JP6452320B2 - Urethane (meth) acrylate-based compound, active energy ray-curable resin composition, and coating agent composition - Google Patents

Description

  The present invention relates to a urethane (meth) acrylate-based compound, and more specifically, after being applied on a substrate and dried, for example, it is not sticky in an uncured state even when a load is applied at 40 ° C. higher than normal temperature. That is, the present invention relates to a urethane (meth) acrylate compound capable of forming a tack-free coating surface, an active energy ray-curable resin composition containing the same, and a coating agent composition using the same. .

Conventionally, an active energy ray-curable resin composition has been widely used as a coating agent, an adhesive agent, an anchor coating agent, or the like on various substrates in order to complete curing by irradiation of an active energy ray for a very short time. Yes.
In certain fields, it is desirable that coatings formed with this composition are non-sticky, i.e. tack free, even in an uncured state that has only been dried. For example, when multicolor printing is performed using an active energy ray-curable ink, if the printed surface is not sticky in a dry state, the printed surface is dried and printed one after another, and finally activated. There exists an advantage that it can harden | cure with an energy ray collectively.

However, many of the active energy ray curable resin compositions are low molecular weight acrylic ester compounds collectively referred to as oligomers, such as urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, (meth). Acrylic acrylate and liquid active energy ray-curable monomer collectively called reactive dilution monomer are mixed, so the coating film until cured is in a liquid state where the coating surface is sticky, It is difficult to apply to this field.
In order to solve these problems, several active energy ray-curable resin compositions that are not sticky even in an uncured state that has just been dried have been proposed.

  For example, Patent Document 1 discloses a reaction product of an isocyanate compound having a melting point of 40 ° C. or more and a (meth) acrylic group that has a (meth) acryloyl group and can react with the isocyanate group, and is softened. An active energy ray-curable component containing a point of 40 ° C. or higher has been proposed, and it is described that there is no tack even when the coated film after drying is touched with a finger.

  Patent Document 2 discloses an isocyanate comprising a hydroxyl group-containing polyfunctional acrylate compound (d) having one or more polymerizable unsaturated bonds and an isocyanate-containing compound (b) having an isocyanate group and an isocyanurate ring structure in one molecule. Unsaturation containing 6 or more polymerizable unsaturated groups in one molecule obtained by reaction of a group-containing urethane compound (c) with a hydroxyl group-containing compound (a) having a hydroxyl group and an isocyanurate ring structure in one molecule The photocurable resin composition which has a urethane compound (A) and a photoinitiator (B) as an essential component is proposed, and even if it touches the coating film after drying with a finger like patent document 1, it is tacky. It is stated that there is no.

JP 2001-329031 A JP-A-2005-281212

  However, in the techniques disclosed in Patent Documents 1 and 2, it is recognized that there is no tack in the touch evaluation under normal conditions with respect to the coating film applied and dried on the substrate, but in recent years, However, even under a high temperature environment, for example, at 40 ° C. or the like, the coating film surface is required to be non-sticky even in a state where a load is applied to the coating film. In the state where the winding pressure is applied, tack-free is not satisfied, and further improvement is required.

  Therefore, the present invention is not tacky in a non-cured state even when a load is applied in a 40 ° C. environment higher than room temperature, for example, after being coated on a substrate and dried under such a background, that is, a tack-free coating film. It is an object of the present invention to provide a urethane (meth) acrylate compound capable of forming a surface, an active energy ray-curable resin composition containing the same, and a coating agent composition.

  However, as a result of intensive studies in view of such circumstances, the present inventors have reacted a polyvalent isocyanate compound containing an alicyclic structure, a hydroxyl group-containing (meth) acrylate compound, an aliphatic diol having 10 or less carbon atoms. In the urethane (meth) acrylate compound, the hydroxyl group-containing (meth) acrylate compound (a2) has one hydroxyl group and the urethane (meth) acrylate compound has a relatively large weight average molecular weight. The present inventors have found that a tack-free coating surface without stickiness can be formed even when a load is applied in an environment of 40 ° C., and the present invention has been completed.

That is, the gist of the present invention is a urethane (meth) acrylate compound obtained by reacting a polyvalent isocyanate compound (a1), a hydroxyl group-containing (meth) acrylate compound (a2), and a diol compound (a3). The polyisocyanate compound (a1) is a polyisocyanate compound containing an alicyclic structure, and the hydroxyl group-containing (meth) acrylate compound (a2) is a hydroxyl group containing one ethylenically unsaturated group (meta ) Urethane compound characterized in that it is an acrylate compound, the diol compound (a3) is an aliphatic diol having a carbon number of 10 or less and a molecular weight of 200 or less , and a weight average molecular weight of 4,300 to 7,900. It relates to a (meth) acrylate compound.

  The present invention also provides an active energy ray-curable resin composition containing the urethane (meth) acrylate compound, and a coating agent composition containing the active energy ray-curable resin composition. Is.

  The urethane (meth) acrylate compound of the present invention and the active energy ray-curable resin composition are not sticky in an uncured state even when a load is applied in a high temperature environment after being applied on a substrate and dried, and tacky. It has an effect that a free coating film surface can be formed, and is particularly useful as a coating agent composition.

The present invention is described in detail below.
In the present invention, (meth) acryl means acryl or methacryl, (meth) acryloyl means acryloyl or methacryloyl, and (meth) acrylate means acrylate or methacrylate.

  The urethane (meth) acrylate compound of the present invention is a urethane (meth) acrylate compound obtained by reacting a polyvalent isocyanate compound (a1), a hydroxyl group-containing (meth) acrylate compound (a2), and a diol compound (a3). A compound.

The polyvalent isocyanate compound (a1) used in the present invention needs to be an alicyclic structure-containing polyvalent isocyanate compound, such as hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, Examples include alicyclic structure-containing polyisocyanates such as norbornene diisocyanate; or trimer compounds or multimeric compounds of these alicyclic structure-containing polyisocyanates. These can be used alone or in combination of two or more.
Among these, isophorone diisocyanate is preferable because it has high reactivity and excellent versatility.

The hydroxyl group-containing (meth) acrylate compound (a2) used in the present invention must be a hydroxyl group-containing (meth) acrylate compound containing one hydroxyl group. For example, 2-hydroxyethyl (meth) acrylate , 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxyalkyl (meth) acrylate such as 6-hydroxyhexyl (meth) acrylate, 2-hydroxyethylacryloyl Phosphate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, caprolactone-modified 2-hydroxyethyl (meth) acrylate, dipropylene glycol (meth) acrylate, fatty acid-modified glycidyl (meth) a Relate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxy propyl (meth) acrylate. These can be used alone or in combination of two or more.
Among these, hydroxyalkyl (meth) acrylate is preferable in that the coating film before curing can be tack-free, particularly preferably 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2 -Hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and more preferably 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate in terms of excellent reactivity and versatility.

  The diol compound (a3) used in the present invention is required to be an aliphatic diol having 10 or less carbon atoms, and the carbon number is preferably 8 or less, more preferably 5 or less. When the number of carbon atoms is too large, the urethane (meth) acrylate compound is crystallized and tends to become cloudy when an active energy ray-curable resin composition solution is obtained.

Examples of the aliphatic diol having 10 or less carbon atoms include:
Ethylene glycol, 1,3-propanediol, 1,4-tetramethylenediol, 1,5-pentamethylenediol, 1,6-hexamethylenediol, 1,9-nonanediol, dimethylolpropane, neopentyl glycol, 2 2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 3-methyl-1,5-pentamethylene An aliphatic diol consisting only of a primary alcohol such as diol, 2,4-diethyl-1,5-pentamethylenediol, 2-methyl-1,8-octanediol;
Aliphatic alcohols such as aliphatic diols composed of primary alcohols and secondary alcohols such as propylene glycol, 1,2-hexanediol, 1,3-tetramethylenediol, and 2-methyl-1,3-trimethylenediol; Can be mentioned. These can be used alone or in combination of two or more.
Among these, ethylene glycol, propylene glycol, 1,3-propanediol, dimethylolpropane, neopentyl are excellent in terms of stability when used as an active energy ray-curable resin composition solution and in terms of excellent versatility. Glycol, 1,2-hexanediol, 2,2-diethyl-1,3-propanediol, 1,4-tetramethylenediol, 1,3-tetramethylenediol, 2-methyl-1,3-trimethylenediol preferable.

The diol compound (a3) does not have a repeating structure of an oxyalkylene structure.
The Tg of the urethane (meth) acrylate compound can be increased, which is preferable in that the coating film tack-free property before curing is sufficiently exhibited.

The molecular weight of the diol compound (a3) is 200 or less, the good Mashiku 50-175, particularly preferably 60-150.
If the molecular weight is too large, the solution stability when the active energy ray-curable resin composition solution is obtained tends to be lowered, and crystallization tends to occur.

Thus, the urethane (meth) acrylate compound of the present invention is obtained by reacting the polyvalent isocyanate compound (a1), the hydroxyl group-containing (meth) acrylate compound (a2), and the diol compound (a3). but in the present invention, the weight average molecular weight of the urethane (meth) acrylate compound, it is necessary that 4,300～7,900.
When the weight average molecular weight is too low, the composition ratio of the hydroxyl group-containing (meth) acrylate compound in the reaction raw material of the urethane (meth) acrylate compound is relatively large, and the tack-free property of the coating film before curing is likely to be lowered. It is not preferable, and even if it is too high, the viscosity of the urethane (meth) acrylate compound becomes too large, and the handleability is lowered, which is not preferable.

In addition, said weight average molecular weight is a weight average molecular weight by standard polystyrene molecular weight conversion, a column is put into a high performance liquid chromatography (Nippon Waters Co., Ltd., "Waters 2695 (main body)" and "Waters 2414 (detector)"). (Shodex GPC KF-806L (exclusion limit molecular weight: 2 × 10 ⁷ , separation range: 100 to 2 × 10 ⁷ , theoretical plate number: 10,000 plates / piece, filler material: styrene-divinylbenzene copolymer, filler) It is measured by using three series of particle diameters: 10 μm)).

  In the present invention, the number of ethylenically unsaturated groups in the urethane (meth) acrylate compound (A) is preferably 1 to 6, particularly preferably 1 to 4, and more preferably 2. . When the number of such ethylenically unsaturated groups is too large, the coating film after drying tends to be sticky.

    The production method of the urethane (meth) acrylate compound of the present invention (hereinafter sometimes referred to as the urethane (meth) acrylate compound (A)) is usually the above polyisocyanate compound (a1) and hydroxyl group-containing. The (meth) acrylate-based compound (a2) and the diol-based compound (a3) may be charged or reacted together in a reactor, and the diol-based compound (a3) and the polyvalent isocyanate-based compound (a1) are reacted. It is useful to react the hydroxyl group-containing (meth) acrylate compound (a2) with a reaction product obtained by reacting in advance in terms of reaction stability and reduction of by-products.

  A known reaction means can be used for the reaction of the diol compound (a3) and the polyvalent isocyanate compound (a1). At that time, for example, the molar ratio of the isocyanate group in the polyvalent isocyanate compound (a1) to the hydroxyl group in the diol compound (a3) is usually 2n: (2n-2) to 2n: 0.1 × (2n− 2) (n is an integer greater than or equal to 2) By obtaining the terminal isocyanate group-containing compound in which the isocyanate group remains, an addition reaction with the hydroxyl group-containing (meth) acrylate compound (a2) is possible. To do.

  The addition reaction of the reaction product obtained by reacting the diol compound (a3) and the polyvalent isocyanate compound (a1) in advance with the hydroxyl group-containing (meth) acrylate compound (a2) is also a known reaction. Means can be used.

The reaction molar ratio between the reaction product and the hydroxyl group-containing (meth) acrylate compound (a2) is, for example, that the polyisocyanate compound (a1) has two isocyanate groups and the hydroxyl group-containing (meth) acrylate compound (a2). ) Has one hydroxyl group, the reaction product: hydroxyl group-containing (meth) acrylate compound (a2) is about 1: 2 to 1: 5, and the isocyanate group of the polyvalent isocyanate compound (a1) is When the number of hydroxyl groups of the hydroxyl group-containing (meth) acrylate compound (a2) is three, the reaction product: hydroxyl group-containing (meth) acrylate compound (a2) is about 1: 3 to 1:10. is there.
In the addition reaction between the reaction product and the hydroxyl group-containing (meth) acrylate compound (a2), the reaction is terminated when the residual isocyanate group content in the reaction system is 0.5% by weight or less. A (meth) acrylate compound (A) is obtained.

  In the reaction between the diol compound (a3) and the polyvalent isocyanate compound (a1), and further the reaction product and the hydroxyl group-containing (meth) acrylate compound (a2), a catalyst is used for the purpose of promoting the reaction. As such a catalyst, for example, dibutyltin dilaurate, dibutyltin diacetate, trimethyltin hydroxide, tetra-n-butyltin, bisacetylacetonate zinc, zirconium tris (acetylacetonate) ethylacetoacetate , Organometallic compounds such as zirconium tetraacetylacetonate, tin octenoate, zinc hexanoate, zinc octenoate, zinc stearate, zirconium 2-ethylhexanoate, cobalt naphthenate, stannous chloride, stannic chloride, acetic acid Metal salts such as potassium, triethyla , Triethylenediamine, benzyldiethylamine, 1,4-diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5,4,0] undecene, N, N, N ′, N′-tetramethyl-1 , 3-butanediamine, N-methylmorpholine, amine catalysts such as N-ethylmorpholine, bismuth nitrate, bismuth bromide, bismuth iodide, bismuth sulfide, etc., and organic bismuth compounds such as dibutyl bismuth dilaurate, dioctyl bismuth dilaurate Bismuth 2-ethylhexanoate, bismuth naphthenate, bismuth isodecanoate, bismuth neodecanoate, bismuth laurate, bismuth maleate, bismuth stearate, bismuth oleate, bismuth linoleate, Bismuth acetate salt, bismuth bisneo neodeca Bismuth-based catalysts such as organic acid bismuth salts such as bismuthate, bismuth disalicylate, and digallic acid bismuth, among others, dibutyltin dilaurate and 1,8-diazabicyclo [5,4,0] undecene are preferred. is there. These may be used alone or in combination of two or more.

  In the reaction between the diol compound (a3) and the polyvalent isocyanate compound (a1), and further in the reaction between the reaction product and the hydroxyl group-containing (meth) acrylate compound (a2), it reacts with an isocyanate group. Organic solvents having no functional group, for example, esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and organic solvents such as aromatics such as toluene and xylene can be used.

  Moreover, reaction temperature is 30-90 degreeC normally, Preferably it is 40-80 degreeC, and reaction time is 2 to 10 hours normally, Preferably it is 3 to 8 hours.

  Thus, the urethane (meth) acrylate compound of the present invention is obtained.

  Such a urethane (meth) acrylate compound is preferably used as an active energy ray-curable resin composition, and if necessary, ethylene other than the photopolymerization initiator (B) and the urethane (meth) acrylate compound (A). An unsaturated monomer (C), a leveling agent, a surface conditioner, a polymerization inhibitor and the like can be blended.

  Examples of the photopolymerization initiator (B) include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) -phenyl- ( 2-hydroxy-2-propyl) ketone, 1-hydroxy-cyclohexyl-phenyl-ketone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 2-hydroxy-2-methyl-1- Acetophenones such as [4- (1-methylvinyl) phenyl] propanone oligomer; benzoin, benzoin Benzoins such as ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3 ', 4 , 4'-tetra (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl Benzophenones such as benzenemethananium bromide and (4-benzoylbenzyl) trimethylammonium chloride; 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dioctane Thioxanthones such as rothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy) -3,4-dimethyl-9H-thioxanthone-9-one mesochloride; 2,4,6 -Trimethylbenzoyl-diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, etc. Acylphosphon oxides; and the like. In addition, as for these photoinitiators (B), only 1 type may be used independently and 2 or more types may be used together.

  These auxiliary agents include triethanolamine, triisopropanolamine, 4,4′-dimethylaminobenzophenone (Michler ketone), 4,4′-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, 4-dimethylaminobenzoic acid. Ethyl, 4-dimethylaminobenzoic acid (n-butoxy) ethyl, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone Etc. can be used in combination.

  Among these, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoin isopropyl ether, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 2-hydroxy-2-methyl-1- It is preferable to use phenylpropan-1-one.

  As content of a photoinitiator (B), it is 0 with respect to 100 weight part of urethane (meth) acrylate type compounds (A) (when the below-mentioned ethylenically unsaturated monomer (C) is included). The amount is preferably 1 to 20 parts by weight, particularly preferably 1 to 15 parts by weight, and particularly preferably 2 to 10 parts by weight. If the content is too small, there is a tendency to cause poor curing, and if it is too large, the solution stability tends to decrease, such as precipitation when used as a coating agent, and embrittlement and coloring problems tend to occur. .

  The ethylenically unsaturated monomer (C) may be any ethylenically unsaturated monomer (excluding the urethane (meth) acrylate compound (A)) having one or more ethylenically unsaturated groups in one molecule. , For example, a monofunctional monomer, a bifunctional monomer, a trifunctional or higher monomer.

  The monofunctional monomer may be any monomer containing one ethylenically unsaturated group, such as styrene, vinyltoluene, chlorostyrene, α-methylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate, acrylonitrile. , Vinyl acetate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, glycidyl (meth) acrylate, lauryl (meth) acrylate , Cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) Acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, n-stearyl (meth) acrylate, benzyl (meth) acrylate, phenol ethylene oxide modified Phthalic acid derivatives such as (meth) acrylate, nonylphenol propylene oxide modified (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate Fester (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, carbitol (meth) acrylate, benzyl (meth) acrylate, caprolactone modified 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, allyl (meth) acrylate , Acryloylmorpholine, 2-hydroxyethylacrylamide, N-methylol (meth) acrylamide, N-vinylpyrrolidone, 2-vinylpyridine, 2- (meth) acryloyloxyethyl acid phosphate monoester, and the like.

  In addition to the monofunctional monomer, there may be mentioned a Michael adduct of acrylic acid or 2-acryloyloxyethyldicarboxylic acid monoester. Examples of the acrylic acid Michael adduct include acrylic acid dimer, methacrylic acid dimer, and acrylic acid trimer. Methacrylic acid trimer, acrylic acid tetramer, methacrylic acid tetramer and the like. Examples of 2-acryloyloxyethyl dicarboxylic acid monoester which is a carboxylic acid having a specific substituent include 2-acryloyloxyethyl succinic acid monoester, 2-methacryloyloxyethyl succinic acid monoester, and 2-acryloyloxyethyl. Examples include phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2-acryloyloxyethyl hexahydrophthalic acid monoester, and 2-methacryloyloxyethyl hexahydrophthalic acid monoester. Furthermore, oligoester acrylate is also mentioned.

  The bifunctional monomer may be any monomer containing two ethylenically unsaturated groups. For example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol Di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, 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 ethylene oxide-modified di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di ( (Meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, hydroxypivalic acid modified neopentyl glycol di (meth) acrylate, isocyanuric acid ethylene oxide modified diacrylate, 2- (meta ) Acryloyloxyethyl acid phosphate diester and the like.

  The tri- or higher functional monomer may be any monomer containing three or more ethylenically unsaturated groups. For example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (meth) acryloyloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly (meth) acrylate, isocyanuric acid ethylene oxide modified triacrylate, ethylene Oxide-modified dipentaerythritol penta (meth) acrylate, ethylene oxide-modified dipentaerythritol hexa (meth) acrylate, ethylene Side modified pentaerythritol tri (meth) acrylate, ethylene oxide modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, caprolactone modified pentaerythritol tri (meth) ) Acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, succinic acid-modified pentaerythritol tri (meth) acrylate, and the like.

  These ethylenically unsaturated monomers (C) may be used alone or in combination of two or more. In addition, the ethylenically unsaturated monomer (C) may be added separately to the urethane (meth) acrylate compound (A), or as a raw material for producing the urethane (meth) acrylate compound (A). A part thereof may be left in the system.

  In the present invention, the content of the ethylenically unsaturated monomer (C) is preferably 100 parts by weight or less, particularly 50 parts by weight with respect to 100 parts by weight of the urethane (meth) acrylate compound (A). Hereinafter, it is further preferably 20 parts by weight or less. When there is too much content of an ethylenically unsaturated monomer (C), there exists a tendency for stickiness to arise on the coating-film surface before hardening by active energy ray irradiation.

  As the leveling agent, a known general leveling agent can be used as long as it has a function of reducing the surface tension and smoothing the coating film surface. For example, a silicone-modified resin, a fluorine-modified resin, an alkyl-modified resin can be used. Resin or the like can be used.

Examples of the surface conditioner include alkyd resins and cellulose acetate butyrate.
Such alkyd resin and cellulose acetate butyrate have an effect of imparting a film-forming property at the time of coating and a solution viscosity adjusting effect.

  Examples of the polymerization inhibitor include p-benzoquinone, naphthoquinone, tolquinone, 2,5-diphenyl-p-benzoquinone, hydroquinone, 2,5-di-t-butylhydroquinone, methylhydroquinone, hydroquinone monomethyl ether, mono-t. -Butyl hydroquinone, pt-butyl catechol, etc. can be mentioned.

  In addition, the active energy ray-curable resin composition of the present invention may contain oil, antioxidant, flame retardant, antistatic agent, stabilizer, reinforcing agent, abrasive, inorganic fine particles, polymer compound, and the like. Is possible.

  Examples of the polymer compound include an acrylic resin, a polyester resin, an epoxy resin, and a polystyrene resin. Among these, an acrylic resin is preferable because of its good compatibility with a urethane (meth) acrylate compound. A resin is preferred.

  Examples of such acrylic resins include (1) homopolymers of (meth) acrylic acid ester monomers, (2) (meth) acrylic acid ester monomers, functional group-containing monomers as necessary, and other copolymerizable properties. Examples thereof include a copolymer containing a monomer as a copolymerization component. Among them, a homopolymer of a (meth) acrylic acid ester monomer is preferable from the viewpoint of compatibility with the urethane (meth) acrylate compound (A). .

  The homopolymer of the (meth) acrylic acid ester monomer is preferably, for example, a homopolymer of alkyl (meth) acrylate, particularly preferably polymethyl (meth) acrylate, and more preferably polymethyl methacrylate. Preferably there is.

  Moreover, as a copolymer containing a (meth) acrylic acid ester monomer, a functional group-containing monomer and other copolymerizable monomer as a copolymerization component as necessary, the content ratio of the copolymerization component is (meta ) Acrylic acid ester monomer is 10 to 100% by weight, especially 20 to 95% by weight, functional group-containing monomer is 0 to 90% by weight, especially 5 to 80% by weight, and other copolymerizable monomers are 0 to 50% by weight. %, Particularly 0 to 40% by weight, is preferred.

  Examples of the functional group-containing monomer include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an amino group-containing monomer, an acetoacetyl group-containing monomer, an isocyanate group-containing monomer, and a glycidyl group-containing monomer.

  The acrylic resin has a weight average molecular weight of usually 5,000 to 3,000,000, preferably 10,000 to 1,000,000, and more preferably 20,000 to 500,000. If the weight average molecular weight is too small, the strength of the coating film tends to decrease or the coating surface before curing by irradiation with active energy rays tends to be sticky. If the weight average molecular weight is too large, the viscosity becomes high and handling becomes difficult. There exists a tendency for compatibility with a (meth) acrylate type compound (A) to fall.

  The active energy ray-curable resin composition of the present invention is also preferably used by blending an organic solvent and adjusting the viscosity. Examples of the organic solvent include alcohols such as methanol, ethanol, propanol, n-butanol and i-butanol, ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone and cyclohexanone, cellosolves such as ethyl cellosolve, toluene and xylene. And the like, glycol ethers such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate, acetates such as methyl acetate, ethyl acetate and butyl acetate, and diacetone alcohol. These organic solvents may be used alone or in combination of two or more.

  The active energy ray-curable resin composition of the present invention can be diluted to usually 3 to 80% by weight, preferably 30 to 60% by weight using the organic solvent, and can be applied to a substrate.

  In producing the active energy ray-curable resin composition, the urethane (meth) acrylate compound (A), the photopolymerization initiator (B) used as necessary, the ethylenically unsaturated monomer (C), The mixing method is not particularly limited, and can be mixed by various methods. For example, the components can be selected as appropriate, for example, the components can be mixed at once, or the optional components can be mixed first and then the remaining components can be mixed.

  The active energy ray-curable resin composition of the present invention is not sticky in an uncured state even when a load is applied in an environment of 40 ° C., which is higher than normal temperature, for example, after being coated on various substrates and dried. It is effectively used as a curable resin composition for forming a coating film for forming a coating film surface, and after coating an active energy ray-curable resin composition on a substrate (diluted with an organic solvent) When the composition is applied, after further drying), the composition is cured by irradiation with active energy rays.

  The coating method is not particularly limited, and examples thereof include wet coating methods such as spray, shower, dipping, roll, spin, screen printing, and ink jet printing.

  As such active energy rays, rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, electromagnetic waves such as X rays and γ rays, electron beams, proton rays, neutron rays, etc. can be used. Curing by ultraviolet irradiation is advantageous from the viewpoint of easy availability and price. In addition, when performing electron beam irradiation, it can harden | cure even without using a photoinitiator (B).

As a method of curing by ultraviolet irradiation, using a high pressure mercury lamp that emits light in a wavelength range of 150 to 450 nm, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless discharge lamp, an LED, etc. What is necessary is just to irradiate about 30-3,000 mJ / cm < ² >.
After the ultraviolet irradiation, heating can be performed as necessary to complete the curing.

  Although it does not specifically limit as a film thickness of a cured coating film, Usually, it is preferable that it is 1-50 micrometers, It is especially preferable that it is 2-40 micrometers, Furthermore, it is 5-30 micrometers.

  Examples of the base material to which the active energy ray-curable resin composition of the present invention is applied include polyolefin resins, polyester resins, polycarbonate resins, acrylonitrile butadiene styrene copolymers (ABS), polystyrene resins, and polyamides. Resins, etc. and their molded products (films, sheets, cups, etc.), metal substrates (metal deposition layers, metal plates (copper, stainless steel (SUS304, SUSBA, etc.), aluminum, zinc, magnesium, etc.)), glass, etc. , And those composite substrates.

  The urethane (meth) acrylate compound (A) of the present invention is applied to a substrate as an active energy ray-curable resin composition and dried, and then, for example, the load is not applied even under an environment of 40 ° C. higher than normal temperature. It is possible to form a tack-free coating surface in a cured state, that is, a cured coating film cured by active energy ray irradiation has excellent surface hardness, and is very useful as a coating agent composition. Useful.

  The coating agent composition preferably contains 2 to 60% by weight of the urethane (meth) acrylate compound (A), particularly preferably 3 to 50% by weight, and more preferably 5 to 40%. % By weight. If the content of the urethane (meth) acrylate compound (A) is too small, the film forming property tends to be poor, and if it is too large, the viscosity of the coating composition tends to increase and the coating property tends to decrease. .

  The active energy ray-curable resin composition of the present invention is not sticky in an uncured state even when a load is applied under a high temperature environment after being applied on a substrate and dried, and forms a tack-free coating surface. In particular, it is very useful as a coating composition.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to a following example, unless the summary is exceeded. In the examples, “parts” and “%” mean weight standards.

  The urethane (meth) acrylate compound (A) was prepared as follows.

<Production of urethane (meth) acrylate compound (A-1)>
In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser, and nitrogen gas inlet, 40 g of ethyl acetate, 38.3 g (0.17 mol) of isophorone diisocyanate (a1), neopentyl glycol (a3: carbon number 5) 14.9 g (0.14 mol), 0.02 g of hydroquinone methyl ether as a polymerization inhibitor, and 0.02 g of dibutyltin dilaurate as a reaction catalyst were allowed to react at 60 ° C. for 2 hours to give 2-hydroxyethyl acrylate (a2) 6 .8 g (0.058 mol) was charged and reacted at 60 ° C. for 3 hours. The reaction was terminated when the residual isocyanate group reached 0.3%, and the urethane (meth) acrylate compound (A-1) ( An ethyl acetate solution (viscosity (20 ° C.) 1,100 mPa · s) having a weight average molecular weight (Mw) of 4,300) was obtained.

<Production of urethane (meth) acrylate compound (A-2)>
In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser and nitrogen gas inlet, 50 g of ethyl acetate, 32.7 g (0.15 mol) of isophorone diisocyanate (a1), neopentyl glycol (a3: carbon number 5) ) 13.8 g (0.13 mol), 0.02 g of hydroquinone methyl ether as a polymerization inhibitor and 0.02 g of dibutyltin dilaurate as a reaction catalyst were added and reacted at 60 ° C. for 2 hours to give 2-hydroxyethyl acrylate (a2) 3 0.5 g (0.030 mol) was added and reacted at 60 ° C. for 3 hours. The reaction was terminated when the residual isocyanate group reached 0.3%, and the urethane (meth) acrylate compound (A-2) ( An ethyl acetate solution (viscosity (20 ° C.) 700 mPa · s) having a weight average molecular weight (Mw) of 7,800) was obtained.

<Production of urethane (meth) acrylate compound (A-3)>
In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser, and nitrogen gas inlet, 40 g of ethyl acetate, 40.8 g (0.18 mol) of isophorone diisocyanate (a1), 1,3-butanediol (a3: 4) 14.9 g (0.17 mol) of carbon number, 0.02 g of hydroquinone methyl ether as a polymerization inhibitor and 0.02 g of dibutyltin dilaurate as a reaction catalyst were allowed to react at 60 ° C. for 2 hours, and 2-hydroxyethyl acrylate ( a2) 4.3 g (0.037 mol) was charged and reacted at 60 ° C. for 3 hours. The reaction was terminated when the residual isocyanate group reached 0.3%, and the urethane (meth) acrylate compound (A- 3) An ethyl acetate solution (viscosity (20 ° C.) 8,900 mPa · s) of (weight average molecular weight (Mw); 7,900) was obtained.

<Production of urethane (meth) acrylate compound (A′-1)>
In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser, and nitrogen gas inlet, 40 g of ethyl acetate, 37.9 g (0.17 mol) of isophorone diisocyanate (a1), 1,6-hexanediol (a3: 6) 18.1 g (0.15 mol) of carbon number, 0.02 g of hydroquinone methyl ether as a polymerization inhibitor and 0.02 g of dibutyltin dilaurate as a reaction catalyst were allowed to react at 60 ° C. for 2 hours to give 2-hydroxyethyl acrylate ( a2) 4.0 g (0.034 mol) was charged and reacted at 60 ° C. for 3 hours. The reaction was terminated when the residual isocyanate group reached 0.3%, and the urethane (meth) acrylate compound (A ′ -1) An ethyl acetate solution (viscosity (20 ° C.) 4,100 mPa · s) of (weight average molecular weight (Mw); 10,400) Obtained.

<Production of urethane (meth) acrylate compound (A'-2)>
In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser, and nitrogen gas inlet, 40 g of ethyl acetate, 34.0 g (0.15 mol) of isophorone diisocyanate (a1), neopentyl glycol (a3: carbon number 5) ) 8.0 g (0.077 mol), 0.02 g of hydroquinone methyl ether as a polymerization inhibitor and 0.02 g of dibutyltin dilaurate as a reaction catalyst, and reacted at 60 ° C. for 2 hours to give 2-hydroxyethyl acrylate (a2) 18 0.0 g (0.15 mol) was charged and reacted at 60 ° C. for 3 hours. The reaction was terminated when the residual isocyanate group became 0.3%, and the urethane (meth) acrylate compound (A′-2) An ethyl acetate solution (viscosity (20 ° C.) 90 mPa · s) having a weight average molecular weight (Mw) of 1,400 was obtained.

<Production of urethane (meth) acrylate compound (A'-3)>
In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser, and nitrogen gas inlet, 40 g of ethyl acetate, 26.6 g (0.12 mol) of isophorone diisocyanate (a1), neopentyl glycol (a3: carbon number 5) ) 10.0 g (0.096 mol), 0.02 g of hydroquinone 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 pentaerythritol triacrylate [pentaerythritol triacrylate And a mixture of pentaerythritol tetraacrylate (hydroxyl value 116.5 mg KOH / g)] (a2) 23.4 g (0.049 mol) and reacted at 60 ° C. for 3 hours, resulting in a residual isocyanate group of 0.3%. When the reaction is over, urethane (medium ) Acrylate compound (A'-3) (weight average molecular weight (Mw); 5,000) to obtain an ethyl acetate solution of (viscosity (20 ° C.) 650 mPa · s).

<Manufacture of active energy ray-curable resin composition>
The above urethane (meth) acrylate compound (A) solution and photopolymerization initiator (B) (1-hydroxy-cyclohexyl-phenyl-ketone (BASF Japan, Irgacure 184)) are shown in Table 1 in terms of solid content. It mix | blended in the ratio and diluted so that the solid content except a photoinitiator might be 40% with ethyl acetate, and the active energy ray-curable resin composition was obtained. The following evaluation was performed about the obtained active energy ray-curable resin composition.

<Stickness of dried coating film (heating)>
The active energy ray-curable resin composition obtained above was applied to a polyethylene terephthalate film substrate (with a thickness of 125 μm) with an easy-adhesion layer so that the cured coating film would be 10 μm with a bar coater, and at 60 ° C. It dried for 3 minutes and obtained the coating film before hardening. A polyethylene terephthalate film (thickness 125 μm) with an easy-adhesion layer was stacked on the coating film, and a 2 cm square glass plate was placed thereon. Further, a weight of ² kg (500 g / cm ² ) was placed on the glass plate and stored in a 40 ° C. hot air dryer under light shielding. It took out from the dryer after a fixed time (60 minutes), checked how much the cured coating film surface was stuck to the polyethylene terephthalate film with an easy-adhesion layer, and evaluated according to the following criteria.
(Evaluation criteria)
○ ・ ・ ・ No sticking △ ・ ・ ・ Slightly sticking ×× With sticking

<Coating hardness>
Furthermore, the active energy ray-curable resin composition obtained above was applied to a polyethylene terephthalate film substrate (thickness 125 μm) with an easy-adhesion layer so that the cured coating film became 10 μm with a bar coater, After drying at a temperature of 3 ° C. for 3 minutes, using one high pressure mercury lamp lamp 80W, two passes of UV irradiation (cumulative irradiation amount 450 mJ / cm ² ) from a height of 18 cm at a conveyor speed of 5.1 m / min, A cured coating was obtained.
About the obtained cured coating film, pencil hardness was evaluated according to JIS K 5600 (load 750 g).
(Evaluation criteria)
○… HB or more ×… B or less

  From the above evaluation results, it is composed of a polyisocyanate compound containing an alicyclic structure, an aliphatic diol having 10 or less carbon atoms, and a hydroxyl group-containing (meth) acrylate compound containing one ethylenically unsaturated group. An active energy ray-curable resin composition of an example containing a urethane (meth) acrylate compound satisfying the condition of a molecular weight of 2,000 to 10,000 is applied on a substrate and dried. Even when a load was applied in an environment of 40 ° C., the tack-free coating surface that was not sticky in an uncured state could be maintained.

  On the other hand, the active energy ray-curable resin composition of Comparative Examples 1 and 2 in which the weight average molecular weight of the urethane (meth) acrylate compound is outside the specific range of the present application, and a hydroxyl group containing more than one ethylenically unsaturated group In the active energy ray-curable resin composition of Comparative Example 3 made of a urethane (meth) acrylate compound obtained by using the containing (meth) acrylate compound, the stickiness of the coating film surface is generated over time. It was an end.

  The active energy ray-curable resin composition of the present invention is not sticky in an uncured state even when a load is applied in an environment of 40 ° C. higher than room temperature, for example, after being coated on a substrate and dried, that is, tack-free. A cured coating film that can form a coating film surface and is cured by irradiation with active energy rays has excellent surface hardness and scratch resistance, and is very useful as a coating agent composition.

Claims (4)

A urethane (meth) acrylate compound obtained by reacting a polyvalent isocyanate compound (a1), a hydroxyl group-containing (meth) acrylate compound (a2), and a diol compound (a3),
A polyvalent isocyanate compound polyvalent isocyanate compound (a1) contains an alicyclic structure,
The hydroxyl group-containing (meth) acrylate compound (a2) is a hydroxyl group-containing (meth) acrylate compound containing one ethylenically unsaturated group,
The diol compound (a3) is an aliphatic diol having 10 or less carbon atoms and a molecular weight of 200 or less ,
A urethane (meth) acrylate compound having a weight average molecular weight of 4,300 to 7,900.   The urethane (meth) acrylate compound according to claim 1, wherein the diol compound (a3) does not have a repeating structure of an oxyalkylene structure. An active energy ray-curable resin composition comprising the urethane (meth) acrylate compound according to claim 1 or 2 . A coating agent composition comprising the active energy ray-curable resin composition according to claim 3 .