JP2015124227A - Active energy ray curable resin composition and coating agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray curable resin composition capable of forming a coating film surface which is in an uncured state and sticky, i.e. tack-free even when loaded at a temperature of 40°C higher than normal temperature after applying on a substrate and drying, and to provide a coating agent composition.SOLUTION: There is provided an active energy ray curable resin composition containing (A) an urethane (meth)acrylate compound obtained by reacting an isocyanate ring structure-containing isocyanate-based compound (a1) and a hydroxyl group-containing (meth)acrylate-based compound (a2), and a synthetic resin (B) where the percentage content (weight percentage) of an urethane bound residue of the hydroxyl group-containing (meth)acrylate compound (a2) is 30 to 45 wt.% in the urethane (meth)acrylate compound (A) and the glass transition temperature of the synthetic resin (B) is 40°C or more.

Description

  The present invention relates to an active energy ray-curable resin composition, and more specifically, after being applied on a substrate and dried, for example, in an uncured state even when a load is applied at 40 ° C. higher than normal temperature. The present invention relates to an active energy ray-curable resin composition capable of forming a non-sticky, that is, tack-free coating surface, and a coating agent composition using the same.

Conventionally, active energy ray-curable resin compositions have been widely used as coating agents, adhesives, anchor coating agents, etc. on various substrates for completing curing by irradiation of active energy rays 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 one after another and then printed repeatedly. 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 generally 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 A photocurable resin composition containing urethane compound (A) and photopolymerization initiator (B) as essential components has been proposed, and as in Patent Document 1, even if the coated film after drying is touched with a finger, tackiness can be achieved. 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 above, 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 roll-to-roll. Considering the case where heat is applied by winding, etc., in recent years, the surface of the coating film is not sticky even under a temperature environment higher than normal temperature, for example, at 40 ° C., even when a load is applied to the coating film. However, in such an environment, tack-free is not satisfied, and further improvement is required.

  Therefore, the present invention is not tacky in an uncured state even when a load is applied at 40 ° C., which is higher than normal temperature, for example, after being coated on a substrate and dried under such a background, that is, a tack-free coating surface. It is an object of the present invention to provide an active energy ray-curable resin composition and a coating agent composition capable of forming a film.

  However, the present inventors have made extensive studies in view of such circumstances, and as a result, urethane (meta) obtained by reacting an isocyanate compound (a1) containing an isocyanurate ring structure and a hydroxyl group-containing (meth) acrylate compound (a2). ) In the acrylate compound (A), a urethane (meth) acrylate compound having a small content of urethane bond residues in the hydroxyl group-containing (meth) acrylate compound (a2) is used, and a specific synthetic resin is further blended. Thus, for example, it was found that a tack-free coating surface without stickiness could be formed even when a load was applied in an environment of 40 ° C., and the present invention was completed.

  That is, the gist of the present invention is a urethane (meth) acrylate compound (A) obtained by reacting an isocyanurate ring structure-containing isocyanate compound (a1) and a hydroxyl group-containing (meth) acrylate compound (a2), and synthesis. An active energy ray-curable resin composition containing a resin (B), the urethane bond residue of a hydroxyl group-containing (meth) acrylate compound (a2) occupying the entire urethane (meth) acrylate compound (A) This invention relates to an active energy ray-curable resin composition having a group content (weight percentage) of 30 to 45% and a synthetic resin (B) having a glass transition temperature of 40 ° C. or higher.

  Moreover, in this invention, the coating agent composition formed by containing the said active energy ray hardening-type resin composition is also provided.

  The active energy ray-curable resin composition of the present invention forms a tack-free coating surface surface that is 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. In particular, it is very useful as a coating 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 active energy ray-curable resin composition of the present invention comprises a urethane (meth) acrylate compound (a) obtained by reacting an isocyanurate ring structure-containing isocyanate compound (a1) and a hydroxyl group-containing (meth) acrylate compound (a2). A) and a synthetic resin (B).

  The isocyanurate ring structure-containing isocyanate compound (a1) used in the present invention is a diisocyanate compound trimerized. Examples of the diisocyanate compound include tolylene diisocyanate, diphenylmethane diisocyanate, and polyphenyl. Aromatic polyisocyanates such as methane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylene diisocyanate, naphthalene diisocyanate; aliphatic such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate Polyisocyanate; hydrogenated diphenylmethane diisocyanate, hydrogenated Xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis alicyclic polyisocyanates such as (isocyanatomethyl) cyclohexane.

Among these diisocyanate compounds, aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate are less yellowed. And alicyclic diisocyanates such as 1,3-bis (isocyanatomethyl) cyclohexane are preferable, and isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, and hexamethylene diisocyanate are more preferable. , Isophorone diisocyanate and hexamethylene diisocyanate in terms of excellent reactivity and versatility
Moreover, these can be used 1 type or in combination of 2 or more types.

  Such isocyanurate ring structure-containing isocyanate compounds include, for example, “VESTANAT T 1890/100” (Degussa, IPDI isocyanurate), “Coronate HX” (Japan Polyurethane Industry, hexamethylene diisocyanate nurate) "Takenate D-127N" (Mitsui Chemicals, hydrogenated xylylene diisocyanate nurate) is readily available from the market.

  Furthermore, in the present invention, the isocyanurate ring structure-containing isocyanate compound (a1) is preferably a solid at 23 ° C. from the viewpoint of affecting the degree of stickiness of the coated film after drying.

The hydroxyl group-containing (meth) acrylate compound (a2) used in the present invention is a compound having one hydroxyl group and one or more (meth) acryloyl groups. 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-hydroxyethyl Acryloyl phosphate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, caprolactone-modified 2-hydroxyethyl (meth) acrylate, dipropylene glycol (meth) acrylate, fatty acid-modified glycidyl (meth) acrylate Polyethylene such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, 1,4-cyclohexanedimethanol monoacrylate, etc. (Meth) acrylate compounds containing one unsaturated group;
(Meth) acrylate compounds containing two ethylenically unsaturated groups such as glycerin di (meth) acrylate, 2-hydroxy-3-acryloyl-oxypropyl methacrylate, and the like;
Pentaerythritol tri (meth) acrylate, caprolactone modified pentaerythritol tri (meth) acrylate, ethylene oxide modified pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, ethylene Examples thereof include (meth) acrylate compounds containing three or more ethylenically unsaturated groups such as oxide-modified dipentaerythritol penta (meth) acrylate.

Among these, a hydroxyl group (meth) acrylate compound having one ethylenically unsaturated group is preferable from the point that the content ratio of the urethane bond residue can be controlled within a certain range, and the stickiness of the coating film after drying can be reduced. Furthermore, hydroxy such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate and the like. Alkyl (meth) acrylate is preferred from the viewpoint of reactivity and versatility, and in particular, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate in that the content of urethane bond residues can be kept lower. Is preferred.
Moreover, these can be used 1 type or in combination of 2 or more types.

  Moreover, as a weight average molecular weight of a hydroxyl-containing (meth) acrylate type compound (a2), 100-200 are preferable at the point which reduces the stickiness of the coating film after drying, and 100-140 are especially preferable.

  The production method of the urethane (meth) acrylate compound (A) is usually charged with the above-mentioned isocyanurate ring structure-containing isocyanate compound (a1) and the hydroxyl group-containing (meth) acrylate compound (a2) in a batch or separately. It is obtained by reacting an isocyanate compound (a1) containing an isocyanurate ring structure with a hydroxyl group-containing (meth) acrylate compound (a2).

  A known reaction means can be used for the reaction of the isocyanurate ring structure-containing isocyanate compound (a1) and the hydroxyl group-containing (meth) acrylate compound (a2). At that time, for example, the reaction molar ratio of the isocyanate compound (a1) containing the isocyanurate ring structure and the hydroxyl group-containing (meth) acrylate compound (a2) is, for example, three isocyanate groups of the isocyanate compound (a1). When the hydroxyl group-containing (meth) acrylate compound (a2) has one hydroxyl group, the isocyanate compound (a1): hydroxyl group-containing (meth) acrylate compound (a2) is about 1: 3.

  In the addition reaction between the isocyanurate ring structure-containing isocyanate compound (a1) and the hydroxyl group-containing (meth) acrylate compound (a2), the reaction is performed when the residual isocyanate group content in the reaction system is 0.5% by weight or less. The urethane (meth) acrylate compound (A) is obtained by terminating the process.

  In the reaction between the isocyanurate ring structure-containing isocyanate compound (a1) and the hydroxyl group-containing (meth) acrylate compound (a2), it is also preferable to use a catalyst for the purpose of accelerating the reaction. Dibutyltin dilaurate, dibutyltin diacetate, trimethyltin hydroxide, tetra-n-butyltin, bis (acetylacetonato) zinc, bis (tetrafluoroacetylacetonato) zinc, zirconium monoacetylacetonate, zirconium ethylacetoacetate, Organic gold such as zirconium tris (acetylacetonate) ethyl acetoacetate, zirconium tetraacetylacetonate, tetramethoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium, tetrabutoxytitanium Compounds, metal salts such as tin octenoate, zinc hexanoate, zinc octenoate, zinc stearate, zirconium 2-ethylhexanoate, cobalt naphthenate, stannous chloride, stannic chloride, potassium acetate, triethylamine, triethylenediamine , Benzyldiethylamine, 1,4-diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5,4,0] undecene, N, N, N ′, N′-tetramethyl-1,3-butane In addition to amine-based catalysts such as diamine, N-methylmorpholine, N-ethylmorpholine, bismuth nitrate, bismuth bromide, bismuth iodide, bismuth sulfide, etc., organic bismuth compounds such as dibutyl bismuth dilaurate, dioctyl bismuth dilaurate, 2- Bismuth ethylhexanoate, bismuth naphthenate, isodecane Bismuth salt, bismuth neodecanoate, bismuth laurate, bismuth maleate, bismuth stearate, bismuth oleate, bismuth linoleate, bismuth acetate, bismuth bisneodecanoate, bismuth disalicylate, di Examples thereof include bismuth-based catalysts such as organic acid bismuth salts such as bismuth gallate, among which dibutyltin dilaurate and 1,8-diazabicyclo [5,4,0] undecene are suitable. These can be used alone or in combination of two or more.

  In the reaction of the isocyanate compound (a1) containing the isocyanurate ring structure and the hydroxyl group-containing (meth) acrylate compound (a2), an organic solvent having no functional group that reacts with the isocyanate group, for example, ethyl acetate. Organic solvents such as esters such as butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and 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, although the urethane (meth) acrylate compound (A) used in the present invention is obtained, the urethane (meth) acrylate compound (A) is a hydroxyl group-containing component of the entire urethane (meth) acrylate compound (A). The content ratio (weight ratio) of the urethane bond residue of the (meth) acrylate compound (a2) is 30 to 45% by weight, and the particularly preferable content ratio is 31 to 40% by weight, and more preferable. The content ratio is 32 to 37% by weight. If the content is too low, the coating film hardness after curing will be insufficient, and if it is too high, stickiness will occur on the surface of the coating before curing by irradiation with active energy rays. When an appropriate amount of the synthetic resin (B) described below is blended within the above range, the coating film after drying will not be sticky. On the contrary, even if the same amount is blended outside the above range, stickiness remains on the coating film surface. Become.

  Here, the content ratio (weight ratio) of the urethane bond residue of the hydroxyl group-containing (meth) acrylate compound (a2) in the entire urethane (meth) acrylate compound (A) is calculated as follows. Shall.

That is, the content ratio (weight ratio) (%) of the urethane bond residue of the hydroxyl group-containing (meth) acrylate compound = {weight average molecular weight of the hydroxyl group-containing (meth) acrylate compound × molar ratio / (isocyanurate ring structure-containing isocyanate system) Compound weight average molecular weight × molar ratio + hydroxyl group-containing (meth) acrylate compound weight average molecular weight × molar ratio)} × 100
However, when the hydroxyl group-containing (meth) acrylate compound contains a hydroxyl group-containing compound having a plurality of ethylenically unsaturated groups as an impurity, the weight average molecular weight is calculated from the hydroxyl value.
In addition, although the urethane bond residue of a hydroxyl-containing (meth) acrylate type compound is what remove | excluded one hydrogen atom from the hydroxyl-containing (meth) acrylate compound, about calculation of the content rate of a urethane bond residue, This is done as described above.

  In the present invention, the number of ethylenically unsaturated groups in the urethane (meth) acrylate compound (A) is preferably 3-9, particularly preferably 3-6, and more preferably 3. . When the number of such ethylenically unsaturated groups is too large, the coating film after drying tends to be sticky.

  Furthermore, it is preferable that the weight average molecular weights of a urethane (meth) acrylate type compound (A) are 1000-3000, Most preferably, it is 1500-2000. If the weight average molecular weight is too small, the coating film hardness after curing tends to decrease, and if it is too large, the coating film after drying tends to be sticky.

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)).

  The synthetic resin (B) used in the present invention has a glass transition temperature of 40 ° C. or higher, preferably 60 to 150 ° C., more preferably 80 to 130 ° C., particularly preferably 90 to 120 ° C., particularly preferably. Is 95-110 ° C. If the glass transition temperature is too low, stickiness occurs on the surface of the coating before curing by irradiation with active energy rays.

  The glass transition temperature can be measured by using a temperature modulation DSC (“DSC 2920” manufactured by TA Instruments). The measurement conditions are such that a sample of about 1 to 5 mg is enclosed in a dedicated aluminum pan, and the temperature is raised between 3 ° C./min in the range of −100 ° C. to 200 ° C.

  Examples of the synthetic resin (B) include acrylic resins, polyester resins, polystyrene resins, and the like. Among them, acrylic resins are preferable in terms of good compatibility with urethane acrylate.

  In acrylic resin, for example, (1) (meth) acrylic acid ester monomer homopolymer, (2) (meth) acrylic acid ester monomer, functional group-containing monomer and other copolymerizable monomer as required In particular, 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.

  Moreover, in this invention, the weight average molecular weights of a synthetic resin (B) are 5000-3 million normally, Preferably it is 10,000-1 million, More preferably, it is 20,000-500,000. 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.

In addition, said weight average molecular weight is a number average molecular weight by standard polystyrene molecular weight conversion, column: Shodex GPC KF-806L (exclusion) in a high performance liquid chromatography (Showa Denko Co., Ltd. make, "Shodex GPC system-11 type | mold"). Limit molecular weight: 2 × 10 ⁷ , separation range: 100 to 2 × 10 ⁷ , theoretical plate number: 10,000 plate / piece, filler material: styrene-divinylbenzene copolymer, filler particle size: 10 μm) Measured by using series.

  About content of the said synthetic resin (B), it is preferable that it is 5-100 weight part with respect to 100 weight part of urethane (meth) acrylate type compounds (A), Especially 20-90 weight part, Furthermore, It is preferable that it is 25-80 weight part. If the content is too small, stickiness tends to occur on the surface of the coating film before curing by irradiation with active energy rays, and if it is too much, the scratch resistance and surface hardness of the cured coating film tend to decrease.

  The active energy ray-curable resin composition of the present invention contains the urethane (meth) acrylate compound (A) and the synthetic resin (B) as essential components, and is further crosslinked by irradiation with active energy rays. By forming a network structure, ethylenically unsaturated monomer (C) is blended in that the balance between hardness and flexibility in the coating film can be adjusted and durability such as water resistance and heat resistance can be improved. It is preferable to do.

  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. The ethylenically unsaturated monomer (C) may be separately blended with the urethane (meth) acrylate compound (A) or the synthetic resin (B), or the urethane (meth) acrylate compound (A). As a production raw material, a part of the raw material may remain in the system at the time of production.

  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.

  In the present invention, in addition to the urethane (meth) acrylate compound (A) and the synthetic resin (B), a photopolymerization initiator (D) may be contained in order to efficiently perform curing with active energy rays. preferable.

  Examples of the photopolymerization initiator (D) include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) -phenyl- (2 -Hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4- Acetophenones such as morpholinophenyl) butanone and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomer; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl Benzoy such as 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] benzenemethananium bromide, (4-benzoylbenzyl) trimethylammonium chloride Benzophenones such as 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy) -3, 4 Thioxanthones such as dimethyl-9H-thioxanthone-9-one mesochloride; 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphos Acylphosphine oxides such as fin oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; In addition, as for these photoinitiators (D), 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 (D), it is 0.1 with respect to 100 weight part of urethane (meth) acrylate type-compounds (A) (when it contains an ethylenically unsaturated monomer (C)). It is preferably ˜40 parts by weight, particularly preferably 1 to 20 parts by weight, particularly preferably 2 to 10 parts by weight.

  If the content of the photopolymerization initiator (D) is too small, curing tends to be poor, and if it is too much, the solution stability tends to decrease such as precipitation when used as a coating agent, and embrittlement or coloring may occur. Problems tend to occur.

  Thus, the active energy ray-curable resin composition containing the urethane (meth) acrylate compound (A) and the synthetic resin (B) of the present invention, preferably further containing an ethylenically unsaturated monomer (C) and a photopolymerization initiator (D). Although a product is obtained, a leveling agent, a surface conditioner, a polymerization inhibitor and the like can be further blended as necessary.

  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. Etc. 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- Examples thereof include butyl hydroquinone and pt-butyl catechol.

  The active energy ray-curable resin composition of the present invention includes oil, antioxidant, flame retardant, antistatic agent, stabilizer, reinforcing agent, abrasive, inorganic fine particles, polymer compound (for example, acrylic resin, It is also possible to blend polyester resin, epoxy resin, etc.).

  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, 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 of the present invention, urethane (meth) acrylate compound (A), synthetic resin (B), ethylenically unsaturated monomer (C) used as necessary, About the mixing method of a photoinitiator (D), it does not specifically limit, It can mix 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 at 40 ° C., which is higher than normal temperature, for example, after being coated on various substrates and dried, that is, a tack-free coating. Effectively used as a curable resin composition for forming a coating film for forming a film surface, after coating an active energy ray-curable resin composition on a substrate (a composition diluted with an organic solvent) In the case of coating, after further drying), it is cured by irradiation with active energy rays.

  The coating method is not particularly limited, and examples thereof include wet coating methods such as spraying, showering, dipping, flow coating, gravure coating, roll coating, spin coating, dispenser, ink jet, and screen 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 (D).

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.

  The thickness of the cured coating film is usually preferably 1 to 50 μm, particularly preferably 2 to 40 μm, more preferably 5 to 30 μm.

  The base material to which the active energy ray-curable resin composition of the present invention is applied includes polyolefin resin, polyester resin, polycarbonate resin, acrylonitrile butadiene styrene copolymer (ABS), polystyrene resin, polyamide. 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 active energy ray-curable resin composition containing the urethane (meth) acrylate compound (A) and the synthetic resin (B) of the present invention is applied on a substrate and dried, and then, for example, higher than room temperature is 40. Even when a load is applied at ℃, it is not sticky in an uncured state, that is, it can form a tack-free coating surface, and the cured coating film cured by active energy ray irradiation has surface hardness and scratch resistance. And is very useful as a coating agent composition.

  The coating agent composition preferably contains the urethane (meth) acrylate compound (A) in an amount of 2 to 60% by weight, particularly preferably 3 to 40% by weight, more preferably 5 to 30%, based on the entire coating agent composition. % By weight. In addition, the coating agent composition may or may not contain an organic solvent. If the content of the urethane (meth) acrylate compound (A) is too small, mechanical properties such as scratch resistance tend to decrease, and if it is too large, the coating film after drying tends to be sticky.

  The active energy ray-curable resin composition of the present invention forms a tack-free coating surface surface that is 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. 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)>
A 4-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet is charged with 269.7 g (0.37 mol) of isophorone diisocyanate trimer (a1) and 266.7 g of ethyl acetate at 50 ° C. Keep warm. After the isophorone diisocyanate trimer (a1) is completely dissolved, 131.2 g (1.13 mol) of 2-hydroxyethyl acrylate, 0.53 g of dibutylhydroxytoluene as a polymerization inhibitor, and 0.04 g of dibutyltin dilaurate as a reaction catalyst are charged. The reaction was terminated when the residual isocyanate group became 0.3% at 60 ° C. to obtain a trifunctional urethane acrylate (A-1).
The content (weight ratio) of the urethane bond residue of the hydroxyl group-containing (meth) acrylate compound in the entire urethane (meth) acrylate compound (A) was 32.6%.

<Production of urethane (meth) acrylate compound (A-2)>
In the production of the urethane (meth) acrylate compound (A-1), except that 131.2 g (1.13 mol) of 2-hydroxyethyl acrylate was changed to 147.1 g (1.13 mol) of 2-hydroxypropyl acrylate. In the same manner, trifunctional urethane acrylate (A-2) was obtained.
The content (weight ratio) of the urethane bond residue of the hydroxyl group-containing (meth) acrylate compound in the entire urethane (meth) acrylate compound (A) was 35.1%.

<Production of urethane (meth) acrylate compound (A-3)>
In the production of the urethane (meth) acrylate compound (A-1), except that 131.2 g (1.13 mol) of 2-hydroxyethyl acrylate was changed to 147.1 g (1.13 mol) of 2-hydroxyethyl methacrylate. In the same manner, trifunctional urethane methacrylate (A-3) was obtained.
The content (weight ratio) of the urethane bond residue of the hydroxyl group-containing (meth) acrylate compound in the entire urethane (meth) acrylate compound (A) was 35.1%.

<Production of urethane (meth) acrylate compound (A-4)>
In the production of the urethane (meth) acrylate compound (A-1), except that 131.2 g (1.13 mol) of 2-hydroxyethyl acrylate was changed to 162.9 g (1.13 mol) of 4-hydroxybutyl acrylate. In the same manner, trifunctional urethane acrylate (A-4) was obtained.
The content (weight ratio) of the urethane bond residue of the hydroxyl group-containing (meth) acrylate compound in the entire urethane (meth) acrylate compound (A) was 37.5%.

Moreover, the following urethane (meth) acrylate type compound (A ') was prepared for the comparative example of a urethane (meth) acrylate type compound (A).
<Production of urethane (meth) acrylate compound (A′-1)>
In the production of the urethane (meth) acrylate compound (A-1), 131.2 g (1.13 mol) of 2-hydroxyethyl acrylate was mixed with pentaerythritol triacrylate and pentaerythritol tetraacrylate (hydroxyl value 118) 536.3 g. Except having changed into (1.13 mol), it carried out similarly and obtained 9 functional urethane acrylate (A'-1).
The content (weight ratio) of the urethane bond residue of the hydroxyl group-containing (meth) acrylate compound in the entire urethane (meth) acrylate compound (A) was 66.4%.

As synthetic resin (B), it prepared as follows.
<Acrylic resin (B-1)>
A suitable amount of 40 g of ethyl acetate (solvent), 20 g of methyl methacrylate, and azobisisobutyronitrile (AIBN) as a polymerization initiator are added to a reactor equipped with a thermometer, a stirring device, a nitrogen introducing tube, a dropping funnel and a reflux condenser. The resulting mixture was heated to 80 ° C. while stirring under a nitrogen stream to initiate polymerization, and polymerized for 9 hours while successively adding AIBN. Thereafter, 10 g of ethyl acetate, 20 g of methyl methacrylate and appropriate amounts of AIBN were added for further polymerization, and diluted with ethyl acetate to obtain an acrylic resin (B-1) solution (concentration 40%).
The obtained acrylic resin (B-1) (polymethyl methacrylate) had a glass transition temperature (Tg) of 105 ° C. and a weight average molecular weight (in terms of polystyrene) of 43,000.
The glass transition temperature and the weight average molecular weight were measured as described above.

The following were prepared as the photopolymerization initiator (D).
(D-1): 1-hydroxy-cyclohexyl-phenyl-ketone (BASF Japan, Irgacure 184)

[Examples 1 to 4, Comparative Examples 1 to 4]
The urethane (meth) acrylate compound (A) and the synthetic resin (B) are blended as shown in Table 1, adjusted with ethyl acetate so that the solid content concentration becomes 50%, and active energy ray curing. A mold resin composition was obtained.
About the obtained active energy ray hardening-type resin composition, the stickiness of the dry coating film was evaluated as follows.

(The stickiness of dry coating)
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. The surface of the coating was touched with a finger and evaluated according to the following criteria.
○ ・ ・ ・ No stickiness △ ・ ・ ・ Slight stickiness × ・ ・ ・ With stickiness In addition, a polyethylene terephthalate film (thickness 125 μm) with an easy-adhesion layer is layered on the above coating film, and a 2 cm square glass plate is formed thereon. placed. 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. After a certain time (10 minutes, 30 minutes, 60 minutes), it was taken out from the dryer, and it was confirmed 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.
○ ・ ・ ・ No sticking △ ・ ・ ・ Slightly sticking ×× With sticking

Furthermore, a photopolymerization initiator (D) (in terms of solid content) is blended in the active energy ray-curable resin composition as shown in Table 1, and an easy-adhesion layer is formed so that the cured coating film becomes 10 μm with a bar coater. After coating the attached polyethylene terephthalate film substrate (thickness 125 μm) and drying at 60 ° C. for 3 minutes, using a high pressure mercury lamp 80 W and one lamp, a conveyor speed of 5.1 m / min from a height of 18 cm And 2 passes of ultraviolet irradiation (accumulated dose 450 mJ / cm ² ) to obtain a cured coating film.
About the obtained cured coating film, the coating-film physical property was evaluated as follows.

(Pencil hardness)
About said hardened coating film, pencil hardness was evaluated according to JISK5600 (load 750g).
Table 2 shows the evaluation results of Examples and Comparative Examples.

  From the above evaluation results, the active energy ray-curable resin composition of the example obtained by blending the synthetic resin (B) with the urethane (meth) acrylate compound (A) was applied onto a substrate and dried, then, 40 Comparative Examples 2 to 4 that do not contain a synthetic resin (B) are able to maintain a tack-free coating surface that is not sticky in an uncured state even when a load is applied at ℃. Of course, in the active energy ray-curable resin composition of Comparative Example 1 using a urethane (meth) acrylate compound that does not satisfy the urethane (meth) acrylate compound (A), the surface of the coating film with the passage of time. It was sticky and did not satisfy the object of the present invention.

  The active energy ray-curable resin composition of the present invention is not sticky in an uncured state even when a load is applied at 40 ° C., which is higher than normal temperature, for example, after being applied on a substrate and dried. A cured coating film that can form a 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 (6)

  Contains a urethane (meth) acrylate compound (A) obtained by reacting an isocyanurate ring structure-containing isocyanate compound (a1) and a hydroxyl group-containing (meth) acrylate compound (a2), and a synthetic resin (B). An active energy ray-curable resin composition, which is a urethane bond residue content ratio (weight ratio) of the hydroxyl group-containing (meth) acrylate compound (a2) in the entire urethane (meth) acrylate compound (A). Is 30 to 45% by weight, and the glass transition temperature of the synthetic resin (B) is 40 ° C. or higher.   The active energy ray-curable resin composition according to claim 1, wherein the isocyanurate ring structure-containing isocyanate compound (a1) is solid at 23 ° C.   3. The active energy ray-curable resin composition according to claim 1, wherein the hydroxyl group-containing (meth) acrylate compound (a2) is a (meth) acrylate compound having one ethylenically unsaturated group. .   The active energy according to any one of claims 1 to 3, wherein the content of the synthetic resin (B) is 5 to 100 parts by weight with respect to 100 parts by weight of the urethane (meth) acrylate compound (A). A linear curable resin composition.   The active energy ray-curable resin composition according to any one of claims 1 to 4, wherein the synthetic resin (B) is polymethyl (meth) acrylate.   A coating agent composition comprising the active energy ray-curable resin composition according to claim 1.