1-7)>

In a 4-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 42.9 g of ethyl acetate, 29.6 g (0.15 mol) of hydrogenated xylene diisocyanate (a2), and tricyclodecane dimethanol ( A3-1) (weight average molecular weight (Mw) 196) 19.9 g (0.10 mol), bifunctional polyester polyol (a3-2) (hydroxyl price 63.9 mgKOH/g, weight average molecular weight (Mw) 5,000) 44.5 g (0.025 mol), 0.02 g of hydrogenated methyl ether as a polymerization inhibitor, and dibutyltin dilaurate as a reaction catalyst 0.02 g, the reaction was allowed to proceed at 60 ° C for 2 hours, and 6.0 g (0.052 mol) of 2-hydroxyethyl acrylate (a1) was placed, and the reaction was allowed to proceed at 60 ° C for 3 hours, and the reaction was terminated when the residual isocyanate group became 0.3% or less. An ethyl acetate solution (A1-7) of a urethane (meth) acrylate type compound (weight average molecular weight (Mw); 14,000) (solid content concentration 70%, viscosity (20 ° C) 53,000 mPa.s) was obtained. ).

<Production Example 11: urethane (meth) acrylate compound (A1-8)>

In a 4-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 42.9 g of ethyl acetate, 32.9 g (0.17 mol) of hydrogenated xylene diisocyanate (a2), and 1,2-hexanediol were placed. (a3-1) (weight average molecular weight (Mw) 118) 13.0 g (0.11 mol), bifunctional polyester polyol (a3-2) (hydroxyl price 63.9 mgKOH/g, weight average molecular weight (Mw) 5,000) 48.4 g (0.028 mol), 0.02 g of hydrogenated methyl ether as a polymerization inhibitor, and 0.02 g of dibutyltin dilaurate as a reaction catalyst were reacted at 60 ° C for 2 hours, and 2-hydroxyethyl acrylate was placed ( A1) 6.5 g (0.056 mol), the reaction was allowed to proceed at 60 ° C for 3 hours, and the reaction was terminated when the residual isocyanate group became 0.3% or less to obtain a urethane (meth) acrylate compound (weight average molecular weight (Mw) 14,000) ethyl acetate solution (A1-8) (solid content concentration 70%, viscosity (20 ° C) 123,000 mPa.s).

Next, the following is prepared as a particulate synthetic resin filler (B).

(B-1): Polyurethane microparticles (average particle diameter 6.2 μm: glass transition temperature - 52 ° C)

(B-5): Polyethylene wax (particle size 5~10μm)

The following was prepared as a photopolymerization initiator (D).

(D-1): 1-hydroxy-cyclohexyl-phenyl-ketone ("Irgacure 184", manufactured by BASF JAPAN Co., Ltd.)

Prepare the following as a leveling agent (E).

(E-1): Polyether modified polydimethyl siloxane (BYK-UV3510, manufactured by BYK Chemical Co., Ltd.)

The following was prepared as an organic solvent (F).

(F-1): ethyl acetate

(F-2): isopropyl alcohol

[Embodiment 12]

27.0 parts of the urethane (meth)acrylate compound (A1-6) obtained in the above Production Example 9, 12.7 parts of the fine synthetic resin filler (B-1), and a particulate synthetic resin filler (B- 5) 4.9 parts, 1.3 parts of photopolymerization initiator (D-1), 0.5 part of coating agent (E-1), 35.9 parts of organic solvent (F-1), and 17.7 parts of organic solvent (F-2) On the other hand, the solid content concentration was 40%, and an active energy ray-curable resin composition was obtained.

[Example 13]

27.0 parts of the urethane (meth)acrylate compound (A1-7) obtained in the above Production Example 10, 12.7 parts of the fine synthetic resin filler (B-1), and a particulate synthetic resin filler (B- 5) 4.9 parts, 1.3 parts of photopolymerization initiator (D-1), 0.5 part of coating agent (E-1), 35.9 parts of organic solvent (F-1), and 17.7 parts of organic solvent (F-2) On the other hand, the solid content concentration was 40%, and an active energy ray-curable resin composition was obtained.

[Embodiment 14]

27.0 parts of the urethane (meth)acrylate compound (A1-8) obtained in the above Production Example 11, 12.7 parts of the particulate synthetic resin filler (B-1), and a particulate synthetic resin filler (B- 5) 4.9 parts, 1.3 parts of photopolymerization initiator (D-1), 0.5 part of coating agent (E-1), 35.9 parts of organic solvent (F-1), and 17.7 parts of organic solvent (F-2) On the other hand, the solid content concentration was 40%, and an active energy ray-curable resin composition was obtained.

The active energy ray-curable resin composition obtained in the above Examples 12 to 14 was applied to a polycarbonate substrate (manufactured by Nippon Testpanel Co., Ltd.) with an applicator to make the cured coating film 10 μm thick, and dried at 90 ° C for 3 minutes. Using a high-pressure mercury lamp 80 W and a lamp, two pulses of ultraviolet irradiation (additional irradiation amount: 800 mJ/cm ² ) were carried out from a height of 18 cm at a conveyor speed of 3.4 m/min to obtain a cured coating film.

Using the above-mentioned cured coating film, the soft hand feeling of the cured coating film, the substrate adhesion, the surface hardness, the alkali resistance, and the ethanol resistance were evaluated as follows.

<soft hand (hand touch)>

The evaluation of the soft hand (feel touch) was carried out in the same manner as the evaluation criteria described above, and the evaluation results are shown in Table 3 below.

<Substrate adhesion>

The evaluation of the substrate adhesion was carried out in the same manner as the above-described evaluation criteria, and the evaluation results are shown in Table 3 below.

<surface hardness>

Using the above-mentioned hardened coating film, the pencil hardness of the surface of the coating film was measured in accordance with JIS K 5600-5-4. The measurement results are shown together with the evaluation knots in Table 3 below.

(evaluation benchmark)

○: The pencil hardness is the hardness above HB.

×: pencil hardness is lower than HB hardness

<Alkaline resistance>

A 5% aqueous NaOH solution was prepared by dropping 3 drops (0.1 ml) in a dropper at a place on the hardened coating film, and after standing at room temperature for 5 hours, it was washed with running water, and the droplet marks were visually confirmed. The evaluation results are shown in Table 3 below.

(evaluation benchmark)

○: visual observation of no dissolved marks

×: The coating film abnormalities such as dissolution marks were visually observed.

<Ethanol resistance>

In one place on the hardened coating film, 3 drops (0.04 ml) were dropped by a dropper, and after standing at room temperature for 5 hours, it was washed with running water, and the droplet marks were visually confirmed. The evaluation results are shown in Table 3 below.

(evaluation benchmark)

○: visual observation of no dissolved marks

×: The coating film abnormalities such as dissolution marks were visually observed.

According to the above evaluation results, it was found that the active energy ray-curable resin of Examples 12 to 14 in which the urethane (meth)acrylate compound (A1) was blended with the particulate synthetic resin filler (B) was obtained. A hardened coating film which has a soft hand feeling and an excellent appearance in appearance, and which is excellent in adhesion, hardness, alkali resistance, and alcohol resistance is obtained.

Further, in the formation of such hardened coating films, it has a low energy source, a high production speed, and a solution stability as a coating agent, and has a significant advantage over conventional thermosetting coatings.

In the foregoing embodiments, the specific aspects of the present invention have been described, but the foregoing embodiments are merely illustrative and not limiting. A wide variety of variations that are apparent to those skilled in the art are within the scope of the invention.

[Industrial use]

When used as a coating agent, the active energy ray-curable resin composition of the present invention can obtain an active energy ray-curable resin composition excellent in workability at the time of coating or productivity at the time of curing, and has a hardening property. The coating layer obtained afterwards has an effect of moist soft hand touch, and is particularly useful as a coating agent in the non-optical field.

Claims (12)

An active energy ray-curable resin composition comprising a urethane (meth) acrylate-based compound (A) and a particulate synthetic resin filler (B). The active energy ray-curable resin composition according to the first aspect of the invention, wherein the urethane (meth) acrylate-based compound (A) has a weight average molecular weight of 1,000 to 50,000. The active energy ray curable resin composition according to claim 1 or 2, wherein the urethane (meth) acrylate compound (A) is a hydroxyl group-containing (meth) acrylate system The compound (a1), the polyvalent isocyanate compound (a2), and the polyol compound (a3) are reacted. The active energy ray-curable resin composition according to claim 3, wherein the polyol-based compound (a3) contains a polyol compound (a3-1) having a weight average molecular weight of less than 500 and a weight average molecular weight of 500 to 20,000. The polyol compound (a3-2). The active energy ray-curable resin composition according to claim 1 or 2, wherein the particulate synthetic resin filler (B) contains at least one of a polyurethane filler and a polyethylene filler. The active energy ray-curable resin composition according to claim 1 or 2, wherein the fine particle-shaped synthetic resin filler (B) has an average particle diameter of 1 to 30 μm. The active energy ray-curable resin composition according to claim 1 or 2, wherein the particulate synthetic resin filler (B) has a glass transition temperature of -140 to 40 °C. The active energy ray-curable resin composition according to claim 1 or 2, wherein the content of the particulate synthetic resin filler (B) is relative to the urethane (meth) acrylate compound (A) 100 parts by weight is 25 to 400 parts by weight. A coating agent composition comprising the active energy ray-curable resin composition according to any one of claims 1 to 8. The coating agent composition of claim 9, which comprises an ethylenically unsaturated monomer (C), a photopolymerization initiator (D), and an organic solvent. The coating composition of claim 9 or 10, wherein the content of the urethane (meth) acrylate-based compound (A) is 2 to 60% by weight. A laminate comprising a substrate and a coating layer comprising the coating composition of any one of claims 9 to 11.