TW201905121A - Curing composition for coating and laminate - Google Patents

Abstract

An objective of the present invention is to provide a curable composition for coating which is excellent in adhesion to a substrate and also excellent in surface curability of a coating film even when a coating film is formed on a base material of a low surface energy material such as polyolefin or the like. The curable composition for coating of the present invention is a composition containing a polymer (a), a monomer (b) and a curing catalyst (c), wherein the curing catalyst (c) is an organoborane-amine complex (c-1) or a mixture (c-2) of a carboxylic acid salt of a transition metal and a polyamine having a tertiary amino group, and each component is contained in a specified amount.

Description

   Coating hardening composition and laminated body   

The present invention relates to a curable composition for coating and a laminated body.

In recent years, researches on replacing structures from metal to resin materials or using resin materials for structures / molded articles have been actively conducted. Among them, materials / materials having affinity for polyolefins such as polypropylene are attracting attention.

However, although conventional coating agents can regulate the wettability of the liquid and the hardening of the coating film when coating the polyolefin, the improvement of the surface adhesion is a major issue, and various materials and materials are being used. Discussion. However, the characteristics have not been fully realized, and there is a need for improvement.

Therefore, in Patent Document 1, a thermosetting resin composition is proposed in which (A) a polymer component having two or more polymerizable substituents and (B) a compound having one or more polymerizable substituents (C) A living polymerization initiator is obtained by curing, and it is disclosed in Patent Document 1 that the thermosetting resin composition is used for electrical insulation and fixation of coils for electrical equipment such as motors and transformers.

    [Prior technical literature]         [Patent Literature]    

[Patent Document 1] Japanese Patent Laid-Open No. 2010-144109

It is an object of the present invention to provide a coating hardening composition which is excellent in adhesion to a substrate even when a coating film is formed on a substrate with a low surface energy material such as polyolefin, and the surface of the coating film Those with excellent hardenability.

As a result of careful research by the present inventors to solve the above-mentioned problems, they have found that the above-mentioned problems can be solved by a coating hardening composition having the following configuration, and have completed the present invention.

The present invention is, for example, the following composition or laminate of [1] to [5].

[1] A hardening composition for coating, containing 25 to 95 parts by mass of a polymer (a) having an unsaturated bond and 5 to 75 parts by mass of a monomer (b) having a polymerizable unsaturated group (only The total amount of the polymer (a) and the monomer (b) is 100 parts by mass) and the curing catalyst (c); wherein the curing catalyst (c) is an organoborane-amine complex (c-1), or a mixture (c-2) of a carboxylic acid salt of a transition metal and a polyamine having a tertiary amine group; the curing catalyst (c) is the organoborane-amine complex (c -1), the total of the aforementioned (a) and (b) contains 0.001 to 0.1 mol per 100 g of the organoborane-amine complex (c-1); the aforementioned hardening catalyst (c) is one of the aforementioned transition metals When a mixture of a carboxylic acid salt and a polyamine having a tertiary amine group (c-2), the total of (a) and (b) above is a carboxylate containing a transition metal and a polyamine having a tertiary amine group per 100 g. In total 0.001 to 0.1 mol, the molar ratio of the carboxylic acid salt of the transition metal and the polyamine having a tertiary amine group (the carboxylic acid salt of the transition metal: a polyamine having a tertiary amine group) is 1: 0.05 to 1: 5; The acid value of the aforementioned polymer (a) is less than 0.1 mg-KOH / g, which has a polymerizable property. When the monomer (b) having a saturated group does not have an acid group, and the hardening catalyst (c) is an organoborane-amine complex (c-1), the aforementioned composition is an organoborane-amine complex The molar ratio (c-1: d) of the substance (c-1) and the compound (d) having an acid group is in a range of 1: 0.01 to 1: 5 to contain the aforementioned compound (d) having an acid group.

[2] The coating curable composition according to [1], wherein the polymer (a) is an unsaturated polyester resin.

[3] A laminated body comprising a base material and a coating film of the hardening composition for coating described in [1] or [2] formed adjacent to the base material.

[4] The laminated body according to [3], wherein the substrate is a substrate of a low surface energy material.

[5] The laminated body according to [4], wherein the low surface energy material is polyolefin.

According to the present invention, it is possible to provide a hardening composition for coating, which is excellent in adhesion to a substrate even when a coating film is formed on a substrate with a low surface energy material such as polyolefin, and the surface of the coating film It is also excellent in hardenability.

Hereinafter, the curable composition for coating of this invention is demonstrated. Hereinafter, the coating curable composition of the present invention is also simply referred to as a "composition". In addition, acrylic acid and methacrylic acid are collectively referred to as "(meth) acrylic acid", and acrylate and methacrylic acid ester are collectively referred to as "(meth) acrylic acid ester".

    <Coating curable composition>    

The composition of the present invention contains a specific polymer (a) (hereinafter, also simply referred to as "polymer (a)"), a specific monomer (b) (hereinafter, also simply referred to as "monomer ( b) ") and a specific curing catalyst (c) (hereinafter, also referred to as" curing catalyst (c) "). The composition of the present invention contains a specific compound (d) (hereinafter, also simply referred to as "compound (d)") as an essential component in a specific case described later. In addition, the composition of the present invention may further contain other components as necessary.

    [Polymer (a)]    

The polymer (a) contains an unsaturated bond.

The unsaturated bond in the polymer (a) is preferably a polymerizable carbon / carbon double bond. Furthermore, a polymerizable carbon / carbon double bond is also called an ethylenically unsaturated bond.

Examples of the polymer (a) include unsaturated polyester resin, vinyl ester resin, diallyl phthalate prepolymer, urethane (meth) acrylate resin, and polyester (meth) acrylate resin. , Polybutadiene, polyisoprene, isoprene-isobutene copolymer, acrylonitrile-butadiene copolymer. The polymer (a) may be used singly or in combination of two or more kinds. The polymer (a) is preferably an unsaturated polyester resin, a diallyl phthalate prepolymer, an isoprene-isobutylene copolymer, and an acrylonitrile-butadiene copolymer. Among them, the unsaturated polyester resin Since it has both the surface hardening property and the film-forming property of the coating film required for the development and adhesion of the low surface energy substrate, it is particularly preferable.

The unsaturated polyester resin is not particularly limited, and can be obtained, for example, by condensing a polybasic acid such as a dibasic acid with a polyhydric alcohol.

The aforementioned polybasic acid is preferably a dibasic acid, and specifically, examples thereof include α, β-unsaturated dibasic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, and itaconic anhydride; phthalic acid , Phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydrophthalic acid, cyclopentadiene-malay Anhydride adduct, succinic acid, malonic acid, glutaric acid, adipic acid, sebacic acid, 1,10-sebacic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid Saturated dibasic acids such as 2,3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, and dialkyl esters thereof are not particularly limited. As the dibasic acid, one species may be used, or two or more species may be used.

Examples of the polyhydric alcohols include ethylene glycols such as ethylene glycol, diethylene glycol, and polyethylene glycol, propylene glycols such as propylene glycol, dipropylene glycol, and polypropylene glycol, 2-methyl-1,3-propanediol, and 1 Adduct of 1,3-butanediol, bisphenol A and propylene oxide or ethylene oxide, glycerol, trimethylolpropane, 1,3-propanediol, 1,2-cyclohexanediol, 1,3 -Cyclohexanediol, 1,4-cyclohexanediol, p-xylylene glycol, dicyclohexyl-4,4'-diol, 2,6-decahydronaphthalene glycol, ginseng (2-hydroxyethyl) tris Polyisocyanate, etc.

Polyols may be used singly, or two or more kinds may be used. Moreover, it can also be modified with an epoxy resin, diisocyanate, dicyclopentadiene, etc. as needed.

The vinyl ester resin is not particularly limited, and examples thereof include a polyester obtained by reacting an epoxy (meth) acrylate and a polyester at a terminal carboxyl group with an epoxy compound containing an α, β-unsaturated carboxylate group ( (Meth) acrylate. The (meth) acrylic epoxy ester can be obtained from an epoxy resin and acrylic acid or methacrylic acid. The polyester having a terminal carboxyl group can be obtained from a saturated dicarboxylic acid and / or an unsaturated dicarboxylic acid and a polyol. obtain.

The diallyl phthalate prepolymer is not particularly limited, and examples thereof include diallyl phthalate, that is, a prepolymer obtained by polymerizing diallyl phthalate and copolymerizing with other monomers as necessary. Polymer.

The aforementioned urethane (meth) acrylate resin is not particularly limited. For example, a polyisocyanate can be reacted with a polyhydroxy compound or a polyol before being reacted with a hydroxyl-containing (meth) acrylic compound and It is obtained by reacting a hydroxyl-containing allyl ether compound as required. Moreover, after reacting a hydroxyl-containing (meth) acrylic compound with a polyhydroxy compound or a polyhydric alcohol, it can also be made to react with a polyisocyanate.

The polyester (meth) acrylate resin is not particularly limited, and can be obtained, for example, by reacting an end of an unsaturated or saturated polyester with a (meth) acrylic compound.

The preparation conditions, reaction conditions, and the like of each raw material when the polymer (a) is obtained are not particularly limited as long as they are appropriately adjusted.

The weight average molecular weight (Mw) of the polymer (a) measured by the gel permeation chromatography method (GPC method) is a polystyrene conversion value, and is preferably 800 to 150,000. From the viewpoint of considering both the surface hardenability and the film-forming property of the coating film required for developing the adhesiveness of the substrate, the Mw is preferably within the aforementioned range.

The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the polymer (a) measured by the GPC method is preferably 1.0 to 20.0, more preferably 1.5 to 18.0, and even more preferably 1.5. To 15.0.

The polymer (a) preferably has an acid value of 0 to 70.0 mg-KOH / g, and more preferably 0 to 55.0 mg-KOH / g. Within the aforementioned range, it is preferable because it is easy to obtain good compatibility with the monomer and the curing catalyst and it is easy to obtain good solubility in the solvent.

As the polymer (a), commercially available products can be used. As for the commercially available products, examples of the unsaturated polyester include Rigolac manufactured by Showa Denko Corporation, POLYHOPE manufactured by Japan Composite Corporation, and U-PICA manufactured by U-PICA Corporation of Japan. ; DAISO-DAP, DAISO-ISO DAP manufactured by Osaka Soda Co., Ltd. as the diallyl phthalate prepolymer; JSR BUTYL manufactured by JSR Co., Ltd. as the isoprene-isobutylene copolymer; acrylonitrile-butadiene copolymerization Examples of the material include Nipol NBR manufactured by Japan Zeon Corporation.

    [Monomer (b)]    

The coating curable composition of the present invention contains a monomer (b) having a polymerizable unsaturated group. The composition of the present invention can form a coating film on the surface of a substrate or the like by polymerizing the monomer (b) and the polymer (a) together.

Examples of the monomer (b) include monomers other than (meth) acrylic monomers and (meth) acrylic monomers. Here, the so-called (meth) acrylic acid single system has a monomer of acrylfluorenyl (H ₂ C = CH-CO-) or methacrylfluorenyl (H ₂ C = CCH ₃ -CO-).

As the (meth) acrylic monomer system, at least one monomer selected from acrylic monomers and methacrylic monomers can be used.

Examples of the (meth) acrylic monomer include a (meth) acrylic monomer having a polar group and a (meth) acrylic monomer having no polar group.

The polar group preferably contains at least one atom selected from oxygen, nitrogen, and sulfur, and more preferably contains at least one atom selected from oxygen and nitrogen.

Examples of the (meth) acrylic monomer having a polar group include an oxygen-containing (meth) acrylic monomer, a nitrogen-containing (meth) acrylic monomer, and a sulfur-containing (meth) acrylic monomer. Oxygen (meth) acrylic monomer, nitrogen-containing (meth) acrylic monomer.

Examples of the oxygen-containing (meth) acrylic monomer include: tetrahydrofuran methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, and methoxy (meth) acrylate Ethyl ester, phenoxyethyl (meth) acrylate, (3-ethyloxetane-3-yl) methyl (meth) acrylate, neopentyl tetrakis (meth) acrylate, Neopentaerythritol tri (meth) acrylate, (meth) acrylic acid, β-carboxyethyl acrylate, 2-propenyloxyethyl-succinic acid, 2-propenyloxyethyl-phthalic acid, 2 -Acrylic acid oxyethyl acid phosphate, 3- (meth) acryl methoxypropyltrimethoxysilane, 3- (meth) acryl methoxypropyltriethoxysilane.

Examples of nitrogen-containing (meth) acrylic monomers include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, acrylamide, and dimethyl (methyl) ) Acrylamide, (meth) acrylamidomorpholine.

Examples of the sulfur-containing (meth) acrylic monomer include 2-methylthioethyl (meth) acrylate.

Examples of the (meth) acrylic monomer having no polar group include (meth) acrylate. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, (formyl) Base) isobutyl acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylic acid Monofunctional (meth) acrylic acid such as cyclohexyl ester, dicyclopentyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isoamyl (meth) acrylate, and benzyl (meth) acrylate Esters; neopentaerythritol tetra (meth) acrylate, dinepentaerythritol hexa (meth) acrylate, 1,2-ethylene glycol di (meth) acrylate, 1,6-hexanediol di (Meth) acrylate, 1,12-dodecanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, Multifunctional (meth) acrylates such as butyl di (meth) acrylate and hexyl di (meth) acrylate.

The (meth) acrylic acid monomer may be used individually by 1 type, and may use 2 or more types.

Examples of the monomer other than the (meth) acrylic monomer include vinyl esters such as vinyl acetate and vinyl propionate; unsaturated carboxylic compounds such as maleic acid and fumaric acid; maleic anhydride, fumaric anhydride, and the like Unsaturated carboxylic anhydride compounds; olefins such as ethylene, propylene, isobutylene; halogenated olefins such as vinyl chloride, vinylidene chloride; styrene monomers such as styrene, α-methylstyrene, and divinylbenzene; Diene monomers such as butadiene, isoprene, and chloroprene; allyl monomers such as diallyl phthalate and diallyl isophthalate; N-phenylmalein amine.

The monomer other than the (meth) acrylic monomer may be used individually by 1 type, and may use 2 or more types.

The monomer (b) is preferably compatible with the polymer (a) and the hardening catalyst (c). Although the detailed mechanism is not clear, the point is to obtain good hardenability and adhesion to the substrate. In other words, it is based on tetrahydrofuran methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, and N-phenyl horse Rhenimine, maleic acid and maleic anhydride are particularly preferred.

    [Hardening catalyst (c)]    

The coating curable composition of the present invention contains a curing catalyst (c). The composition of the present invention is capable of carrying out the polymerization reaction of the polymer (a) and the monomer (b) by generating radicals from the curing catalyst (c), and curing of the composition is started.

The hardening catalyst (c) is an organoborane-amine complex (c-1), or a mixture (c-2) of a carboxylic acid salt of a transition metal and a polyamine having a tertiary amine group. Hereinafter, description will be made in order.

(Organoborane-amine complex (c-1))

The so-called organoborane-amine complex (c-1) is a complex formed by an organoborane and an amine. Examples of the organoborane constituting the organoborane-amine complex (c-1) include compounds represented by BR ₃ . In the aforementioned formulae, R is each independently an alkyl group, a cycloalkyl group, an alkoxy group, or a phenyl group having 1 to 8 carbon atoms.

Examples of the organoborane system include triethylborane, tributylborane, trihexylborane, and monomethoxydiethylborane. The organic borane is preferable because the alkyl borane can obtain good hardening properties and substrate adhesion in the atmosphere.

The amine of the organoborane-amine complex may have at least one amine group in the molecule, and preferably has two or three amine groups.

Examples of the amine include monoamines such as diethylamine, dibutylamine, triethylamine, and methoxypropylamine; and polyamines such as 1,3-diaminopropane and diethylene triamine.

The organoborane-amine complex can be not only the complex formed by the aforementioned organoborane and amine, but also a complex having an organborane and an amine in the same molecule and forming a complex in the same molecule.组合。 The compound. Examples of such an organoborane-amine complex include compounds represented by the following formula (A).

In formula (A), the arrow from N to B indicates a coordination key.

Specific examples of the organoborane-amine complex include triethylborane-1,3-diaminopropane complex, triethylborane-diethylene triamine complex, and N-butylborane-3-methoxy-1-propylamine complex and the like.

The organoborane-amine complex can be used alone or in combination of two or more.

(Mixture of carboxylate of transition metal and polyamine with tertiary amine group (c-2))

In the present invention, a mixture (c-2) of a carboxylate of a transition metal and a polyamine having a tertiary amine group may be used instead of the organoborane-amine complex (c-1) as a curing catalyst ( c).

Examples of the transition metal constituting the carboxylate of the transition metal include iron, copper, zinc, nickel, cobalt, manganese, and chromium, and iron or copper is preferred. That is, the carboxylate of the transition metal is preferably iron carboxylate or copper carboxylate.

The valence of the metal constituting the carboxylate of the transition metal is usually divalent or less, preferably monovalent or divalent. When the aforementioned metal is iron, bivalence is preferred, and when it is copper, monovalence is preferred.

Examples of carboxylates of transition metals include acetates of transition metals, formate salts of transition metals, oxalates of transition metals, stearates of transition metals, 2-ethylhexanoate of transition metals, and transition metals. The metal naphthenate and transition metal benzoate are preferably the transition metal acetate and the transition metal formate, and more preferably the transition metal acetate.

The carboxylate salt of the transition metal may be contained in the adhesive composition as a hydrate.

Specific examples of carboxylic acid salts of transition metals include iron (II) acetate, copper (I) acetate, iron (II) formate, copper (I) formate, iron (II) oxalate, copper (I) oxalate, and stearic acid. Iron (II), copper (I) stearate, bis (2-ethylhexanoate) iron (II), bis (2-ethylhexanoate) copper (I), iron (II) naphthenate, ring Copper (I) alkanoate and the like are preferably iron (II) acetate, copper (I) acetate, iron (II) formate, and more preferably iron (II) acetate and copper (I) acetate.

The carboxylate of the transition metal may be used singly or in combination of two or more kinds.

The polyamine having a tertiary amine group has two or more amines in the molecule.

The polyamine having a tertiary amine group has two or more amines in the molecule, but usually has two to six amines in the molecule, preferably two to four, more preferably two or three. When the number of amines in the molecule of the polyamine is within the aforementioned range, it is preferable because sufficient hardenability and good adhesiveness can be exhibited.

Polyamines with a tertiary amine group have at least one tertiary amine group, more preferably at least two tertiary amine groups, and even more preferably at least two tertiary amine groups and not having a tertiary amine group. Amine.

Examples of polyamines with tertiary amine groups include: N, N, N ', N'-tetramethylethylenediamine, N, N, N', N ", N" -N "pentamethyldiethylene Triamine, p- [2- (dimethylamino) ethyl] amine, N, N-dimethyl-1,2-ethanediamine, 1,1,4,7,10,10-hexa Methyltriethylene tetramine, 1,4,8,11-tetramethyl-1,4,8,11-tetraazocyclotetradecane, ginseng (2-pyridylmethyl) amine, N, N, N ', N'-(2-pyridylmethyl) ethylenediamine, preferably N, N, N ', N'-tetramethylethylenediamine, N, N, N ', N ", N" -pentamethyldiethylene triamine, ginseng [2- (dimethylamino) ethyl] amine.

The polyamines having a tertiary amine group may be used alone or in combination of two or more.

The combination of a carboxylate of a transition metal and a polyamine having a tertiary amine group is not particularly limited, but examples of the mixture (c-2) include: iron (II) acetate and N, N, N ', N'-tetra A mixture of methyl ethylene diamine, a mixture of iron (II) acetate and N, N, N ', N ", N" -pentamethyl diethylene triamine, iron (II) acetate and a reference [2 -(Dimethylamino) ethyl] amine mixture, copper (I) acetate and N, N, N ', N ", N" -pentamethyldiethylene triamine, copper acetate (I ) And a mixture of [2- (dimethylamino) ethyl] amine.

    [Compound (d) having an acid group]    

The hardening composition for coating of the present invention has an acid value of the polymer (a) of less than 0.1 mg-KOH / g, and the monomer (b) having a polymerizable unsaturated group has no acid group and is used for hardening. In the case (X) where the catalyst (c) is an organoborane-amine complex (c-1) (hereinafter, also referred to as "the case where the condition (X) is satisfied"), it is a compound containing an acid group ( d) as an essential ingredient.

In addition, in the coating hardening composition of the present invention, the polymer (a) has an acid value of less than 0.1 mg-KOH / g, and the monomer (b) having a polymerizable unsaturated group has no acid group. In the case (X) where the curing catalyst (c) is an organoborane-amine complex (c-1) (hereinafter, also referred to as "the case where the condition (X) is not satisfied"), it may include The compound (d) having an acid group is used as an optional component.

The aforementioned compound (d) having an acid group means a compound having an acid group in its molecule, and does not correspond to the aforementioned compounds (a), (b), and (c).

The compound (d) can be widely used if it is a compound known as an organic acid or an inorganic acid.

In the present invention, the acid group may be any acid group, and examples thereof include a carboxyl group, a phosphate group, a sulfo group, a carboxylic acid anhydride group known as an acid anhydride group, a disulfonic acid anhydride group, and a pyrophosphate group.

The compound (d) may have at least one acid group in the molecule, preferably has 1 to 6 acid groups in the molecule, and more preferably has 1 to 4 acid groups.

Examples of the compound (d) include carboxylic acid-containing compounds such as acetic acid, citric acid, formic acid, lactic acid, glutaric acid, phthalic acid, succinic acid, and ricinoleic acid; carboxylic anhydride-containing compounds such as acetic anhydride, phthalic anhydride, and succinic anhydride; Sulfonic acid-containing compounds such as acids, methanesulfonic acid, and benzenesulfonic acid; phosphoric acid-containing compounds such as phosphoric acid, monoalkyl phosphates, and dialkyl phosphates.

    〔Other ingredients〕    

The composition of the present invention may further contain other components as necessary.

Other components include, for example, a plasticizer, a smoothing agent, a hardening accelerator, a hardener, a tackifier, a film-forming aid, a release agent, a filler, an antifoaming agent, a heat resistance imparting agent, a flame retardancy imparting agent, Antistatic agents, conductivity imparting agents, ultraviolet absorbers, antioxidants, polymerization inhibitors, antifogging agents, antibacterial / mildewproof agents, photocatalysts, dyes, pigments, coupling agents, shake modifiers, flexibility imparting agents, Reinforcing materials (fibers, cloths, nonwovens, etc.), hardening monomers / oligomers other than (meth) acrylic monomers, solvents, etc.

组成 Composition, manufacturing method, use, etc. of the composition≫

The composition of the present invention is a composition containing the aforementioned polymer (a), monomer (b), and curing catalyst (c).

The composition of the present invention contains 25 to 95 parts by mass of the polymer (a) and 5 to 75 parts by mass of the monomer (b). However, the total of the polymer (a) and the monomer (b) is 100 parts by mass.

The blending amount of the polymer (a) is preferably 25 to 93 parts by mass, more preferably 27 to 93 parts by mass, and particularly preferably 30 to 30 parts by mass relative to 100 parts by mass of the polymer (a) and the monomer (b) in total. 90 parts by mass. The blending amount of the monomer (b) is preferably 7 to 75 parts by mass, more preferably 7 to 73 parts by mass, and particularly preferably 10 to 70 parts by mass. Within the aforementioned range, it is preferable because good hardenability can be obtained in the atmosphere, and the substrate is formed of a low surface energy material with excellent adhesion.

The amount of the curing catalyst (c) contained in the composition of the present invention varies depending on the type of the curing catalyst (c).

When the hardening catalyst (c) of the composition of the present invention is an organoborane-amine complex (c-1), the total of the polymer (a) and the monomer (b) contains organoborane per 100 g of the system -The amine complex (c-1) is 0.001 to 0.1 mol, preferably 0.002 to 0.1 mol, more preferably 0.003 to 0.08 mol, and most preferably 0.004 to 0.08 mol. Within the aforementioned range, it is preferable because hardenability in the atmosphere and adhesion to the substrate can be exhibited, and a good pot life of the coating liquid is ensured.

When the hardening catalyst (c) of the present invention is a mixture (c-2) of a carboxylic acid salt of a transition metal and a polyamine having a tertiary amine group, the polymer (a) and the monomer (b) The total per 100g is a total of 0.001 to 0.1 mol of a carboxylic acid salt containing a transition metal and a polyamine having a tertiary amine group, preferably 0.002 to 0.09 mol, more preferably 0.002 to 0.08 mol, and particularly preferably 0.004. To 0.08mol. Within the aforementioned range, it is preferable because the hardenability in the atmosphere and the adhesion to the substrate can be exhibited, and at the same time, a good application time of the coating liquid is ensured. The molar ratio of the carboxylic acid salt of the transition metal to the polyamine having a tertiary amine group (the carboxylic acid salt of the transition metal: a polyamine having a tertiary amine group) is 1: 0.05 to 1: 5, preferably 1: 0.1 to 1: 4, more preferably 1: 0.15 to 1: 3.5. Within the aforementioned range, it is preferable because the hardenability in the atmosphere and the adhesion to the substrate can be exhibited, and at the same time, a good application time of the coating liquid is ensured.

When the composition of the present invention satisfies the aforementioned condition (X), the compound (d) is contained as an essential component. When the condition (X) is satisfied, the composition of the present invention is based on the molar ratio (c-1: d) of the organoborane-amine complex (c-1) to the compound (d) of 1: 0.01 to The compound (d) is contained in a range of 1: 5, preferably in a range of 1: 0.03 to 1: 4.5, and more preferably in a range of 1: 0.05 to 1: 4. Within the aforementioned range, it is preferable because the hardenability in the atmosphere and the adhesion to the substrate can be exhibited, and at the same time, a good application time of the coating liquid is ensured.

When the composition of the present invention does not satisfy the condition (X), the compound (d) may be contained as an optional component. When the condition (X) is not satisfied and the curing catalyst (c) is an organoborane-amine complex (c-1), the composition of the present invention is the aforementioned organoborane-amine complex (c- 1) The molar ratio (c-1: d) to the compound (d) is usually in the range of 1: 0 to 1: 5, preferably in the range of 1: 0 to 1: 4.5, more preferably 1: 0 to The compound (d) is contained at 1: 4. Within the aforementioned range, it is preferable because the hardenability in the atmosphere and the adhesion to the substrate can be exhibited, and at the same time, a good application time of the coating liquid is ensured. When the condition (X) is not satisfied and the curing catalyst (c) is a mixture (c-2) of a carboxylic acid salt of a transition metal and a polyamine having a tertiary amine group, the composition of the present invention is as described above. The molar ratio of the carboxylic acid salt of the transition metal to the compound (d) (the carboxylic acid salt of the transition metal: d) is usually in the range of 1: 0 to 1: 5, preferably in the range of 1: 0 to 1: 4.5, More preferably, the compound (d) is contained from 1: 0 to 1: 4. Within the aforementioned range, it is preferable because the hardenability in the atmosphere and the adhesion to the substrate can be exhibited, and at the same time, a good application time of the coating liquid is ensured.

When the composition of the present invention contains the other components described above, the amount is not particularly limited as long as the effects of the present invention are exhibited. Regarding the amount of other components (except for the solvent), when the total of the polymer (a) and the monomer (b) is 100 parts by mass, the other components are contained in a range of 0.01 to 50 parts by mass.

When the composition of the present invention contains a solvent, when the total amount of the polymer (a) and the monomer (b) is 100 parts by mass, the solvent is contained in a range of 10 to 1900 parts by mass.

The manufacturing method of the composition of this invention is not specifically limited. The aforementioned composition can usually be obtained by mixing the components constituting the composition, that is, the polymer (a), the monomer (b), the curing catalyst (c), and the compound (d) and other components as required. obtain.

The polymer (a), the monomer (b), the compound (d), and the hardening catalyst (c), as needed, will start a polymerization reaction when they are brought into contact by mixing or the like, that is, a hardening reaction, Therefore, it is preferable to obtain the hardening composition for coating by mixing the components just before use, or to make the polymer (a), the monomer (b), the compound (d), and the hardening catalyst as needed. (c) Adhesive prepared as a two-liquid or multi-component type (a part of the components can be solid or powder) in a non-contact manner, and the two or all components are mixed just before use .

The temperature at which the composition of the present invention is hardened is usually -20 to 80 ° C, preferably 0 to 60 ° C. The composition of the present invention can be hardened at normal temperature (for example, 10 to 30 ° C.). Therefore, the composition of the present invention can be used as a normal temperature curing type composition for coating. Therefore, it is easy to form a coating film on a substrate, and a heat-resistant material can also be used as the substrate.

The composition of the present invention can be applied to various substrates, and a coating film can be obtained by hardening the composition. That is, the laminated system of this invention has a base material and the coating film of the hardening composition for coating formed adjacent to the said base material.

In addition, the composition of the present invention obtains a coating film by hardening, and the composition of the present invention can shorten the curing maturation time compared with the conventional hardening composition for coating. In addition, the composition of the present invention is easy to adjust the safety under normal temperature / atmospheric environment, and the liquid application time after the composition is prepared, so the handleability is also excellent.

The laminated body of the present invention is a substrate having a low surface energy material, the adhesiveness between the coating film and the substrate is excellent, and the surface hardening property of the coating film is also excellent, so it can be used for various applications.

The substrate can be made of various materials, such as polypropylene, polyethylene and other polyolefins, acrylonitrile butadiene styrene copolymer, nylon, polyacetal, and carbon fiber reinforced thermoplastic (CFRTP) Wait.

The composition of the present invention can be suitably used in the case of coating a substrate with a low surface energy material. Examples of the low surface energy material include polyolefins such as polypropylene, polyethylene, polysiloxane, and polytetrafluoroethylene.

The laminated body of the present invention can be used for various applications by appropriately selecting the shape of the base material, the conditions of the secondary processing, and the like, for example, parts and components constituting various structures such as electrical equipment, automobiles, vehicles, ships, and residential equipment.

[Example]

Next, the present invention will be described in more detail by showing examples, but the present invention is not limited thereto.

    [Examples 1 to 25, Comparative Examples 1 to 12]    

In each of the examples and comparative examples, the components were measured and mixed so as to become the formulations described in Tables 1 to 4, respectively. In addition, in Tables 1-4, a part means a mass part.

In Tables 1 to 4, the "mol" of the curing catalyst (C) and the compound (D) means the curing catalyst (C when the total of the polymer (A) and the monomer (B) is 100 g) ) And the mol (amount) of the compound (D).

Specifically, the polymer (A), the monomer (B), and the solvent are measured and put into a glass container, and the components are mixed until the components are uniformly dissolved (about 10 minutes) as the coating agent main agent.

The hardening catalyst (C) is metered / input into the obtained coating agent main agent, and mixed for 1 minute until it is uniformly dissolved or dispersed to prepare a hardening composition for coating. The liquid application time of the hardening composition for coating was evaluated by the following method.

In the examples and comparative examples using the compound (D), the coating base agent obtained by metering / mixing the polymer (A), the monomer (B), the compound (D), and the solvent was measured / The hardening catalyst (C) was added and mixed for 1 minute to prepare a hardening composition for coating.

The obtained hardening composition for coating was applied to a polypropylene sheet (25 mm × 100 mm × 1.6 mm thick) with a bar coater. After coating, it was allowed to stand for 20 hours at 23 ° C and in the air to be cured and matured. The evaluation of the coating surface after hardening and ripening and the evaluation of the adhesion between the substrate and the coating film were performed on the following criteria.

(Liquid pot life)

The prepared hardening composition for coating was stored in a closed glass container at 23 ° C.

After the preparation, the thickened state of the liquid after 1 hour of storage was visually observed to evaluate the liquid applicable time. In addition, in the following Tables 1 to 4, the "liquid application time" is described as "liquid life".

◎: No liquid thickening / appearance change

○: Slight increase in liquid viscosity, but can be applied

△: It can be seen that the liquid is thickened, and surface streaks or rough surfaces are generated after coating

×: Liquid hardens and cannot be applied

(Coated surface)

Check and evaluate the adhesion / tackiness of the coated surface after curing with finger touch.

◎: No stickiness / sticky feeling

○: Slightly sticky / tacky

△: Sticky / tacky feel, fingers attached after touching

×: Obvious sticky / tacky odor, unreacted odor

(Adhesiveness)

An adhesive tape was attached to the coating surface (coating film) of the coating sample after curing and ripening, and left to stand for 1 hour in a 23 ° C / 50% RH environment.

After standing, Shimadzu Autograph AG-X used a 10 kN load cell to peel off the adhesive tape at a tensile speed of 1 cm / minute, and visually confirmed and evaluated the residue of the coating film on the polypropylene sheet.

◎: The coating agent is not peeled off, and the residue remains 100% by area

○: A little coating agent peeled off, and the residue was less than 100% to 80% or more in terms of area.

△: The coating agent is peeled off, and the residue is less than 80% to 50% by area

×: The coating agent is peeled off, and the residue is less than 50% to 0% in terms of area

The results of Examples and Comparative Examples are shown in Tables 1 to 4.

In Tables 1 to 4, the mol of the curing catalyst (C) and the compound (D) means the total of the polymer (A) and the monomer (B) per 100 g of the curing catalyst (C) and compound ( D) The number of moles.

The details of each component described in Tables 1 to 4 are shown below.

(Polymer (A))

U-PICA 8510: U-PICA 8510 (unsaturated polyester resin), Mw20000, Mw / Mn4.10, acid value 18.5mg-KOH / g, manufactured by U-PICA, Japan

DG774-E: DG774-E (unsaturated polyester resin), Mw4000, Mw / Mn2.00, acid value 43.0mg-KOH / g, manufactured by Dali Polymer Industry Co., Ltd.

DN281: DN281 (unsaturated polyester resin), Mw33000, Mw / Mn6.70, acid value 0mg-KOH / g, manufactured by Dali Polymer Industry Co., Ltd.

GV150: UBE GV150 (saturated polyester), Mw14000, Mw / Mn2.40, acid value 6mg-KOH / g made by U-PICA, Japan

S400: Kanevinyl S400 (polyvinyl chloride) manufactured by Kaneka, Mw62000, Mw / Mn2.00, acid value 0mg-KOH / g

The aforementioned U-PICA 8510, DG774-E, and DN281 correspond to the aforementioned polymer (a).

(Monomer (B))

St: Styrene manufactured by NS STYRENE MONOMER

n-pmid: Imilex P (N-phenylmaleimide) manufactured by Japan Catalyst Corporation

MMA: Acryester M (methyl methacrylate) manufactured by Mitsubishi Chemical Corporation

THF-MA: Lightester THF (tetrahydrofuran methyl methacrylate) manufactured by Kyoeisha Chemical Co., Ltd.

THF-A: VISCOAT # 150 (tetrahydrofuran methyl acrylate) manufactured by Osaka Organic Chemical Industry Co., Ltd.

DMAA: DMAA (Dimethacrylamide) manufactured by KJ Chemical Co., Ltd.

BZMA: Acryester BZ (benzyl methacrylate) manufactured by Mitsubishi Chemical Corporation

MAA: methacrylic acid manufactured by Mitsubishi Chemical Corporation

Maleic anhydride: manufactured by Tokyo Chemical Industry Co., Ltd.

The monomer (B) corresponds to all the above-mentioned monomers (b).

(Hardening catalyst (C))

TEB-DAP: TEB-DAP (triethylborane-1,3-diaminopropane complex) manufactured by BASF Corporation. Molecular weight: 172.12

Fe (Ac) 2: Iron (II) acetate manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight: 173.9

TMEDA: Tetramethylethylene diamine manufactured by Guangrong Chemical Industry Co., Ltd. Molecular weight: 116.24

TEB-DAP is equivalent to the above-mentioned (c-1), and it is equivalent to the above-mentioned (c-2) by using Fe (Ac) 2 and TMEDA in combination.

(Compound (D))

GluOH: Glutaric acid M manufactured by Tokyo Chemical Industry Co., Ltd .: 132.12 Succinic anhydride: Succinic anhydride M manufactured by Tokyo Chemical Industry Co., Ltd .: 100.07 GluOH and succinic anhydride correspond to the compound (d) described above.

(hardener)

L-45: Isocyanate hardener manufactured by Soken Chemical Co., Ltd.

TPA-100: Duranate TPA-100 isocyanate-based hardener manufactured by Asahi Kasei Chemicals Corporation

TD-75: Isocyanate hardener manufactured by Soken Chemical Co., Ltd.

(Solvent)

MEK: MEK (methyl ethyl ketone) manufactured by Maruzan Petrochemical Co., Ltd.

From the results of Tables 1 to 4, it can be seen that the curable composition for coating of the present invention is excellent in adhesion to the adherend (polyolefin), and is also excellent in surface hardenability. Moreover, since the hardening composition for coating of this invention can be used in normal temperature and atmospheric environment, it can be used as a normal temperature hardening type coating agent which can apply polyolefin etc.

Claims (5)

    A hardening composition for coating, comprising 25 to 95 parts by mass of a polymer (a) having an unsaturated bond and 5 to 75 parts by mass of a monomer (b) having a polymerizable unsaturated group. The total of the substance (a) and the monomer (b) is 100 parts by mass and the curing catalyst (c); the curing catalyst (c) is an organoborane-amine complex (c-1) Or a mixture (c-2) of a carboxylic acid salt of a transition metal and a polyamine having a tertiary amine group; when the curing catalyst (c) is the organoborane-amine complex (c-1), The total of the aforementioned (a) and (b) contains 0.001 to 0.1 mol per 100 g of the organoborane-amine complex (c-1); the curing catalyst (c) is a carboxylic acid salt of the transition metal and has For a mixture (c-2) of a polyamine having a tertiary amine group, the total of the aforementioned (a) and (b) per 100 g is a carboxylic acid salt containing a transition metal and a polyamine having a tertiary amine group in a total amount of 0.001 to 0.1 mol, molar ratio of carboxylic acid salt of transition metal to polyamine having tertiary amine group (carboxylate of transition metal: polyamine having tertiary amine group) is 1: 0.05 to 1: 5; the aforementioned polymer (a) The acid value is less than 0.1 mg-KOH / g, and it has a polymerizable unsaturated group. When the body (b) does not have an acid group and the hardening catalyst (c) is an organoborane-amine complex (c-1), the composition is based on the organoborane-amine complex (c- 1) The molar ratio (c-1: d) to the compound (d) having an acid group is in the range of 1: 0.01 to 1: 5 to contain the aforementioned compound (d) having an acid group.         The hardening composition for coating as described in the first claim, wherein the polymer (a) is an unsaturated polyester resin.         A laminated body comprising: a base material; and a coating film of a hardening composition for coating as described in item 1 or 2 of a patent application range formed adjacent to the base material.         The laminated body according to item 3 of the scope of patent application, wherein the substrate is a substrate of a low surface energy material.         The laminated body according to item 4 of the scope of patent application, wherein the aforementioned low surface energy material is polyolefin.