JP2022077644A - (meth)acrylic resin, coating, cured product and article - Google Patents

Abstract

To provide a (meth)acrylic resin having excellent dryability and weather resistance, a coating, a cured product and an article.SOLUTION: A (meth)acrylic resin is prepared by copolymerizing a polymerizable compound containing a polyfunctional methacrylate compound (A) and a compound having a polymerizable unsaturated group (B), different from the compound (A), in the presence of polymerization initiators (C), represented by formulas (1), (2) and (3), having an average amount of degradation X in the range of 0.00025-0.001 mol per unit time (minutes) in dropping reaction time.SELECTED DRAWING: None

Description

The present invention relates to (meth) acrylic resins, paints, cured products and articles.

Conventionally, various printing methods typified by lithographic printing, letterpress, intaglio printing, and stencil printing have been adopted in order to obtain printed matter based on paper, plastic, metal, etc., and inks based on this printing method are used. ing. In recent years, with the background of shortened delivery time of printed matter and environmental friendliness, the alternative use of oil-based ink, which has been conventionally used, to active energy ray-curable printing ink, which is quick-drying and does not use a solvent, is expanding. In particular, emphasis is placed on high-speed printing, and further speeding up of printing speed is desired.

In addition, diallyl phthalate resin has been widely used as a binder resin for active energy ray-curable printing ink, but in recent years, toxicity of diallyl phthalate, which is a raw material of the diallyl phthalate resin, has been pointed out, and toxicity instead There is a need to develop resin materials that are not concerned.

As the binder resin for active energy ray-curable printing ink other than the diallyl phthalate resin, for example, a polyfunctional isocyanate compound and 2-hydroxyethyl acrylate are reacted at a ratio of an excess of isocyanate groups, and then the obtained reaction is carried out. A urethane acrylate resin obtained by reacting an acid diol and a polyol with a residual isocyanate group of a product is known (see, for example, Patent Document 1). Such a urethane acrylate resin does not leave 2-hydroxyethyl acrylate, which is highly irritating to the skin, in the resin, and is excellent in safety and hygiene in handling printing inks, but has excellent drying properties, weather resistance, etc. The various performances of were not sufficient.

Therefore, a material having excellent drying property and weather resistance has been required.

Japanese Unexamined Patent Publication No. 2001-151848

An object to be solved by the present invention is to provide a (meth) acrylic resin, a paint, a cured product and an article having excellent drying properties and weather resistance.

As a result of diligent studies to solve the above problems, the present inventors have obtained a polyfunctional (meth) acrylate compound and a polymerizable compound containing a compound having a polymerizable unsaturated group other than the compound as a polymerization initiator. It is a (meth) acrylic resin obtained by copolymerizing in the presence of the above, and per unit time (minutes) in the dropping reaction time of the polymerization initiator represented by the formulas (1), (2) and (3). The present invention has been completed by finding that the above-mentioned problems can be solved by using a (meth) acrylic resin characterized in that the average decomposition amount of the above is in a specific range.

That is, in the present invention, a polymerizable compound containing a polyfunctional (meth) acrylate compound (A) and a compound (B) having a polymerizable unsaturated group other than the compound (A) is used as a polymerization initiator (C). A (meth) acrylic resin obtained by copolymerizing in the presence of the polymer, which is represented by the following formulas (1), (2) and (3), and has a unit time (unit time) in the dropping reaction time of the polymerization initiator (C). It relates to a (meth) acrylic resin, a paint, a cured product and an article, wherein the average decomposition amount X per minute) is in the range of 0.00025 to 0.001 mol.

（１）

(1)

（２）

(2)

（３）

(3)

n: Drop reaction time (minutes)
X _k : Decomposition amount (mol) of the polymerization initiator k minutes after the start of dropping.
Y _k : Amount of polymerization initiator present in the reaction field k minutes after the start of dropping (g)
Q: Amount of polymerization initiator charged (g)
A: Frequency factor of polymerization initiator (1 / h)
E: Activation energy of polymerization initiator (J / mol)
R: Gas constant 8.314 (J / K · mol)
T: Reaction temperature (° C)
M: Molecular weight of polymerization initiator (g / mol)

Since the (meth) acrylic resin of the present invention has excellent drying properties and weather resistance, it can be suitably used for printing inks, paints and the like.

The (meth) acrylic resin of the present invention contains a polymerizable compound containing a polyfunctional (meth) acrylate compound (A) and a compound (B) having a polymerizable unsaturated group other than the compound (A) as a polymerization initiator. It is obtained by copolymerizing in the presence of (C).

Examples of the compound (A) include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and tris [(meth) acryloyloxyethyl]. Isocyanurate, glycerintri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) ) Acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane hexa (meth) acrylate, etc. Can be mentioned. These compounds (A) can be used alone or in combination of two or more. Among these, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, and trimethylolpropane tetra (Meta) acrylate is preferred.

The amount of the compound (A) used is in the range of 10 to 90 mol% in the raw material of the (meth) acrylic resin, and a (meth) acrylic resin having excellent drying properties and weather resistance can be obtained. The range of ~ 50 mol% is preferable.

Examples of the compound (B) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl. (Meta) acrylate, hydroxypentyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3-butoxypropyl (meth) acrylate, 2-hydroxy-3-methoxypropyl (meth) acrylate , 2- (meth) acryloyloxyethyl-2-hydroxyethylphthalate, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, An aliphatic (meth) acrylate compound such as polypropylene glycol mono (meth) acrylate, glycerin mono (meth) acrylate, glycerin di (meth) acrylate, trimethylol propandi (meth) acrylate, and pentaerythritol tri (meth) acrylate; acrylic. 4-Hydroxyphenyl acid, β-hydroxyphenethyl acrylate, 4-hydroxyphenethyl acrylate, 1-phenyl-2-hydroxyethyl acrylate, 3-hydroxy-4-acetylphenyl acrylate, 2-hydroxy-3-phenoxypropyl Aromatic ring-containing (meth) acrylate compounds such as acrylates; the (meth) acrylate compounds and various types such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether. Polyether-modified (meth) acrylate compounds obtained by ring-open polymerization with a cyclic ether compound; lactone-modified (meth) acrylate compounds obtained by polycondensation of the (meth) acrylate compound with a lactone compound such as ε-caprolactone. Compounds having hydroxyl groups and polymerizable unsaturated groups, such as polyol acrylate compounds such as monohydroxy (meth) acrylate compounds, trimethylol propane mono (meth) acrylates, pentaerythritol mono (meth) acrylates, and pentaerythritol di (meth) acrylates. (Meta) acrylic acid, Examples thereof include β-carboxyethyl (meth) acrylate, (meth) acrylic acid dimer, ω-carboxy-polycaprolactone mono (meth) acrylate, maleic acid, itaconic acid and other compounds having a carboxyl group and a polymerizable hydroxyl group.

Further, as the compound (B), monofunctional acrylates and bifunctional acrylates other than those exemplified above, and aromatic compounds having a polymerizable unsaturated group can also be used.

Examples of the monofunctional acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, and hexyl. (Meta) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isopentyl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, etc. Alkyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl methacrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, tricyclodecanemonomethylol (meth) having 1 to 18 carbon atoms. Examples thereof include acrylate, acryloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and (meth) acryloylmorpholine.

Examples of the bifunctional acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and di. Propylene Glycol Di (Meta) Acrylic, Tripropylene Glycol Di (Meta) Acrylic, Polypropylene Glycol Di (Meta) Acrylic, Butylene Glycol Di (Meta) Acrylic, Pentyl Glycol Di (Meta) Acrylic, Neopentyl Glycol Di (Meta) Acrylic, Hydroxypivalyl hydroxypivalate di (meth) acrylate, hydroxypivalyl hydroxypivalate dicaprolactonate di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,2-hexanediol di (meth) Acrylate, 1,5-hexanediol di (meth) acrylate, 2,5-hexanediol di (meth) acrylate, 1,7-heptanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,2-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,2-decanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1, 12-Dodecanediol di (meth) acrylate, 1,2-dodecanediol di (meth) acrylate, 1,14-tetradecanediol di (meth) acrylate, 1,2-tetradecanediol di (meth) acrylate, 1,16- Hexadecanediol di (meth) acrylate, 1,2-hexadecanediol di (meth) acrylate, 2-methyl-2,4-pentanediol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) Acrylate, 2-methyl-2-propyl-1,3-propanediol di (meth) acrylate, 2,4-dimethyl-2,4-pentanediol di (meth) acrylate, 2,2-diethyl-1,3- Propane dioldi (meth) acrylate, 2,2,4-trimethyl-1,3-pentanediol di (meth) acrylate, dimethylol octanedi (meth) acrylate, 2-ethyl-1,3-hexanediol di ( Meta) acrylate, 2,5-dimethyl-2,5-hexane Didioldi (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanedioldi (meth) acrylate, 2,4-diethyl-1, 5-Pentanediol di (meth) acrylate, tricyclodecanedimethylol di (meth) acrylate, tricyclodecanedimethylol dicaprolactonate di (meth) acrylate, bisphenol A tetraethylene oxide adduct di (meth) acrylate, bisphenol F tetraethylene oxide adduct di (meth) acrylate, bisphenol S tetraethylene oxide adduct di (meth) acrylate, water-added bisphenol A tetraethylene oxide adduct di (meth) acrylate, water-added bisphenol F tetraethylene oxide adduct di (Meta) acrylate, water-added bisphenol A di (meth) acrylate, water-added bisphenol F di (meth) acrylate, bisphenol A tetraethylene oxide adduct dicaprolactonate di (meth) acrylate, bisphenol F tetraethylene oxide adduct deca Examples thereof include prolaconate di (meth) acrylate.

Examples of the aromatic compound having a polymerizable unsaturated group include styrene, alkyl-substituted styrene, halogen-substituted styrene, benzyl (meth) acrylate, phenyl (meth) acrylate, and phenoxyethyl (meth) acrylate. , Phenoxypolyethylene glycol (meth) acrylice, biphenyl (meth) acrylicate, nonylphenyl (meth) acrylicate, nonylphenoxyethyl (meth) acrylicate, nonylphenoxypolyethylene glycol (meth) acrylice -To, cumylphenol (meth) acrylic, cumylphenoxyethyl (meth) acrylicate, cumylphenoxy polyethylene glycol (meth) acrylicate, o-phenylphenol (meth) acrylicate. , Ethoxylated o-phenylphenyl (meth) acrylate, tribromophenyl (meth) acrylate, and EO-modified tribromophenyl (meth) acrylate, vinyl toluene and the like.

These compounds (B) can be used alone or in combination of two or more. Among these, since a (meth) acrylic resin having excellent drying properties and weather resistance can be obtained, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate can be obtained. , Tart-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid, styrene, benzyl (Meta) Acrylate and vinyl toluene are preferable.

The amount of the compound (B) used is in the range of 10 to 90 mol% in the raw material of the (meth) acrylic resin, and a (meth) acrylic resin having excellent drying properties and weather resistance can be obtained. The range of ~ 90 mol% is preferable.

As the polymerization initiator (C), the average decomposition amount X per unit time (minutes) in the dropping reaction time represented by the following formulas (1), (2) and (3) is 0.00025 to 0. Those in the range of 001 mol are used.

（１）

(1)

（２）

(2)

（３）

(3)

n: Drop reaction time (minutes)
X _k : Decomposition amount (mol) of the polymerization initiator k minutes after the start of dropping.
Y _k : Amount of polymerization initiator present in the reaction field k minutes after the start of dropping (g)
Q: Amount of polymerization initiator charged (g)
A: Frequency factor of polymerization initiator (1 / h)
E: Activation energy of polymerization initiator (J / mol)
R: Gas constant 8.314 (J / K · mol)
T: Reaction temperature (° C)
M: Molecular weight of polymerization initiator (g / mol)

The dropping reaction time n in the formulas (1) and (3) is preferably 60 to 600 (minutes) because a (meth) acrylic resin having excellent drying properties, ink fluidity, and high-speed printing suitability can be obtained. ..

As the frequency factor A of the polymerization initiator in the formula (2), a (meth) acrylic resin having excellent drying properties, ink fluidity, and high-speed printing suitability can be obtained. Therefore, 1.000 × 10 ¹² to 1. 000 × 10 ²⁵ (1 / h) is preferable.

The activation energy E of the polymerization initiator in the formula (2) is 100,000 to 200,000 J / because a (meth) acrylic resin having excellent drying properties, ink fluidity, and high-speed printing suitability can be obtained. mol is preferable.

The reaction temperature T in the formula (2) is preferably 60 to 180 (° C.) because a (meth) acrylic resin having excellent drying properties, ink fluidity, and high-speed printing suitability can be obtained.

The molecular weight M of the polymerization initiator in the formulas (2) and (3) is 50 to 1,000 g / g because a (meth) acrylic resin having excellent drying properties, ink fluidity, and high-speed printing suitability can be obtained. mol is preferable.

Examples of the polymerization initiator (C) include 2,2'-azobis (2-methylpropionamidine) dihydrochloride and 2,2'-azobis (2- (2-imidazolin-2-yl) propane) di. Hydrochloride, 2,2'-azobis (2-methyl-N- (2-hydroxyethyl) propionamide), 2,2'-azobis (N- (2-propenyl) -2-methylpropionamide), 2, Azo initiators such as 2'-azobis (N-butyl-2-methylpropionamide), azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), methylethylketone peroxide, methylisobutyrieketone. Ketone peroxide compounds such as peroxide, acetylacetone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, 1,1-bis (tert-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis ( tert-Hexylperoxy cyclohexane, 1,1-bis (tert-butylperoxy) -2-methylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, 2,2-bis (tert-butylperoxy) Peroxyketal compounds such as oxy) butane, butyl 4,4-bis (tert-butylperoxy) pentanate, 1,1-di (tert-hexylperoxy) cyclohexane, 1,1,3,3-tetramethyl Hydroperoxide compounds such as butylhydroperoxide, cumenehydroperoxide, tert-butylhydroperoxide, p-menthan hydroperoxide, diisopropylbenzenehydroperoxide, dicumyl peroxide, 2,5-dimethyl-2,5 -Bis (tert-butylperoxy) hexane, 1,3-bis (tert-butylperoxyisopropyl) hexane, tert-butylcumyl peroxide, di-tert-butyl peroxide, di-tert-hexyl peroxide, 2,5 -Dialkyl peroxide compounds such as dimethyl-2,5-bis (tert-butylperoxy) hexin-3, diisobutyryl peroxide, bis-3,5,5-trimethylhexanol peroxide, dilauroyl peroxide, dibenzoylper Diacyl peroxide such as oxide, m-toluylbenzoyl peroxide, succinic acid peroxide, etc. Combination, 1,1,3,3-tetramethylbutylperoxyneodecanoate, α-cumylperoxyneodecanoate, tert-butylperoxyneodecanoate, tert-hexylperoxyneodecanoate , Tert-Butylperoxyneoheptanoate, tert (hexylperoxypivalate, tert-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, tert- Amylperoxy-2-ethylhexanoate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyisobutyrate, di-tert-butylperoxyhexahydroterephthalate, 1,1,3 3-Tetramethylbutylperoxy-3,5,5-trimethylhexanoate, tert-amylperoxy3,5,5-trimethylhexanoate, tert-butylperoxy-3,5,5-trimethylhexanoate , Tert-Butylperoxyacetate, tert-butylperoxybenzoate, dibutylperoxytrimethyl adipate, di-tert-butylperoxide, 2,5-dimethyl-2,5-di-2-ethylhexanoylperoxyhexane, tert -Hexylperoxy-2-ethylhexanoate, tert-hexylperoxyisopropyl monocarbonate, tert-butylperoxylaurate, tert-butylperoxyisopropylmonocarbonate, tert-butylperoxy-2-ethylhexylmonocarbonate, Peroxide initiators such as peroxyester compounds such as 2,5-dimethyl-2,5-di-benzoylperoxyhexane, tert-hexylperoxybenzoate, tert-hexylperoxy-acetate, 2-methyl- Acetphenone-based initiators such as 1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one and 1-hydroxycyclohexylphenylketone, benzoin-based initiators such as benzoin and benzoinethyl ether, and benzophenone such as benzophenone. Examples thereof include a system initiator, a phosphorus-based initiator such as acylphosphine oxide, and a sulfur-based initiator such as thioxanthone.

These polymerization initiators (C) may be used alone or in combination of two or more. Further, among these, a compound represented by the following general formula (C-1) in the molecule is preferable because a (meth) acrylic resin having excellent drying property and weather resistance can be obtained.

[In the formula (C-1), R ¹ and R ² are independently hydrogen atoms or hydrocarbon groups having 1 to 3 carbon atoms, and Y ¹ and Y ² are independent methyl groups, respectively. Alternatively, it is a nitrile group which is a polar group, and Z ¹ and Z ² are independently polar groups such as a methyl group, an imidazoline group, an amidin group and an amide group. ]

Examples of the compound represented by the general formula (C-1) include 2,2'-azobis (2-methylpropionamidine) dihydrochloride and 2,2'-azobis (2- (2-imidazolin-2). -Il) Propane) dihydrochloride, 2,2'-azobis (2-methyl-N- (2-hydroxyethyl) propionamide), 2,2'-azobis (N- (2-propenyl) -2-methyl) Propionamide), 2,2'-azobis (N-butyl-2-methylpropionamide) and the like. Among these, azobisisobutyronitrile and 2,2'-azobis (2-methylbutyronitrile) azobisisobuty are obtained because a (meth) acrylic resin having further excellent drying and weather resistance can be obtained. Lonitrile, 2,2'-azobis (2-methylbutyronitrile) is preferred.

The method for producing the (meth) acrylic resin of the present invention is to copolymerize the compound (A) and the polymerizable compound containing the compound (B) in the presence of the polymerization initiator (C). , The average decomposition amount X per unit time (minutes) of the polymerization initiator (C) represented by the formulas (1), (2) and (3) in the dropping reaction time is 0.00025 to 0.001 mol. As long as it is within the above range, it can be produced by a known method without particular limitation, and various conditions in the production can be appropriately set according to the raw materials to be used and the amount thereof. For example, a method of first adding a part of raw materials to a reaction vessel, heating the mixture, and then performing a polymerization reaction while dropping the remaining raw materials to produce the product. A method of producing by carrying out a polymerization reaction while dropping a mixture of raw materials to be used, an organic solvent is added to a reaction vessel, and the mixture is heated to a temperature higher than the boiling point of the organic solvent under closed pressure conditions, and then the mixture of raw materials used for the reaction is prepared. Examples thereof include a method of producing by performing a polymerization reaction while dropping.

The (meth) acrylic resin of the present invention can be used as a one-component curable paint, and is also two-component curable containing the (meth) acrylic resin of the present invention and a curing agent such as an amino resin or a polyisocyanate compound. It can also be used as a mold paint.

Further, it can also be used as an active energy ray-curable coating material containing the (meth) acrylic resin, the acrylate monomer and the photopolymerization initiator of the present invention.

Examples of the isocyanate compound include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; norbornan diisocyanate, isophorone diisocyanate, and water. Alicyclic diisocyanate compounds such as supplemented xylylene diisocyanate and hydrogenated diphenylmethane diisocyanate; tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalenedi isocyanate, 4,4'-diisocyanato-3, Aromatic diisocyanate compounds such as 3'-dimethylbiphenyl and o-trizine diisocyanate; polymethylenepolyphenylpolyisocyanate having a repeating structure represented by the following structural formula (1); these isocyanurate modified products, biuret modified products, allophanates. Examples include denatured compounds. Further, these isocyanate compounds may be used alone or in combination of two or more.

［式（１）中、Ｒ^１はそれぞれ独立して、水素原子、または炭素原子数１～６の炭化水素基の何れかである。Ｒ^２はそれぞれ独立して、炭素原子数１～４のアルキル基、または構造式（１）で表される構造部位と＊印が付されたメチレン基を介して連結する結合点の何れかである。ｌは０または１～３の整数であり、ｍは１～１５の整数である。］

[In the formula (1), R ¹ is either a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms independently. Each of R ² is independently an alkyl group having 1 to 4 carbon atoms, or a bond point connected to a structural site represented by the structural formula (1) via a methylene group marked with *. be. l is an integer of 0 or 1 to 3, and m is an integer of 1 to 15. ]

Examples of the acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, and 2-ethylhexyl (meth). An aliphatic mono (meth) acrylate compound such as acrylate and octyl (meth) acrylate; an alicyclic mono (meth) acrylate compound such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and adamantyl mono (meth) acrylate; Heterocyclic mono (meth) acrylate compounds such as meta) acrylates and tetrahydrofurfuryl acrylates; benzyl (meth) acrylates, phenyl (meth) acrylates, phenylbenzyl (meth) acrylates, phenoxy (meth) acrylates, phenoxyethyl (meth). Aromatic mono (meth) acrylate compounds such as acrylates, phenoxyethoxyethyl (meth) acrylates, 2-hydroxy-3-phenoxypropyl (meth) acrylates, phenoxybenzyl (meth) acrylates, and phenylphenoxyethyl (meth) acrylates. (Meta) Acrylate Compound: A polyoxyalkylene chain such as a (poly) oxyethylene chain, a (poly) oxypropylene chain, or a (poly) oxytetramethylene chain was introduced into the molecular structure of the various mono (meth) acrylate monomers. (Poly) Oxyalkylene-modified mono (meth) acrylate compound; A lactone-modified mono (meth) acrylate compound in which a (poly) lactone structure is introduced into the molecular structure of the various mono (meth) acrylate compounds; ethylene glycol di (meth). An aliphatic di (meth) acrylate compound such as acrylate, propylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate; 1,4-cyclohexane. Alicyclic di (meth) acrylates such as dimethanol di (meth) acrylates, norbornan di (meth) acrylates, norbornan dimethanol di (meth) acrylates, dicyclopentanyl di (meth) acrylates, and tricyclodecane dimethanol di (meth) acrylates. (Meta) acrylate compound; Aromatic di (meth) ac of biphenol di (meth) acrylate, bisphenol di (meth) acrylate, etc. Relate compound; Poly in which (poly) oxyalkylene chains such as (poly) oxyethylene chain, (poly) oxypropylene chain, and (poly) oxytetramethylene chain are introduced into the molecular structure of the various di (meth) acrylate compounds. Oxyalkylene-modified di (meth) acrylate compound; lactone-modified di (meth) acrylate compound in which a (poly) lactone structure is introduced into the molecular structure of the various di (meth) acrylate compounds; trimetylol propantri (meth) acrylate, An aliphatic tri (meth) acrylate compound such as glycerin tri (meth) acrylate; (poly) oxyethylene chain, (poly) oxypropylene chain, (poly) oxytetra in the molecular structure of the aliphatic tri (meth) acrylate compound. A (poly) oxyalkylene-modified tri (meth) acrylate compound introduced with a (poly) oxyalkylene chain such as a methylene chain; a lactone-modified compound having a (poly) lactone structure introduced into the molecular structure of the aliphatic tri (meth) acrylate compound. Tri (meth) acrylate compounds; tetrafunctional or higher functional aliphatic poly (meth) acrylate compounds such as pentaerythritol tetra (meth) acrylate, ditrimethylol propanetetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate; A tetrafunctional or higher (poly) in which a (poly) oxyalkylene chain such as a (poly) oxyethylene chain, a (poly) oxypropylene chain, or a (poly) oxytetramethylene chain is introduced into the molecular structure of a poly (meth) acrylate compound. Oxyalkylene-modified poly (meth) acrylate compounds; examples thereof include tetrafunctional or higher functional lactone-modified poly (meth) acrylate compounds in which a (poly) lactone structure is introduced into the molecular structure of the aliphatic poly (meth) acrylate compound. These acrylate monomers may be used alone or in combination of two or more.

Examples of the photopolymerization initiator include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-. Hydroxy-2-methyl-1-propane-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethane-1-one, diphenyl (2,4,6-trimethoxybenzoyl) phosphenyl Oxide, 2,4,6-trimethylbenzoyldiphenylphosphenyl oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphenyl oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1- On, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone and the like can be mentioned.

Examples of commercially available products of the other photopolymerization initiator include "Omnirad 1173", "Omnirad 184", "Omnirad 127", "Omnirad 2959", "Omnirad 369", "Omnirad 379", and "Omnirad 90". "Omnirad 4265", "Omnirad 1000", "Omnirad 651", "Omnirad TPO", "Omnirad 819", "Omnirad 2022", "Omnirad 2100", "Omnirad 2100", "Omnirad 754", "Omnirad" "Omnirad 81" (manufactured by IGM Resins); "KAYACURE DETX", "KAYACURE MBP", "KAYACURE DMBI", "KAYACURE EPA", "KAYACURE OA" (manufactured by Nippon Kayaku Co., Ltd.); "Vicure 10" "Vicure 55" (manufactured by Stoffa Chemical); "Trigonal P1" (manufactured by Akzo Nobel), "SANDORAY 1000" (manufactured by SANDOZ); "DEAP" (manufactured by Upjon Chemical), "QuantaQuant" , "Chemistry EPD" (manufactured by Ward Brenkinsop); "Runtecure 1104" (manufactured by Runtec) and the like. These photopolymerization initiators may be used alone or in combination of two or more.

The amount of the photopolymerization initiator added is preferably in the range of 0.5 to 20% by mass in the active energy ray-curable resin composition, for example.

Further, since the active energy ray-curable resin composition can improve the curability of the cured coating film of the active energy ray-curable resin composition, if necessary, a photosensitizer is further added to cure the active energy ray-curable resin composition. It can also improve sex.

Examples of the photosensitizer include 2,4,6-trimethylbenzophenone, 2,3,4-trimethylbenzophenone, 4-phenylbenzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 4- (1,3-). Acryloyl-1,4,7,10,13-pentaoxotridecyl) benzophenone, methyl-o-benzoylbenzoate, [4- (methylphenylthio) phenyl] phenylmethanone, (4-benzoylbenzyl) trimethylammonium chloride, 2-Hydroxy-2-methyl-1-phenylpropane-1-one, 1- (4-isopropylphenyl) 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-hydroxy-cyclohexyl-phenylketone , 2-Hydroxy-2-methyl-1-styrylpropan-1-one polymer, diethoxyacetophenone, dibutoxyacetophenone, benzoinmethyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin normal butyl ether, aliphatic Examples thereof include amine compounds such as amines and aromatic amines, urea compounds such as o-tolylthiourea, sulfur compounds such as sodium diethyldithiophosphate and s-benzylisothiuronium-p-toluenesulfonate. These photosensitizers can be used alone or in combination of two or more.

The cured product of the present invention can be obtained by irradiating the paint with heat treatment or active energy rays. The conditions for the heat treatment are not particularly limited, and may be appropriately selected depending on the type of resin and curing agent used. For example, it is preferable to perform the heat treatment in the range of 60 to 180 ° C, and more preferably the range of 60 to 120 ° C. The curing time varies depending on the curing temperature and the like, but is preferably in the range of, for example, 80 to 120 ° C. for 10 to 30 minutes.

Examples of the active energy ray include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When ultraviolet rays are used as the active energy rays, they may be irradiated in an atmosphere of an inert gas such as nitrogen gas or in an air atmosphere in order to efficiently carry out the curing reaction by the ultraviolet rays.

As an ultraviolet ray generation source, an ultraviolet lamp is generally used from the viewpoint of practicality and economy. Specific examples thereof include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, and LEDs.

The integrated light amount of the active energy rays is not particularly limited, but is preferably 0.1 to 50 kJ / m ² , and more preferably 0.5 to 10 kJ / m ² . When the integrated light amount is in the above range, it is preferable because the generation of the uncured portion can be prevented or suppressed.

The irradiation of the active energy rays may be performed in one step or may be divided into two or more steps.

The article of the present invention has a coating film made of the cured product. Examples of the article include plastic molded products such as mobile phones, home appliances, automobile interior / exterior materials, and OA equipment, semiconductor devices, display devices, image pickup devices, and the like.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The present invention is not limited to the examples listed below.

In this example, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured under the following conditions using a gel permission chromatograph (GPC).

Measuring device; HLC-8220 manufactured by Tosoh Corporation
Column; Guard column H _XL -H manufactured by Tosoh Corporation
+ TSKgel G5000HXL manufactured by Tosoh Corporation
+ TSKgel G4000HXL manufactured by Tosoh Corporation
+ TSKgel G3000HXL manufactured by Tosoh Corporation
+ TSKgel G2000HXL manufactured by Tosoh Corporation
Detector; RI (Differential Refractometer)
Data processing: SC-8010 manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Solvent tetrahydrofuran
Flow velocity 1.0 ml / min Standard; Polystyrene sample; 0.4% by mass in terms of resin solid content Tetrahydrofuran solution filtered through a microfilter (100 μl)

(Example 1: Synthesis of acrylic resin (1))
170 parts by mass of xylene was placed in a flask equipped with a stirring rod, a temperature sensor, and a condenser, dry nitrogen was flowed, and the temperature was raised to 140 ° C. while stirring. Trimethylolpropane triacrylate (hereinafter abbreviated as "TMPTA") 60 parts by mass, acrylic acid 1 part by mass, styrene 8 parts by mass, methylmethacrylate 31 parts by mass, tert-butylperoxybenzoate (manufactured by Nichiyu Co., Ltd. " PERBUTHYL Z ”, frequency factor A; 2.47 × 10 ¹⁸ 1 / h, activation energy E; 141,300 J / mol, molecular weight M; 194 mol / g) 40 parts by mass, 40 parts by mass of xylene mixed xylene solution is added dropwise. The acrylic polymerization reaction was carried out by dropping from the funnel over 4 hours. After confirming that the viscosity and the non-volatile content became constant, the reaction was stopped and the mixture was cooled to room temperature. The obtained polymerization solution was subjected to solvent removal treatment with a thin film distillation apparatus to obtain an acrylic resin (1) having a number average molecular weight (Mn) of 1,100 and a weight average molecular weight (Mw) of 21,300. The average decomposition amount X per unit time (minutes) during the dropping reaction time of the polymerization initiator was 0.000797 mol. [In formula (1), n; 240 minutes, in formula (2), Y _k ; calculated by formula (3) (Q; 40 g, M; 194 g / mol), A; 2.47 × 10 ¹⁸ 1 / h. , R; 8.314J / K · mol, T; 140 (° C.)]

(Example 2: Synthesis of acrylic resin (2))
110.5 parts by mass of toluene was charged in a pressure-resistant flask equipped with a stirring rod, a temperature sensor, and a condenser, dry nitrogen was flowed, and the temperature was raised to 130 ° C. while stirring. 30 parts by mass of TMPTA, 1 part by mass of acrylic acid, 18 parts by mass of styrene, 31 parts by mass of methyl methacrylate, 20 parts by mass of normal butyl methacrylate, tert-butylperoxy-2-ethylhexanoate ("PERBUTHYLO" manufactured by Nichiyu Co., Ltd. , Frequency factor A; 1.23 × 10 ¹⁷ 1 / h, activation energy E; 126,000 J / mol, molecular weight M; 216 mol / g) 15 parts by mass, 50 parts by mass of toluene A mixed toluene solution was added from the dropping funnel. Acrylic polymerization was carried out by dropping over 4 hours. Then, it kept at 160 degreeC for 2 hours, reduced the pressure and cooled to room temperature. The obtained polymerization solution was subjected to solvent removal treatment with a thin film distillation apparatus to obtain an acrylic resin (2) having a number average molecular weight (Mn) of 1,300 and a weight average molecular weight (Mw) of 14,700. The average decomposition amount X per unit time (minutes) during the dropping reaction time of the polymerization initiator was 0.000287 mol.

(Example 3: Synthesis of acrylic resin (3))
115 parts by mass of toluene was charged in a pressure-resistant flask equipped with a stirring rod, a temperature sensor, and a condenser, dry nitrogen was flowed, and the temperature was raised to 160 ° C. while stirring. TMPTA 50 parts by mass, acrylic acid 1 part by mass, styrene 10 parts by mass, 2-hydroxymethylmethacrylate 8 parts by mass, methylmethacrylate 31 parts by mass, tert-butylperoxybenzoate (“PERBUTHYL Z” manufactured by Nichiyu Co., Ltd., frequency factor A 2.47 × 10 ¹⁸ 1 / h, activation energy E; 141,300 J / mol, molecular weight M; 194 mol / g) 20 parts by mass, 50 parts by mass of toluene A mixed toluene solution was added from the dropping funnel over 4 hours. Acrylic polymerization was carried out by dropping. Then, it kept at 160 degreeC for 2 hours, reduced the pressure and cooled to room temperature. The obtained polymerization solution was subjected to solvent removal treatment with a thin film distillation apparatus to obtain an acrylic resin (3) having a solid content hydroxyl value of 35, a number average molecular weight (Mn) of 1,200, and a weight average molecular weight (Mw) of 20,700. The average decomposition amount X per unit time (minutes) during the dropping reaction time of the polymerization initiator was 0.000425 mol.

(Example 4: Synthesis of acrylic resin (4))
115 parts by mass of toluene was charged in a pressure-resistant flask equipped with a stirring rod, a temperature sensor, and a condenser, dry nitrogen was flowed, and the temperature was raised to 160 ° C. while stirring. TMPTA 55 parts by mass, acrylic acid 1 part by mass, styrene 24 parts by mass, vinyl toluene 10 parts by mass, benzyl acrylate 10 parts by mass, di-tert-butyl peroxide (“PERBUTHYLD” manufactured by Nichiyu Co., Ltd., frequency factor A; 2. 33 × 10 ¹⁹ 1 / h, activation energy E; 155,800 J / mol, molecular weight M; 146 mol / g) 20 parts by mass, 50 parts by mass of toluene A mixed toluene solution was added dropwise from the dropping funnel over 4 hours. Acrylic polymerization was performed. Then, it kept at 160 degreeC for 2 hours, reduced the pressure and cooled to room temperature. The obtained polymerization solution was subjected to solvent removal treatment with a thin film distillation apparatus to obtain an acrylic resin (4) having a number average molecular weight (Mn) of 2,800 and a weight average molecular weight (Mw) of 38,300. The average decomposition amount X per unit time (minutes) during the dropping reaction time of the polymerization initiator was 0.000533 (mol).

(Comparative Example 1: Synthesis of acrylic resin (R1))
160 parts by mass of toluene was charged in a flask equipped with a stirring rod, a temperature sensor, and a condenser, dry nitrogen was flowed, and the temperature was raised to 105 ° C. while stirring. , Acrylic acid 3 parts by mass, styrene 40 parts by mass, vinyl toluene 30 parts by mass, benzyl acrylate 27 parts by mass, tert-butylperoxy-2-ethylhexanoate ("PERBUTHYLO" manufactured by Nichiyu Co., Ltd., frequency factor A 1.23 × 10 ¹⁷ 1 / h, activation energy E; 126,000 J / mol, molecular weight M; 216 mol / g) 20 parts by mass, 20 parts by mass of toluene A mixed toluene solution was added from the dropping funnel over 4 hours. Acrylic polymerization was carried out by dropping. After confirming that the viscosity and the non-volatile content became constant, the reaction was stopped and the mixture was cooled to room temperature. The obtained polymerization solution was subjected to solvent removal treatment with a thin film distillation apparatus to obtain an acrylic resin (R1) having a number average molecular weight (Mn) of 1,200 and a weight average molecular weight (Mw) of 4,200. The average decomposition amount X per unit time (minutes) during the dropping reaction time of the polymerization initiator was 0.000351 (mol).

(Comparative Example 2: Synthesis of acrylic resin (R2))
146 parts by mass of toluene was charged in a flask equipped with a stirring rod, a temperature sensor, and a condenser, dry nitrogen was flowed, and the temperature was raised to 105 ° C. while stirring. TMPTA 50 parts by mass, acrylic acid 1 part by mass, styrene 18 parts by mass, methyl methacrylate 31 parts by mass, tert-butylperoxybenzoate (“PERBUTHYL Z” manufactured by Nichiyu Co., Ltd., frequency factor A; 2.47 × 10 ¹⁸ 1 / h, Activation energy E; 141,300 J / mol, molecular weight M; 194 mol / g) 4 parts by mass, 10 parts by mass of toluene A mixed toluene solution was added dropwise from the dropping funnel to perform acrylic polymerization. The resin viscosity in the flask clearly increased from 2 hours after the start of the dropping, and then gelled. As a result, an acrylic resin could not be obtained. Similar to Example 1, the average decomposition amount X per unit time (minutes) during the dropping reaction time of the polymerization initiator calculated assuming that the mixed toluene solution was dropped for 4 hours was 0.0000118 (mol). )Met.

(Comparative Example 3: Synthesis of Acrylic Resin (R3))
200 parts by mass of xylene was placed in a flask equipped with a stirring rod, a temperature sensor, and a condenser, dry nitrogen was flowed, and the temperature was raised to 140 ° C. while stirring. TMPTA 60 parts by mass, acrylic acid 1 part by mass, styrene 8 parts by mass, methyl methacrylate 31 parts by mass, tert-butylperoxybenzoate (“PERBUTHYL Z” manufactured by Nichiyu Co., Ltd., frequency factor A; 2.47 × 10 ¹⁸ 1 / h, Activation energy E; 141,300 J / mol, molecular weight M; 194 mol / g) 70 parts by mass and 55 parts by mass of xylene was added dropwise from the dropping funnel over 4 hours to carry out an acrylic polymerization reaction. .. After confirming that the viscosity and the non-volatile content became constant, the reaction was stopped and the mixture was cooled to room temperature. The obtained polymerization solution was subjected to solvent removal treatment with a thin film distillation apparatus to obtain an acrylic resin (R3) having a number average molecular weight (Mn) of 550 and a weight average molecular weight (Mw) of 6,700. The average decomposition amount X per unit time (minutes) during the dropping reaction time of the polymerization initiator was 0.00140 (mol).

Table 1 shows the compositions of the acrylic resins (1) to (4) obtained in Examples 1 to 4 and the acrylic resins (R1) to (R3) obtained in Comparative Examples 1 to 3.

The abbreviations in Table 1 indicate the following.
STM: Styrene MMA: Methyl methacrylate nBMA: Normal butyl methacrylate V-Toluene: Vinyl toluene BZA: benzyl acrylate MMA: Methyl methacrylate TMPTA: Trimethylolpropane Triacrylate AA: Acrylic acid HEMA: 2-Hydroxyethyl methacrylate ABN-E: 2, 2'-azobis (2-methylbutyronitrile)
PO: tert-butylperoxy-2-ethylhexanoate PZ: tert-butylperoxybenzoate PD: di-tert-butylperoxide

In addition, "-" in "number average molecular weight", "weight average molecular weight" and "dispersity" in Table 1 indicates that measurement is impossible due to gelation.

(Examples 5 to 8: Preparation of printing inks (1) to (4))
After mixing each component in the ratio shown in Table 2 below and stirring with a mixer (single-axis dissolver), the mixture is kneaded using a 3-roll mill to obtain printing inks (1) to (4). rice field.

(Comparative Examples 4 and 5: Preparation of printing inks (R1) and (R2))
After mixing each component in the ratio shown in Table 2 below and stirring with a mixer (single-axis dissolver), the mixture is kneaded using a 3-roll mill to obtain printing inks (R1) and (R2). rice field.

The following evaluation was performed using the printing inks obtained in the above Examples and Comparative Examples.

[Evaluation method of ink drying property]
Using a simple color expander (“RI tester” manufactured by Hoei Seiko Co., Ltd.), using 0.10 ml of the printing ink, spread evenly on the rubber roll and metal roll of the RI tester, and use transparent PET tack paper (DIC Co., Ltd.). A color-developed product was produced by spreading the color evenly on the surface of "Dytac UVPET Transparent 25EMH-S") manufactured in an area of about 220 cm2. After the printing ink was applied, the developed matter was irradiated with ultraviolet rays (UV) to cure the printing ink, and a printed matter was obtained. Specifically, using a water-cooled metal halide lamp (output 100 W / cm 1 lamp) and a UV irradiation device equipped with a belt conveyor (manufactured by Eye Graphics Co., Ltd., attached to a cold mirror), the colored object is placed on the conveyor. It was passed directly under the lamp (irradiation distance 11 cm) under the predetermined conditions described below. The ultraviolet irradiation amount under each condition was measured using an ultraviolet integrated light amount system (“UNIMETER UIT-150-A / receiver UVD-C365” manufactured by Ushio, Inc.).

As for the dryness, it was confirmed whether or not the surface of the cured product was scratched with the nail immediately after UV irradiation. The coating material was UV-irradiated while changing the conveyor speed (m / min) of the UV irradiation device, and evaluated according to the following evaluation criteria according to the conveyor speed (m / min) that does not cause damage even if it is strongly rubbed with a nail after curing. .. The larger the value of the conveyor speed, the better the drying property.

A: The conveyor speed was 50 m / min or more.
B: The conveyor speed was 30 m / min or more and less than 40 m / min.
C: The conveyor speed was less than 30 m / min.

Table 2 shows the compositions and evaluation results of the printing inks (1) to (4) produced in Examples 5 to 8 and the printing inks (R1) and (R2) produced in Comparative Examples 4 and 5.

The abbreviations in Table 2 indicate the following.
EOTMPTA: Trimethylolpropane EO-modified triacrylate

The details of each component used in the preparation of the printing ink are as follows.
EOTMPTA: Trimethylolpropane EO-modified triacrylate pigment: "SYMULER FAST YELLOW 4342" manufactured by DIC Corporation
Constituent pigment: Hydrous magnesium silicate ("High Filler # 5000PJ" manufactured by Matsumura Sangyo Co., Ltd.)
Wax: Polyolefin wax (Shamrock wax "S-381-N1")
Polymerization inhibitor: N-nitrosophenylhydroxylamisialuminum salt (“Q-1301” manufactured by Wako Pure Chemical Industries, Ltd.)
Polymerization Initiator (Y-1): α-Aminoalkylphenone (“Irgacure 907” manufactured by BASF)
Polymerization Initiator (Y-2): 4,4'-Bisdimethylaminobenzophenone ("EAB-SS" manufactured by Daido Kasei Co., Ltd.)

(Examples 9 to 12: Preparation of paints (1) to (4))
The paints <clear coating agent> (1) to (4) were prepared by blending each component in the ratio shown in Table 3 below.

(Comparative Examples 6 and 7: Preparation of paints (R1) and (R2))
Each component was blended in the ratio shown in Table 3 below to obtain paints <clear coating agent> (R1) and (R2).

The following evaluation was performed using the paints obtained in the above Examples and Comparative Examples.

[Evaluation methods]
A plastic base material (ABS base material) was coated with a spray gun so as to have a dry film thickness of 10 to 15 μm, heated and dried at 80 ° C. for 20 minutes in a dryer, and then various evaluations were performed.

[Chemical resistance (acid) evaluation method]
One drop of 0.1N sulfuric acid was added dropwise to the surface of the coating film, and the mixture was allowed to stand at room temperature for 24 hours, then the spots were wiped off, and the evaluation was performed visually according to the following evaluation criteria.

A: There was no trace on the surface of the coating film.
B: There were some traces on the surface of the coating film.
C: There was a coating film abnormality such as whitening on the coating film surface.

[Chemical resistance (alkali) evaluation method]
A drop of 0.1N sodium hydroxide aqueous solution was added dropwise to the surface of the coating film, and the mixture was allowed to stand at room temperature for 24 hours, then the spots were wiped off, and the evaluation was performed visually according to the following evaluation criteria.

A: There was no trace on the surface of the coating film.
B: There were some traces on the surface of the coating film.
C: There was a coating film abnormality such as whitening on the coating film surface.

[Evaluation method of MEK rubbing resistance]
Cotton wool soaked in MEK was placed on the surface of the coating film under a load of 500 g, and the traces after 20 reciprocating rubbing were visually evaluated according to the following evaluation criteria.

A: There was no trace on the surface of the coating film.
B: There were some traces on the surface of the coating film.
C: There was a coating film abnormality such as whitening on the coating film surface.

[Evaluation method of weather resistance]
The paint was subjected to an accelerated weather resistance test using a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.). The gloss retention rate (%) was measured from the 60 ° glossiness of the cured coating film after the test for 500 hours and the initial value of 60 ° glossiness.

Table 3 shows the compositions and evaluation results of the paints (1) to (4) prepared in Examples 9 to 12 and the paints (R1) and (R2) prepared in Comparative Examples 6 and 7.

The details of each component used in the preparation of the paint are as follows.
Thinner: Organic solvent metallic pigment mixed with butyl acetate / ethyl acetate / propylene glycol monomethyl ether acetate / Solbesso 100 = 30/20/30/20 (weight ratio): "ALPASSE 7160N" manufactured by Toyo Aluminum K.K.
Polyisocyanate-based curing agent: "Barknock DN-980" manufactured by DIC Corporation

Examples 5 to 8 shown in Table 2 are examples of printing inks using the acrylic resin of the present invention. It was confirmed that the printing ink containing the acrylic resin of the present invention has excellent drying properties.

Examples 9 to 12 shown in Table 3 are examples of paints using the acrylic resin of the present invention. It was confirmed that the paint containing the acrylic resin of the present invention has excellent chemical resistance, MEK rubbing resistance and weather resistance in a well-balanced manner.

On the other hand, Comparative Example 4 is an example of a printing ink using an acrylic resin that does not use the polyfunctional (meth) acrylate compound (A). It was confirmed that this printing ink had extremely insufficient ink drying property.

Comparative Example 5 is an example of a printing ink using an acrylic resin in which the average decomposition amount X per unit time (minutes) in the dropping reaction time of the polymerization initiator is outside the range of 0.00025 to 0.001 mol. .. It was confirmed that this printing ink had extremely insufficient ink drying property.

Comparative Example 6 is an example of a paint using an acrylic resin that does not use the polyfunctional (meth) acrylate compound (A). It was confirmed that this paint had significantly insufficient chemical resistance, MEK rubbing resistance and weather resistance.

Comparative Example 7 is an example of a paint using an acrylic resin in which the average decomposition amount X per unit time (minutes) in the dropping reaction time of the polymerization initiator is outside the range of 0.00025 to 0.001 mol. It was confirmed that this paint had significantly insufficient chemical resistance, MEK rubbing resistance and weather resistance.

Claims (6)

A polymerizable compound containing a polyfunctional (meth) acrylate compound (A) and a compound (B) having a polymerizable unsaturated group other than the compound (A).
A (meth) acrylic resin obtained by copolymerizing in the presence of a polymerization initiator (C).
The average decomposition amount X per unit time (minutes) of the polymerization initiator (C) represented by the following formulas (1), (2) and (3) in the dropping reaction time is 0.00025 to 0.001 mol. A (meth) acrylic resin characterized by being in the range of.

(1)

(2)

(3)
n: Drop reaction time (minutes)
X _k : Decomposition amount (mol) of the polymerization initiator k minutes after the start of dropping.
Y _k : Amount of polymerization initiator present in the reaction field k minutes after the start of dropping (g)
Q: Amount of polymerization initiator charged (g)
A: Frequency factor of polymerization initiator (1 / h)
E: Activation energy of polymerization initiator (J / mol)
R: Gas constant 8.314 (J / K · mol)
T: Reaction temperature (° C)
M: Molecular weight of polymerization initiator (g / mol) The (meth) acrylic resin according to claim 1, wherein the amount of the compound (A) used is in the range of 10 to 90 mol% in the polymerizable compound. A coating material comprising the (meth) acrylic resin according to claim 1 or 2. An article painted with the paint according to claim 3. A printing ink comprising the (meth) acrylic resin according to claim 1 or 2. A printed matter printed with the printing ink according to claim 5.