JP2010024255A - Active energy ray-curing resin composition and coating agent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an active energy ray-curing resin composition for forming a coating layer excellent in coating film hardness as well as curability, and to provide a coating agent composition using the composition. <P>SOLUTION: The active energy ray-curing resin composition comprises a urethane (meth)acrylate compound (A) having at least three ethylenically unsaturated groups in the molecule, a thiol compound (B) and silica (C). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an active energy ray-curable resin composition containing a urethane (meth) acrylate-based compound and a coating agent composition using the same, and more specifically, forms a coating layer having excellent hardness of a cured coating film. The present invention relates to an active energy ray-curable resin composition useful for coating and a coating agent composition using the same.

Conventionally, urethane (meth) acrylate compounds have been used as coating layers for optical films because they are cured by irradiation with active energy rays and have high flexibility and wear resistance. With regard to, there is a demand for further higher hardness.
On the other hand, the hard coat layer provided on the film for imparting hard coat performance is obtained, for example, by irradiating and curing an active energy ray on the acrylate-based photosensitive resin composition, Curing shrinkage and heat / humidity shrinkage easily occur during the curing, and the film provided with the hard coat layer is prone to curl.

As one method for solving such a problem, low curl of the hard coat layer has been studied, and by adding specific silica fine particles to the ionizing radiation sensitive resin composition, low curl of the hard coat layer is studied. Is known to be achieved (see, for example, Patent Document 1).
Similarly, polyfunctional urethane (meth) acrylate was used as a compound containing a polymerizable unsaturated group-containing compound and fine particles such as silica, and colloidal silica having a primary particle size of 1 to 200 nm was added thereto. A film having a cured coating layer of a radiation curable resin composition is also known.

JP 2004-182765 A JP 2001-113649 A

However, a cured coating film obtained by irradiating active energy rays to a composition in which silica particles are blended with a urethane (meth) acrylate compound can achieve low curl by blending silica particles, but on the other hand, active energy rays. The reaction rate of ethylenically unsaturated groups due to irradiation was not sufficient, and as a result, the problem of insufficient coating film hardness occurred.
Therefore, in the present invention, under such a background, active energy ray curing that achieves low curl and further increases the hardness of the coating film by adding silica particles to the urethane (meth) acrylate compound. An object of the present invention is to provide a mold resin composition.

  However, in the present invention, as a result of intensive studies in view of such circumstances, the active energy ray-curable resin composition in which silica particles are used in combination with a urethane (meth) acrylate compound, and the thiol compound is further used in combination. It has been found that a cured coating film obtained from a product exhibits low curl properties and also exhibits high curability and high hardness, thereby completing the present invention.

  That is, the gist of the present invention is characterized by comprising a urethane (meth) acrylate compound (A) having three or more ethylenically unsaturated groups, a thiol compound (B) and silica (C). The present invention relates to an active energy ray-curable resin composition.

  In addition, when a thiol compound is used in combination with a urethane (meth) acrylate compound, it is considered that there is a risk of inferior storage stability of the compound, and until now, no attempt was made to use a thiol compound together. However, in this invention, it discovered that it had favorable coating-film physical property by using both together.

  Since the active energy ray-curable resin composition of the present invention contains a urethane (meth) acrylate compound (A), a thiol compound (B) and silica (C), a cured coating obtained by irradiation with active energy rays. The film exhibits high curability and high hardness, and exhibits an excellent effect in suppressing curing shrinkage.

Hereinafter, the present invention will be described in detail.
The urethane (meth) acrylate compound (A) used in the present invention only needs to have three or more ethylenically unsaturated groups, and specifically, in the hydroxyl group-containing (meth) acrylate compound (a1). It is obtained by reacting a hydroxyl group with an isocyanate group of the polyvalent isocyanate compound (a2).
Each component which comprises this urethane (meth) acrylate type compound is demonstrated.

It does not specifically limit as said hydroxyl-containing (meth) acrylate type compound (a1), For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4 -Hydroxyalkyl (meth) acrylates such as hydroxybutyl (meth) acrylate and 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) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene Recall mono (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, glycerin di (meth) acrylate, 2-hydroxy-3-acryloyl-oxypropyl methacrylate, 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 oxide modified dipentaerythritol penta (Meth) acrylate etc. are mentioned.
Among these, it is preferable to use one or more compounds containing three or more ethylenically unsaturated groups from the viewpoint of the hardness of the cured coating film. Furthermore, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meta) It is particularly preferred to use acrylates).

  The polyvalent isocyanate compound (a2) is not particularly limited, and examples thereof include aromatic, aliphatic, and alicyclic polyisocyanates, among which tolylene diisocyanate, diphenylmethane diisocyanate, and hydrogenation. Diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis (Isocyanatomethyl) cyclohexane, phenylene diisocyanate, lysine diisocyanate, lysine tri Polyisocyanates such as socyanate, naphthalene diisocyanate or the like, trimer compounds or multimeric compounds of these polyisocyanates, allophanate type polyisocyanates, burette type polyisocyanates, water-dispersed polyisocyanates (for example, "Aqua" Nate 100 ”,“ Aquanate 110 ”,“ Aquanate 200 ”,“ Aquanate 210 ”, etc.), or reaction products of these polyisocyanates and polyols. Among these, aliphatic polyisocyanate compounds are preferably used, and in particular, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated xylylene diisocyanate are less in yellowing of the cured coating film and less in curing shrinkage. Further preferably used.

  Examples of such polyols include, but are not limited to, alkylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, and polybutylene glycol. Compounds, 1,6-hexanediol, neopentyl glycol, cyclohexanedimethanol, hydrogenated bisphenol A, polycaprolactone, trimethylolethane, trimethylolpropane, polytrimethylolpropane, pentaerythritol, polypentaerythritol, sorbitol, mannitol, Polyvalent alcohols such as glycerin, polyglycerin, polytetramethylene glycol A polyether polyol having at least one structure of block or random copolymerization of polyethylene oxide, polypropylene oxide, ethylene oxide / propylene oxide; the polyhydric alcohol or polyether polyol and maleic anhydride, maleic acid, fumaric acid, Polyester polyols that are condensation products with polybasic acids such as itaconic anhydride, itaconic acid, adipic acid, and isophthalic acid; caprolactone-modified polyols such as caprolactone-modified polytetramethylene polyol; polyolefin-based polyols; polybutadiene-based such as hydrogenated polybutadiene polyols A polyol etc. are mentioned. Among these, polyethylene glycol derivatives are preferably used, and polyethylene glycol and polyethylene glycol monomethyl ether are particularly preferably used.

  Furthermore, as such polyols, for example, 2,2-bis (hydroxymethyl) butyric acid, tartaric acid, 2,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxyethyl) propionic acid, 2,2-bis (hydroxypropyl) propionic acid, dihydroxymethylacetic acid, bis (4-hydroxyphenyl) acetic acid, 4,4-bis (4-hydroxyphenyl) pentanoic acid Also included are carboxyl group-containing polyols such as homogentisic acid, sulfonic acid group or sulfonate group-containing polyols such as sodium 1,4-butanediol sulfonate, and the like.

  When using the reaction product of polyisocyanate and polyol, for example, it may be used as a terminal isocyanate group-containing polyisocyanate obtained by reacting the polyol with the polyisocyanate. In the reaction between the polyisocyanate and the polyol, a metal catalyst such as a tin-based catalyst such as dibutyltin dilaurate or dioctyltin dilaurate or a bismuth-based catalyst, 1,8-diazabicyclo [5.4.0] undeca is used for the purpose of promoting the reaction. It is also preferable to use amine catalysts such as -7-ene and 1,5-diazabicyclo [4.3.0] non-5-ene, nitrogen-containing heterocyclic compounds such as imidazole, and the like.

  And in order to obtain the urethane (meth) acrylate type compound (A) containing the 3 or more ethylenically unsaturated group of this invention, the said hydroxyl-containing (meth) acrylate type compound (a1) and polyvalent isocyanate The compound (a2) may be appropriately selected and used so that the number of ethylenically unsaturated groups is 3 or more. For example, when a compound having one ethylenically unsaturated group is used as the hydroxyl group-containing (meth) acrylate compound (a1), a triisocyanate compound is used as the polyvalent isocyanate compound (a2) instead of a diisocyanate compound. That's fine.

  The urethane (meth) acrylate compound (A) having 3 or more ethylenically unsaturated groups is preferably a urethane (meth) acrylate compound having 4 or more ethylenically unsaturated groups, particularly Is preferably a urethane (meth) acrylate compound having 6 or more ethylenically unsaturated groups from the viewpoint of the hardness of the cured coating film. Among these, for example, urethane (meth) acrylate having 6 ethylenically unsaturated groups obtained by reacting pentaerythritol triacrylate and isophorone diisocyanate is particularly preferable. Moreover, the upper limit of the ethylenically unsaturated group which a urethane (meth) acrylate type compound contains is 30 normally, Preferably it is 25 or less.

  The weight average molecular weight of the obtained urethane (meth) acrylate compound (A) is preferably 500 to 50000, and more preferably 1000 to 30000. If the weight average molecular weight is too small, the cured coating film tends to be brittle, and if it is too large, the viscosity tends to be high and difficult to handle.

In addition, said weight average molecular weight is a weight average molecular weight by standard polystyrene molecular weight conversion, a column: Shodex GPC KF-806L (high-performance liquid chromatography (the Showa Denko company make, "Shodex GPC system-11 type | mold")). Exclusion 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 this series.

  Next, the thiol compound (B) will be described.

  The thiol compound (B) is not particularly limited as long as it has one or more thiol groups in one molecule. For example, mercaptopropionate, mercaptobutyrate, mercaptoisobutyrate, thioglyco Rate and the like.

  Examples of mercaptopropionate include methyl mercaptopropionate, methoxybutyl mercaptopropionate, octyl mercaptopropionate, tridecyl mercaptopropionate, ethylene glycol bis (2-mercaptopropionate), 1,2-propylene glycol bis (2 -Mercaptopropionate), diethylene glycol bis (2-mercaptopropionate), 1,4-butanediol bis (2-mercaptopropionate), 1,8-octanediol bis (2-mercaptopropionate), Trimethylolpropane tris (2-mercaptopropionate), pentaerythritol tetrakis (2-mercaptopropionate), dipentaerythritol hexakis (2-mercaptopropionate) Ethylene glycol bis (3-mercaptopropionate), 1,2-propylene glycol bis (3-mercaptopropionate), diethylene glycol bis (3-mercaptopropionate), 1,4-butanediol bis (3-mercapto) Propionate), 1,8-octanediol bis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexa Kiss (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), tris- (ethyl-3-mercaptopropionate) isocyanurate, methyl-3-mercaptopropionate, 2- Ethylhexyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, stearyl-3-mercaptopropionate and the like.

  Examples of mercaptobutyrate include ethylene glycol bis (3-mercaptobutyrate), 1,2-propylene glycol bis (3-mercaptobutyrate), diethylene glycol bis (3-mercaptobutyrate), and 1,4-butanediol bis. (3-mercaptobutyrate), 1,8-octanediol bis (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol hexa Kiss (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2, 4,6 (1H, 3H, 5H) -tri Emissions, and the like.

  Examples of mercaptoisobutyrate include ethylene glycol bis (3-mercaptoisobutyrate), 1,2-propylene glycol bis (3-mercaptoisobutyrate), diethylene glycol bis (3-mercaptoisobutyrate), and 1,4. -Butanediol bis (3-mercaptoisobutyrate), 1,8-octanediol bis (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptoisobutyrate), pentaerythritol tetrakis (3-mercaptoiso) Butyrate), dipentaerythritol hexakis (3-mercaptoisobutyrate), ethylene glycol bis (2-mercaptoisobutyrate), 1,2-propylene glycol bis (2-mercaptoisobutyrate), diethylene Recall bis (2-mercaptoisobutyrate), 1,4-butanediol bis (2-mercaptoisobutyrate), 1,8-octanediol bis (2-mercaptoisobutyrate), trimethylolpropane tris (2- Mercaptoisobutyrate), pentaerythritol tetrakis (2-mercaptoisobutyrate), dipentaerythritol hexakis (2-mercaptoisobutyrate) and the like.

  Examples of the thioglycolate include ethylene glycol bisthioglycolate, butanediol bisthioglycolate, hexanediol bisthioglycolate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthioglycolate, dipentaerythritol hexakisthioglycol. Rate and the like.

  As other thiol compounds, for example, β-mercaptopropionic acid, thioglycolic acid, ammonium thioglycolate, thioglycolate monoethanolamine, methyl thioglycolate, octyl thioglycolate, methoxybutyl thioglycolate, 2-mercapto Propionic acid and the like can be mentioned, and PEMP-20 (polyfunctional thiol manufactured by Sakai Chemical Co., Ltd.), DPMP-20 (polyfunctional thiol manufactured by Sakai Chemical Co., Ltd.) and the like are used because of excellent storage stability.

  Among the above thiol compounds, mercaptopropionate is preferable in terms of excellent curability, and in particular, tetraethylene glycol bis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis. (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tris- (ethyl-3-mercaptopropionate) isocyanurate are preferred, and trimethylolpropane tris (3-mercapto) Propionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate) are preferred, and in particular, dipentaerythritol hexakis ( - mercaptopropionate) are preferred.

Moreover, the thiol compound which has a 2 or more thiol group is preferable at the point which is excellent in coating film hardness, The thiol compound which has a 3 or more thiol group is especially preferable, Furthermore, the thiol compound which has a 4 or more thiol group is preferable. A thiol compound having 6 or more thiol groups is particularly preferable.
In addition, there exists a tendency for the reaction rate of the ethylenically unsaturated group in a cured coating film to increase, and the cure rate of a cured coating film to increase, so that the number of thiol groups increases. Furthermore, a thiol compound having 10 or more thiol groups is not preferable because the thiol groups remain without reacting and the durability of the cured coating film tends to be lowered.
The thiol compound of the present invention is particularly preferably a mercaptopropionate having 6 or more mercapto groups from the viewpoint of curability and coating film hardness.

  Said thiol compound (B) may be used independently and may use 2 or more types together.

  In the present invention, the content of the thiol (B) is 100 parts by weight of a curable component, that is, a urethane (meth) acrylate compound (A) (in the case of containing an ethylenically unsaturated monomer (E) described later, urethane). The total amount of the (meth) acrylate compound (A) and the ethylenically unsaturated monomer (E) is preferably 100 to 100 parts by weight, and more preferably 0.5 to 30 parts by weight. Parts, particularly preferably 1 to 15 parts by weight. If the content is too small, the hardness of the cured coating film tends not to be improved, and if it is too large, the hardness of the cured coating film tends to decrease.

Next, silica (C) will be described.
Silica (C) in the present invention is not particularly limited, and includes fine powder silica not containing a dispersion medium, silica sol in which silica is dispersed in a dispersion medium, and those obtained by surface modification with a coupling agent or the like. It is done.

  Such a dispersion medium is not particularly limited. For example, alcohols such as methanol, ethanol, propanol, n-butanol and i-butanol, cellosolves such as ethyl cellosolve, glycol ethers such as propylene glycol monomethyl ether, acetone, Ketones such as methyl isobutyl ketone, methyl ethyl ketone and cyclohexanone, polyhydric alcohols such as ethylene glycol and derivatives thereof, acrylates such as 2-hydroxyethyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxypropyl acrylate and 4-hydroxybutyl acrylate In addition to these, water, ethyl acetate, butyl acetate, toluene, xylene, diacetone alcohol and the like can be mentioned. Among these, propanol, n-butanol, i-butanol, methyl isobutyl ketone, methyl ethyl ketone, and toluene are preferable in terms of the coating film appearance.

  Further, the concentration as the dispersion is preferably 10 to 70% by weight, and particularly preferably 15 to 40% by weight. If the concentration is too low, the composition viscosity after blending becomes low, which is problematic from the viewpoint of coating suitability. When it is too high, the dispersion tends to be inferior in stability.

These silicas (C) may be used alone or in combination of two or more.
For example, when two or more types of silica sols in which silica is dispersed in a dispersion medium are used in combination, silica sol in which the dispersion medium is a glycol ether such as propylene glycol monomethyl ether, and the dispersion medium is a ketone such as methyl ethyl ketone or an alcohol such as methanol. The silica sol is a combination of silica sol, the dispersion medium is a ketone such as methyl ethyl ketone, and the silica sol is a dispersion medium being an alcohol such as methanol, and the dispersion medium is selected from two or more alcohols such as methanol. It is preferable from the viewpoint of the appearance of the coating film to use a silica sol which is a liquid.

The average particle size of silica (C) used in the present invention is preferably 200 nm or less, particularly 100 nm or less, more preferably 1 to 100 nm, and particularly preferably 1 to 50 nm from the viewpoint of the transparency of the cured coating film. . When the average particle diameter of silica (C) is too large, the transparency of the coating film tends to be inferior.
The average particle diameter is an average particle diameter measured by the BET method.

  In the present invention, the content of the silica (C) is 100 parts by weight of a curable component, that is, a urethane (meth) acrylate compound (A) (in the case of containing an ethylenically unsaturated monomer (E) described later, urethane). The total amount of the (meth) acrylate compound (A) and the ethylenically unsaturated monomer (E) is preferably 100 to 500 parts by weight, more preferably 10 to 300 parts by weight, particularly preferably. Is 20 to 200 parts by weight. When the content is too small, curing shrinkage tends to increase, and when the content is too large, the cured coating film tends to become brittle.

  The active energy ray-curable resin composition of the present invention contains the urethane (meth) acrylate compound (A), thiol compound (B) and silica (C), but is cured by ultraviolet irradiation. When performing, it is preferable to contain a photoinitiator (D).

  The photopolymerization initiator (D) is not particularly limited as long as it generates radicals by the action of light. For example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 2- Hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylenephenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy 2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) Phenyl] -2-morpholinopropane-1, benzoin, benzoin methyl ether, benzoin Tyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3'-dimethyl -4-methoxybenzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, camphorquinone, dibenzosuberone, 2-ethylanthraquinone, 4 ', 4 "-diethylisophthalo Phenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, α-acyloxime ester, acylphosphine Examples include oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, among which benzyldimethyl ketal, 1 -Hydroxycyclohexyl phenyl ketone, benzoyl isopropyl ether, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one are preferred. These photopolymerization initiators (D) may be used alone or in combination of two or more.

  Further, triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (Michler ketone), 4,4'-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, 4-dimethylamino as an auxiliary for the photopolymerization initiator Ethyl benzoate, ethyl 4-dimethylaminobenzoate (n-butoxy), isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, etc. It can also be used in combination.

  In this invention, content of the said photoinitiator (D) contains a sclerosing | hardenable component, ie, urethane (meth) acrylate type compound (A) 100 weight part (after-mentioned ethylenically unsaturated monomer (E). In the case, it is preferably 1 to 20 parts by weight, more preferably 1 to 15 parts by weight with respect to the urethane (meth) acrylate compound (A) and the ethylenically unsaturated monomer (E) in a total of 100 parts by weight). Particularly preferred is 1 to 10 parts by weight. If the content is too small, the curing rate in the case of ultraviolet curing tends to be extremely slow, and if it is too large, the curability is not improved and is useless.

  In the present invention, in addition to urethane (meth) acrylate compound (A), thiol compound (B), silica (C) and photopolymerization initiator (D), ethylenically unsaturated monomer (E) is contained. It is also preferable from the viewpoint of exhibiting the effect of the present invention, and more preferable from the viewpoint of further improving the hard coat performance.

  Examples of the ethylenically unsaturated monomer (E) include ethylenically unsaturated monomers having one or more ethylenically unsaturated groups in one molecule, such as monofunctional monomers, bifunctional monomers, and trifunctional or more monomers. It is done.

  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, furfuryl (meth) acrylate, carbitol (meth) acrylate, benzyl (meth) acrylate, butoxyethyl (meth) acrylate, allyl (meth) acrylate, acryloylmorpholine, 2-hydroxyethylacrylamide, N- Examples include methylol (meth) acrylamide, N-vinylpyrrolidone, 2-vinylpyridine, 2- (meth) acryloyloxyethyl acid phosphate monoester and the like.

  In addition to the above, a Michael adduct of acrylic acid or a 2-acryloyloxyethyl dicarboxylic acid monoester may also be mentioned. Examples of the acrylic acid Michael adduct include acrylic acid dimer, methacrylic acid dimer, acrylic acid trimer, and 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, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) Examples include acrylate, diglycidyl phthalate di (meth) acrylate, hydroxypivalic acid-modified neopentyl glycol di (meth) acrylate, isocyanuric acid ethylene oxide-modified diacrylate, and 2- (meth) acryloyloxyethyl acid phosphate diester.

  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.

  In addition to the above, hyperbranched acrylate, dendrimer acrylate, epoxy acrylate, polyester acrylate, and the like can also be used as the ethylenically unsaturated monomer (E).

  Said ethylenically unsaturated monomer (E) may be used independently and may use 2 or more types together. Among these ethylenically unsaturated monomers (E), it is preferable to use an ethylenically unsaturated monomer containing two or more ethylenically unsaturated groups in terms of the hardness of the cured coating film.

  The content of the ethylenically unsaturated monomer (E) is preferably 500 parts by weight or less, more preferably 200 parts by weight or less, particularly preferably 100 parts by weight or less with respect to 100 parts by weight of the urethane (meth) acrylate compound (A). Preferably it is 0-100 weight part or less. If the content is too large, the cured coating tends to be brittle, which is not preferable.

  In the present invention, the urethane (meth) acrylate compound (A), thiol compound (B), silica (C), photopolymerization initiator (D), and ethylenically unsaturated monomer (E) are also included. It is also preferable to add a polymerization inhibitor (F) from the viewpoint of sample stability.

  Although it does not specifically limit as a polymerization inhibitor (F), For example, radical scavengers, such as a hindered phenol and a hindered amine, a phosphorus system secondary oxidative degradation inhibitor, diethyl hydroxylamine, sulfur, t-butylcatechol, triiodine Potassium halide, N-nitrosophenylhydroxyamine aluminum salt and the like. Among these, N-nitrosophenylhydroxyamine aluminum salt is preferable from the viewpoint of storage stability and curability of the sample. The said polymerization inhibitor (F) may be used independently and may use 2 or more types together.

  The content of the polymerization inhibitor (F) is preferably 0.001 to 2 parts by weight, more preferably 0.005 to 0.5 parts by weight, particularly preferably 100 parts by weight of the thiol compound (B). Is 0.01 to 0.3 parts by weight. When the content is too small, the polymerization inhibiting effect tends to be insufficient, and when the content is too large, the curability tends to be inferior.

  The urethane (meth) acrylate compound (A), thiol compound (B), silica (C), photopolymerization initiator (D), ethylenically unsaturated monomer (E), and polymerization inhibitor (F). Other than the above, polymers such as polymethyl methacrylate, silane coupling agents, fillers, electrolyte salts, dyes and pigments, oils, plasticizers, waxes, desiccants, dispersants, wetting agents, emulsifiers, gelling agents , Stabilizers, antifoaming agents, leveling agents, thixotropic agents, antioxidants, flame retardants, fillers, reinforcing agents, matting agents, crosslinking agents, UV absorbers, light stabilizers, etc. It is. In addition, in order to impart antistatic properties and conductivity, it is also possible to blend a metal salt such as a lithium salt, a conductive filler such as a metal oxide, a conductive polymer, an antistatic agent, and the like.

Examples of the ultraviolet absorber include benzotriazole compounds such as benzophenone compounds, TINUVIN 900, 928, 1130 (manufactured by Ciba Specialty Chemicals), TINUVIN 400, 405, 460, 477DW, 479 (Ciba Specialty Chemicals). And the like, and the like.
Examples of the light stabilizer include hindered amine compounds such as TINUVIN111FDL, 292, 123, 144, 152, 5100 (manufactured by Ciba Specialty Chemicals).
These ultraviolet absorbers and light stabilizers may be used alone or in combination of two or more.
Moreover, what introduce | transduced active energy ray reactive groups, such as a (meth) acryloyl group, into these compounds is preferable from a durable point.

  Examples of the leveling agent include acrylic additives, silicone additives, modified silicone additives, fluorine additives, and the like.

  Specific examples of the acrylic additive include BYK-354 (manufactured by Big Chemie), Polyflow No. 7, no. 3, no. 54, no. 50E, No. 48, no. 300, no. 95, no. 460, no. 90, no. 90D-50, no. 64, no. 85S, No. 77, no. 75 (manufactured by Kyoeisha) and the like.

  Specific examples of the silicon-based additive and the modified silicon-based additive include TEGORad 2100, 2200N, 2250, 2300, 2500, 2600, 2700 (manufactured by Degussa), BYK-300, 333, UV3500, UV3510, UV3570, and Silken3700 ( Manufactured by Big Chemie), polyflow KL series (manufactured by Kyoeisha) such as polyflow KL-245, 260, 270, 280, 505, 510, 600, 800, granol 100, 115, 200, 400, 410, 420, 440, 450, Granol series (manufactured by Kyoeisha) such as B-1484, Floren TW-4000, ATF-2 (manufactured by Kyoeisha) and the like can be mentioned.

As specific examples of the fluorine-based additive, Megafac F-177, F-470, 475, 477, 479, 487 (manufactured by DIC), Fantent FTX-245F, 222F, 218G, 240G, 218, 240D ( Neos), BYK-340 (Bic Chemie) and the like.
These acrylic additives, silicone additives, modified silicone additives, and fluorine additives may be used alone or in combination of two or more. Moreover, what introduce | transduced active energy ray reactive groups, such as a (meth) acryloyl group, into these compounds is preferable from a durable point.

Although it does not specifically limit as a metal salt, For example, lithium salt, sodium salt, potassium salt, rubidium salt, cesium salt, magnesium salt, calcium salt etc. are mentioned.
Specifically, for example, Li (CF ₃ SO ₂ ) ₂ N, Li (CF ₃ SO ₂ ) ₃ C, LiCF ₃ SO ₃ , Mg {(CF ₃ SO ₂ ) ₂ N} ₂ , LiBF ₄ , LiClO ₄ , LiPF ₆ , LiAsF ₆ , LiSbF ₆ , LiB (C ₆ H ₅ ) ₄ , Mg {(CF ₃ SO ₂ ) ₃ C} ₂ , Mg (CF ₃ SO ₃ ) _{2 and the} like.

Among them, a metal _{salt, Li (CF 3 SO 2)} 2 N, Li (CF 3 SO 2) 3 C, LiCF 3 SO 3, LiBF 4, LiClO 4, LiPF 6, LiAsF 6, LiSbF 6, LiB (C _A lithium salt having a high degree of ion dissociation such as ₆ H ₅ ) ₄ and a lithium imide compound such as Li (CF ₃ SO ₂ ) ₂ N are preferable in terms of antistatic properties.

Thus, an active energy ray-curable resin composition containing the urethane (meth) acrylate compound (A), thiol compound (B) and silica (C) of the present invention is obtained.
This composition can be used by blending an organic solvent and adjusting the viscosity as necessary. Examples of such organic solvents include alcohols such as methanol, ethanol, propanol and n-, i-butanol, ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone and cyclohexanone, cellosolves such as ethyl cellosolve, toluene, xylene and the like. Aromatic ethers, glycol ethers such as propylene glycol monomethyl ether, acetates such as ethyl acetate and butyl acetate, and diacetone alcohol. These organic solvents may be used alone or in combination of two or more.

  When two or more types are used in combination, a combination of glycol ethers such as propylene glycol monomethyl ether and ketones such as methyl ethyl ketone and alcohols such as methanol, a combination of ketones such as methyl ethyl ketone and alcohols such as methanol, methanol From the viewpoint of the appearance of the coating film, it is preferable to use two or more alcohols such as alcohols in combination.

  In producing the active energy ray-curable resin composition of the present invention, urethane (meth) acrylate compound (A), thiol compound (B), silica (C), photopolymerization initiator (D), ethylenic The method for mixing the unsaturated monomer (E) and the polymerization inhibitor (F) is not particularly limited and can be mixed by various methods. Especially, since mixing (A), (E), and (B) without adding (F) may cause gelation, (1) A mixture of (A), (E), and (C) (B) and (F) mixed in advance, and finally (D) is mixed, (2) (F) is added to the mixture of (A), (E) and (C) and mixed. (B) is added, and finally (D) is mixed. (3) (F) is added to the mixture of (A) and (E), and (B) and (C) are added. Finally, (D) is mixed. (4) (B) and (F) mixed in advance are added to the mixture of (A) and (E), (C) is added, and (D) is finally added. A method of mixing these is preferably used. Further, using an organic solvent such as methyl isobutyl ketone, (i) a solution in which the organic solvent (F) is dissolved is prepared. (Ii) (A) and (E) are weighed, and (i) (Iii) The solution obtained in (ii) is added and mixed, (B) is added and mixed, (iv) (C) is added and mixed, and (v) (D) is added in this order. It is particularly preferred to do this.

The active energy ray-curable resin composition of the present invention is cured by irradiating active energy rays after applying it to an object.
Such an object is not particularly limited. For example, polyolefin resin such as polyethylene, polypropylene, polycyclopentadiene, polycarbonate, polyester, ABS resin, acrylic resin and the like (film, sheet, cup, etc.) ), Metal, glass and the like.

  In addition, polyethylene terephthalate film, especially polyethylene terephthalate film with easy adhesion treatment, triacetyl cellulose film, acrylic resin film, resin film containing alicyclic structure such as “ZEONOR” manufactured by ZEON Corporation or “ARTON” manufactured by JSR Corporation, etc. Application to this optical film is also useful in the present invention, and from the viewpoint of refractive index, the effect of the present invention is remarkably exhibited when applied to such an optical film.

  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 if it does not use 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 30-3000mJ / cm < ² >.
After the ultraviolet irradiation, heating can be performed as necessary to complete the curing.

  Thus, the active energy ray-curable resin composition containing the urethane (meth) acrylate compound (A), the thiol compound (B) and the silica (C) of the present invention is excellent in curling resistance and coated. Excellent film hardness and excellent curability, paint, adhesive, adhesive, adhesive, ink, protective coating, anchor coating, magnetic powder coating binder, sandblast coating It is useful as various film forming materials such as plate materials. Among them, it is very useful to use as a coating agent for optical applications using a plastic or film as a base material.

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 basis unless otherwise specified.

Synthesis example of urethane (meth) acrylate compound (A) [urethane (meth) acrylate compound [A-1]]
In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser and nitrogen gas inlet, 150.0 g (0.67 mol) of isophorone diisocyanate, 0.8 g of 2,6-di-tert-butylcresol, dibutyltin dilaurate 0.05 g was charged, and 850.0 g (1.90 mol) of pentaerythritol triacrylate (hydroxyl value 125.4 mg KOH / g) (manufactured by Osaka Organic Chemical Industry Co., Ltd., “Biscoat # 300”) at 60 ° C. or less for about 1 hour. The reaction was terminated when the residual isocyanate group reached 0.3%, and urethane (meth) acrylate compound [A-1] was obtained (resin concentration 100). %).
The weight average molecular weight of the obtained urethane (meth) acrylate compound [A-1] was 1100.

[Urethane (meth) acrylate compound [A ']]
A four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet is charged with 482.9 g (2.17 mol) of isophorone diisocyanate, 0.8 g of 4-methoxyphenol, and 0.13 g of dibutyltin dilaurate, At 60 ° C. or lower, 517.1 g (4.45 mol) of hydroxyethyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., “HEA”) was added dropwise in about 1 hour, and reacted at 60 ° C. for 8 hours. The reaction was terminated when it reached 3%, and urethane (meth) acrylate compound [A ′] was obtained (resin concentration 100%).
The weight average molecular weight of the obtained urethane (meth) acrylate compound [A ′] was 730.

The following were prepared as the thiol compound (B).
[Thiol compound [B-1]]
Tetraethylene glycol bis (3-mercaptopropionate) (manufactured by Sakai Chemical Co., Ltd., polyfunctional thiol “EGMP-4”)
[Thiol compound [B-2]]
Trimethylolpropane tris (3-mercaptopropionate) (manufactured by Sakai Chemical Co., Ltd., polyfunctional thiol “TMMP”)
[Thiol compound [B-3]]
Pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by Sakai Chemical Industry Co., Ltd., polyfunctional thiol “PEMP”)
[Thiol compound [B-4]]
Dipentaerythritol hexakis (3-mercaptopropionate) (manufactured by Sakai Chemical Co., Ltd., polyfunctional thiol “DPMP”)
[Thiol compound [B-5]]
Multifunctional thiol (manufactured by Sakai Chemical Co., Ltd. “DPMP-20P”)

The following were prepared as silica (C).
[Silica [C-1]]
Silica sol using methyl isobutyl ketone as a dispersion medium (manufactured by Nissan Chemical Co., Ltd., organosilica sol “MIBK-ST”, average particle size of 10 to 15 nanometers, concentration 30%)

The following were prepared as the photopolymerization initiator (D).
[Photoinitiator [D-1]]
1-hydroxycyclohexyl phenyl ketone (Ciba Specialty Chemicals, “Irgacure 184”)

The following were prepared as the ethylenically unsaturated monomer (E).
[Ethylenically unsaturated monomer [E-1]]
Dipentaerythritol pentaacrylate (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate)

The following were prepared as a polymerization inhibitor (F).
[Polymerization inhibitor [F-1]]
N-nitrosophenylhydroxyamine aluminum salt

Example 1
[Active energy ray-curable resin composition]
Said urethane (meth) acrylate type compound (A-1), thiol compound (B-1), silica (C-1), photoinitiator (D-1), ethylenically unsaturated monomer (E-1) The polymerization inhibitor (F-1) was blended at a ratio shown in Table 1 in terms of solid content, and diluted with methyl isobutyl ketone so that the solid content excluding the photopolymerization initiator and the polymerization inhibitor was 40%, An active energy ray-curable resin composition was obtained.

The obtained active energy ray-curable resin composition was placed on a polymethyl methacrylate (PMMA) plate with a bar coater No. No. 40 was applied so that the film thickness after drying was 12 μm, dried at 90 ° C. for 3 minutes, and then from a height of 18 cm to 5.1 m / min using a high pressure mercury lamp 80 W and one lamp. A three-pass ultraviolet irradiation (peak illuminance 65 mW / cm ² , integrated irradiation amount 230 mJ / cm ² ) was carried out at a conveyor speed, a cured coating film was formed, and the following evaluation was performed.

(Coating hardness)
About the cured coating film, pencil hardness was measured according to JISK5400.

(Abrasion resistance)
About the cured coating film, the degree of damage of the surface after visually reciprocating the steel wool (Bonstar # 0000, manufactured by Nippon Steel Wool Co., Ltd.) with a load of 100 g on the surface of the cured coating film was visually observed. The evaluation criteria are as follows.
○ ・ ・ ・ No scratches or scratches are inconspicuous △ ・ ・ ・ Some scratches are conspicuous × ・ ・ ・ Part of the coating film is peeled off due to scratches

Example 2
An active energy ray-curable resin composition was obtained in the same manner as in Example 1 except that the thiol compound (B-1) was changed to the thiol compound (B-2) in Example 1.

Example 3
An active energy ray-curable resin composition was obtained in the same manner as in Example 1 except that the thiol compound (B-1) was changed to the thiol compound (B-3) in Example 1.

Example 4
An active energy ray-curable resin composition was obtained in the same manner as in Example 1 except that the thiol compound (B-1) was changed to the thiol compound (B-4) in Example 1.

Example 5
An active energy ray-curable resin was obtained in the same manner as in Example 1 except that the thiol compound (B-1) was replaced with the thiol compound (B-5) and the polymerization inhibitor (F-1) was not used. A composition was obtained.

Comparative Example 1
In Example 1, an active energy ray-curable resin composition was obtained in the same manner as in Example 1 except that the thiol compound (B-1) and the polymerization inhibitor (F-1) were not used.

Comparative Example 2
In Example 1, the active energy ray-curable resin composition was obtained in the same manner as in Example 1, except that the urethane (meth) acrylate compound (A-1) was replaced with the urethane (meth) acrylate compound (A ′). Got.

  The compositions of the active energy ray-curable resin compositions of Examples and Comparative Examples are shown in [Table 1], and the evaluation results of the cured coating film are shown in [Table 2].

From the above evaluation results, the cured coating film obtained by curing the active energy ray-curable resin composition of Example 1 is excellent in both coating film hardness and scratch resistance, and can be usefully used as a coating agent. Is.
On the other hand, in Comparative Example 1 using the active energy ray-curable resin composition not containing a thiol compound, the coating film hardness was soft with HB, and the scratch resistance was low. It turns out that it is necessary for the sophistication.
Moreover, in the comparative example 2 using a bifunctional urethane (meth) acrylate type compound, it turns out that the coating-film hardness and abrasion resistance are inferior compared with Example 1. FIG.

  The active energy ray-curable resin composition of the present invention is excellent in coating film hardness and further exhibits an effect of excellent curability, and is a paint, a pressure-sensitive adhesive, an adhesive, an adhesive, an ink, and a protective coating. It is useful as various film forming materials such as a coating agent, an anchor coating agent, a magnetic powder coating binder, a sandblast coating, and a plate material. Among them, it is very useful to use as a coating agent for optical applications using a plastic or film as a base material.

Claims (8)

  An active energy ray-curable resin composition comprising a urethane (meth) acrylate compound (A) having three or more ethylenically unsaturated groups, a thiol compound (B), and silica (C). .   The urethane (meth) acrylate compound (A) has a urethane bond residue of an aliphatic polyvalent isocyanate compound and has 6 or more ethylenically unsaturated groups in the molecule. Item 2. The active energy ray-curable resin composition according to Item 1.   The active energy ray-curable resin composition according to claim 1 or 2, wherein the thiol compound (B) is a mercaptopropionate having 6 or more mercapto groups.   The active energy ray-curable resin composition according to any one of claims 1 to 3, wherein the silica (C) is contained in a silica sol in which silica having an average particle size of 100 nm or less is dispersed in an organic solvent. object.   The active energy ray-curable resin composition according to any one of claims 1 to 4, further comprising a photopolymerization initiator (D).   The active energy ray-curable resin composition according to any one of claims 1 to 5, further comprising an ethylenically unsaturated monomer (E) having two or more ethylenically unsaturated groups.   Furthermore, the polymerization inhibitor (F) is contained, The active energy ray hardening-type resin composition in any one of Claims 1-6 characterized by the above-mentioned.   A coating agent composition comprising the active energy ray-curable resin composition according to claim 1.