JP2016160290A - Resin composition for joining metal substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for joining thermosetting metal substrates which can secure an excellent working environment, is excellent in storage stability, has both adhesiveness to a flexible film and adhesiveness to a hard substrate such as metal, and can obtain sufficient adhesive strength even at a treatment temperature of lower than 200°C; and a laminate using the same.SOLUTION: A resin composition for joining metal substrates contains a copolymer (A), a copolymer (B), and a reactive compound (C); and satisfies the following (1) and (2). (1) Tg of the copolymer (A) is 10°C or higher and lower than 100°C, and is obtained by copolymerizing an unsaturated compound (a1) containing one or more hydroxyl groups in the molecule, and other unsaturated compounds (a3). (2) The copolymer (B) is obtained by copolymerizing an unsaturated compound (a2) having one or more functional groups selected from the group consisting of a carboxyl group and the like, and an unsaturated compound (a3).SELECTED DRAWING: None

Description

  The present invention relates to a resin composition for joining metal base materials and a laminate (for example, a laminated steel plate) using the resin composition.

  Laminated steel sheets made by bonding plastic films with printed or embossed surfaces to steel sheets are used in home appliance cases and interior / exterior building materials for homes. It's being used. These laminated steel sheets are generally manufactured by applying a bonding resin composition to a steel sheet and bonding a plastic film.

In recent years, the types of laminate films tend to diversify, and vinyl chloride films, polyolefin films, fluorine films, polyester films, and the like are used.
Among them, a representative plastic sheet laminated steel sheet is a vinyl chloride (hereinafter sometimes abbreviated as PVC) laminated steel sheet. Conventionally, a PVC laminated steel sheet is a resin composition for joining metal base materials dissolved in a solvent on the steel sheet. Immediately after applying an object and drying at a high temperature of 200 ° C. or higher, a vinyl chloride sheet is bonded by roll pressing.

  Since the resin composition for joining metal base materials used for laminated steel plates is required to have high adhesion, heat resistance and hot water resistance, many studies have hitherto been made on resin compositions for joining metal base materials used therefor. Has been made. For example, Patent Document 1 discloses a resin composition for joining a metal base material for a vinyl chloride-coated steel sheet in which a polyacrylic resin and an epoxy resin are blended. Patent Document 2 discloses a resin composition for joining metal base materials using a polyacrylic resin and ethyleneimine. Patent Document 3 discloses a resin composition for joining a metal substrate using a polyacrylic resin having a carboxyl group, a hydroxyl group, and a glycidyl group. Patent Document 4 discloses a resin composition for joining a metal base material in which a carboxyl group-containing macropolyol and a carbodiimide group-containing compound are blended. Patent Document 5 discloses a resin composition for joining a metal substrate using a copolymer of polyol and polyisocyanate and styrene and maleic anhydride.

  However, Patent Document 1 discloses that in a polyacrylic resin and an epoxy resin, a functional group capable of crosslinking reaction with a glycidyl group is not incorporated in the polyacrylic resin, the curing reactivity of the glycidyl group is poor, and the epoxy resin remains. There are concerns. When the remaining epoxy resin is hydrolyzed, two hydroxyl groups are generated, and the water resistance may be lowered. In Patent Document 2, ethyleneimine has high water solubility, and water resistance may be lowered. In addition, ethyleneimine has poor storage stability and may cause poor adhesion. In Patent Document 3, two or more kinds of functional groups capable of crosslinking reaction are copolymerized in a polyacrylic resin, and pot life and storage stability may be reduced due to self-crosslinking reaction. Patent Document 4 is a system utilizing the reaction between a carboxyl group and a carbodiimide group, but the curing reactivity between the carboxyl group and the carbodiimide group is high, and the storage stability may be deteriorated. If the amount of carbodiimide is reduced, the system is cured. In some cases, the cohesive strength after the reaction is insufficient, and the balance of the adhesive strength cannot be ensured. In Patent Document 5, since the main component of the polyol is polyester, hydrolysis occurs and the cohesive force is insufficient, and the adhesive strength after the water resistance test may be reduced.

  In order to solve these drawbacks, it is possible to increase the bonding strength by increasing the bonding temperature, melting the vinyl chloride resin to be laminated, and increasing the affinity with the metal substrate bonding resin composition. However, there is a case where thermal energy may increase and lead to high costs, and in recent years, a PVC laminated steel sheet having high design properties has been demanded, and a vinyl chloride sheet that has been embossed in advance is laminated. However, there is a problem that the embossing process may be crushed or lost due to high-temperature treatment at 200 ° C or higher at the time of pasting, and the appearance may be damaged, such as loss of gloss. (Less than 200 degreeC) is calculated | required and the resin composition for metal base-material joining excellent in the curing reactivity in low temperature is desired.

Japanese Patent Publication No.59-37034 JP-A-5-287250 Japanese Patent No. 3660477 JP 2010-159339 A Japanese Patent No. 3206946

  The present invention has been made to solve such a problem, and the object thereof is to ensure a good working environment, excellent storage stability, adhesion to a flexible film, and a hard substrate such as metal. A thermosetting metal substrate bonding resin composition capable of obtaining sufficient adhesion strength even at a processing temperature of less than 200 ° C., and the metal substrate bonding resin composition The object is to provide a laminate such as a laminated steel plate used.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above-mentioned goal can be achieved by the following metal base bonding resin composition, and have completed the present invention.

That is, the present invention is a resin composition for joining a metal substrate, comprising a first copolymer (A), a second copolymer (B), and a reactive compound (C), The present invention relates to a resin composition for joining metal substrates, which is (1) and (2).
(1) The first copolymer (A) has a glass transition temperature (Tg) of 10 ° C. or higher and lower than 100 ° C., and
Copolymerized α, β-unsaturated compound (a1) containing one or more hydroxyl groups in the molecule and other copolymerizable α, β-unsaturated compound (a3) (excluding (a2) below) Do it.
(2) an α, β-unsaturated compound (a2) in which the second copolymer (B) has one or more functional groups selected from the group consisting of a carboxyl group, a phosphate group, and a sulfonyl group; Other copolymerized α, β-unsaturated compounds (a3) (excluding the above (a1)) are copolymerized.

  Further, the present invention provides the metal group, wherein the copolymer (A) contains 30 to 99 parts by weight with respect to 100 parts by weight of the total of the copolymer (A) and the copolymer (B). The present invention relates to a resin composition for joining materials.

In the present invention, the copolymer (A) is
In 100 parts by weight of all α, β-unsaturated compounds used for copolymerization,
0.01-20 parts by weight of α, β-unsaturated compound (a1);
The present invention relates to the metal base-bonding resin composition, which is obtained by copolymerizing 80 to 99.99 parts by weight of another copolymerizable α, β-unsaturated compound (a3).

  In the present invention, the copolymer (A) has a weight average molecular weight of 50,000 to 1,000,000, and the copolymer (B) has a weight average molecular weight of 1,000 to 300,000. It is related with the said resin composition for metal base joining characterized by the above-mentioned.

  The present invention also relates to the above resin composition for bonding a metal substrate, wherein the reactive compound (C) is an isocyanate group-containing compound (c1).

  Moreover, this invention relates to the said resin composition for metal base joining characterized by the isocyanate group containing compound (c1) containing block isocyanate (c1-1).

The present invention further contains a silane coupling agent (D),
It is related with the said resin composition for metal base joining characterized by including 0.1-5 weight part of silane coupling agents (D) with respect to 100 weight part of copolymers (A).

Moreover, this invention relates to the laminated body formed by adhere | attaching a 1st base material (K1) and a 2nd base material (K2) with the said resin composition for metal base joining.
However, at least one of the first substrate (K1) and the second substrate (K2) is a metal substrate.

  Moreover, this invention relates to the said laminated body characterized by a metal base material being a steel plate.

  By using the metal substrate-bonding resin composition of the present invention, it is possible to provide a highly durable laminated sheet having excellent adhesive strength even in various substrates centering on a vinyl chloride film. . In particular, when joining a steel sheet and a vinyl chloride film, it is possible to provide a resin composition for joining a metal base material that is excellent in peel strength, processability, and water resistance at a treatment temperature of less than 200 ° C.

Hereinafter, preferred embodiments of the present invention will be described.

The resin composition for joining a metal base material according to the present invention comprises a first copolymer (A) containing a hydroxyl group and a second copolymer containing any one of a carboxyl group, a phosphate group and a sulfonyl group ( B) and the copolymer (A) and at least a reactive compound (C) capable of reacting with the copolymer (A). Details will be described below.

<First copolymer (A)>
The copolymer (A) of the present invention is obtained by copolymerizing an α, β-unsaturated compound, and an α, β-unsaturated compound (a1) containing a hydroxyl group and other copolymerizable α, β- It is a copolymer in which the composition ratio of the unsaturated compound (a3) is adjusted and the glass transition temperature (Tg) is 10 ° C. or higher and lower than 100 ° C.

Of the α, β-unsaturated compound used for copolymerization of the copolymer (A) in 100 parts by weight, the α, β-unsaturated compound (a1) having a hydroxyl group preferably contains 0.01 to 20 parts by weight, It is more preferable to contain 0.1-15 weight part, and it is still more preferable to contain 0.5-10 weight part.
When the amount is less than 0.01 part by weight, it is difficult to obtain a high cohesive force due to a molecular weight improving effect caused by a curing reaction with a functional group contained in the compound (B) described later, In some cases, the cohesive force in the cured coating film is insufficient and the adhesive strength cannot be obtained. When the amount is more than 20 parts by weight, curing shrinkage due to the curing reaction becomes significant, and sufficient adhesive strength may not be obtained. In addition, since the range of 0.5 to 10 parts by weight can not only ensure the internal cohesive force capable of expressing entropy elasticity by the molecular weight improvement effect accompanying the curing reaction of the cured coating film, but also hardly cause curing shrinkage. preferable.
Thus, by giving entropy elasticity to the cured coating film, it is possible to follow the slow expansion and contraction movement of the substrate due to environmental changes, and it is possible to prevent a decrease in adhesive strength.

  In the present application, when “(meth) acryloyl”, “(meth) acrylic acid”, “(meth) acrylate”, “(meth) acryloyloxy”, and “(meth) allyl” are expressed, Unless otherwise stated, “acryloyl and / or methacryloyl”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, “acryloyloxy and / or methacryloyloxy”, and “allyl and / or methallyl”, respectively. ".

  The α, β-unsaturated compound (a1) is not particularly limited as long as it is a compound containing one or more hydroxyl groups and one or more α, β-unsaturated double bond groups in its structure. Not usable. Although not specifically limited, the following compounds are mentioned as specific examples.

  Examples of the α, β-unsaturated compound (a-1) containing one or more hydroxyl groups include 2-hydroxyethyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, and (meth) acrylic acid. 2-hydroxypropyl, 3-hydroxypropyl (meth) acrylate, 1-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, (meth) acrylic acid 4-hydroxybutyl, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, (meth) acrylate 10-hydroxydecyl, (meth) acryl Acid 12-hydroxylauryl, ethyl (meth) acrylate-α- (hydroxy Methyl), monofunctional (meth) acrylic acid glycerol, or (meth) acrylic acid glycidyl laurate, (meth) acrylic acid glycidyl oleate, (meth) acrylic acid glycidyl stearate, etc. By ring-opening addition of ε-caprolactone lactone to the hydroxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound such as acrylate ester or 2- (acryloyloxy) ethyl 6-hydroxyhexanonate (Meth) acrylic acid ester having a hydroxyl group at the terminal or alkylene obtained by repeatedly adding alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the hydroxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound Oxai Adding (meth) aliphatic hydroxyl group-containing acrylic acid ester (meth) acrylate;

For example, (meth) acrylic acid 1,2-cyclohexanedimethanol, (meth) acrylic acid 1,3-cyclohexanedimethanol, (meth) acrylic acid 1,4-cyclohexanedimethanol, (meth) acrylic acid 2-hydroxy- 3-phenoxymethyl, 2-hydroxy-3-phenoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3-phenoxybutyl (meth) acrylate, (meth) 2-hydroxy-3-phenoxydecyl acrylate, 2-hydroxy-3-phenoxyoctadecyl (meth) acrylate, monohydroxyethyl phthalate (meth) acrylate, 2- (4-benzoyl-3-hydroxy) (meth) acrylate Phenoxy) Cyclic groups other than ethyl and hydroxyl groups and heterocycles Having concrete (meth) acrylic acid esters;

For example, 2-hydroxy-4- {2- (meth) acryloyloxy} ethoxybenzophenone, 2-hydroxy-4- {2- (meth) acryloyloxy} butoxybenzophenone, 2,2′-dihydroxy-4- {2- Hydroxyl group-containing benzophenone-based (meth) acrylic esters such as (meth) acryloyloxy} ethoxybenzophenone, 2-hydroxy-4- {2- (meth) acryloyloxy} ethoxy-4 ′-(2-hydroxyethoxy) benzophenone;

For example, 2- (2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl) -5-chloro -2H-benzotriazole, 2- (2'-hydroxy-5 '-(meth) acryloyloxypropylphenyl) -2H-benzotriazole; 2- (2'-hydroxy-5'-(meth) acryloyloxypropylphenyl) -5-chloro-2H-benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5 '-(meth) acryloyloxyethylphenyl) -2H-benzotriazole, and 2- (2'-hydroxy -3'-tert-butyl-5 '-(meth) acryloyloxyethylphenyl) -5-chloro-2H-ben Hydroxyl group-containing benzotriazole-based triazole (meth) acrylic acid esters;

For example, 2,4-diphenyl-6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2-methylphenyl) -6- [2- Hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2-methoxyphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy }]-S-triazine, 2,4-bis (2-ethylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis ( 2-Ethoxyphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2,4-dimethylphenyl) -6- [2- Hydroxy-4- {2- Meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2,4-diethoxylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S- Hydroxyl-containing triazines such as triazine and 2,4-bis (2,4-diethylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy})]-S-triazine (meta ) Acrylic acid esters and the like, and these may be used alone or in combination of two or more.

  Also, for example, hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxyhexyl vinyl ether, hydroxyoctyl vinyl ether, hydroxydecyl vinyl ether, hydroxydodecyl vinyl ether, hydroxyoctadecyl vinyl ether, glyceryl vinyl ether, triethylene glycol monovinyl ether, tetraethylene glycol monovinyl ether , Trimethylolpropane monovinyl ether, pentaerythritol monovinyl ether, or hydroxyl-containing aliphatic vinyl ethers such as alkylene oxide-added vinyl ether having a hydroxyl group at the terminal where alkylene oxide such as ethylene oxide or propylene oxide is repeatedly added

For example, (meth) allyl alcohol, isopropenyl alcohol, dimethyl (meth) allyl alcohol, hydroxyethyl (meth) allyl ether, hydroxypropyl (meth) allyl ether, hydroxybutyl (meth) allyl ether, hydroxyhexyl (meth) allyl ether , Hydroxyoctyl (meth) allyl ether, hydroxydecyl (meth) allyl ether, hydroxydodecyl (meth) allyl ether, hydroxyoctadecyl (meth) allyl ether, glyceryl (meth) allyl ether, or alkylene oxides such as ethylene oxide and propylene oxide Hydroxyl group-containing aliphatic (meth) allyl alcohols such as alkylene oxide addition system (meth) allyl ether having a hydroxyl group at the terminal of repeating addition of Or (meth) allyl ethers;

For example, α, β-unsaturated double bond group-containing compounds having a plurality of hydroxyl groups such as propenediol, butenediol, heptenediol, octenediol, and glycerol di (meth) acrylate;

For example, hydroxyl groups such as N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide, N-hydroxyhexyl (meth) acrylamide, N-hydroxyoctyl (meth) acrylamide, etc. Of (meth) acrylamides;

Examples thereof include monomers having a hydroxyl group and a vinyl group such as vinyl alcohol, but are not particularly limited thereto. These may use only 1 type or may use multiple types together.

  Among the compounds (a1), from the viewpoint of adhesion to the substrate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, ε-caprolactone [Alpha], [beta] -unsaturated double bond group-containing compound having 2 to 18 carbon atoms such as 2-hydroxyethyl addition (1-2) ethyl (meth) acrylate, (meth) acrylic acid 1,2-cyclohexanedimethanol, (meta Acrylic acid 1,3-cyclohexanedimethanol and (meth) acrylic acid 1,4-cyclohexanedimethanol are preferred.

  Among these, from the viewpoint of reactivity with the reactive compound (C) described later, 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferable.

  As the other copolymerizable α, β-unsaturated compound (a3) used for the copolymer (A), α, β containing any of the above (a1) and a carboxyl group, a phosphate group or a sulfonyl group -If it is except unsaturated compound (a2), it will not be limited, However, (alpha), (beta)-unsaturated compound copolymerizable with (a1) is used. However, in the present invention, if the copolymer (A) and the copolymer (B) are included, a copolymer obtained by copolymerizing (a1), (a2) and (a3) is further included. You can leave.

  By using the compound (a3), the glass transition temperature (Tg) of the copolymer (A) is improved to develop a high cohesive force, the polarity of the resin is controlled, and the substrate has a high affinity. By manifesting it, it becomes possible to easily form an adhesive layer having good heat resistance and water resistance. Specific examples are listed below.

  For example, methyl (meth) acrylate, ethyl (meth) acrylate, 1-propyl (meth) acrylate, 2-propyl (meth) acrylate, n-butyl (meth) acrylate, sec- (meth) acrylic acid sec- Butyl, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-amyl (meth) acrylate, iso-amyl (meth) acrylate, n-hexyl (meth) acrylate, (meth) 2-ethylhexyl acrylate, n-octyl (meth) acrylate, iso-octyl (meth) acrylate, n-nonyl (meth) acrylate, (meth) acryl iso-nonyl, decyl (meth) acrylate, (meth) ) Dodecyl acrylate, octadecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate Of (meth) acrylic acid alkyl esters;

For example, cyclohexyl (meth) acrylate, 1-methyl-1-cyclopentyl (meth) acrylate, 1-ethyl-1-cyclopentyl (meth) acrylate, 1-isopropyl-1-cyclopentyl (meth) acrylate, (meth ) 1-methyl-1-cyclohexyl acrylate, 1-ethyl-1-cyclohexyl (meth) acrylate, 1-isopropyl-1-cyclohexyl (meth) acrylate, 1-ethyl-1-cyclooctyl (meth) acrylate Benzyl (meth) acrylate, iso-bornyl (meth) acrylate, phenyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, 2-oxo-1,2-phenylethyl (meth) acrylate, (Meth) acrylic acid 2-oxo-1,2-diphenylethyl, (meth) acrylic acid 1 Naphthyl, 2-naphthyl (meth) acrylate, 1-naphthylmethyl (meth) acrylate, 1-anthryl (meth) acrylate, 2-anthryl (meth) acrylate, 9-anthryl (meth) acrylate, (meth ) 9-anthrylmethyl acrylate, 2-methyladamantyl-2-yl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl (meth) acrylate Oxyethyl, 2-ethyladamantyl-2-yl (meth) acrylate, 2-n-propyladamantyl-2-yl (meth) acrylate, 2-isopropyladamantyl-2-yl (meth) acrylate, (meth) 1- (adamantan-1-yl) -1-methylethyl acrylate, 1- (ada) (meth) acrylic acid Ntan-1-yl) -1-ethylethyl, 1- (adamantan-1-yl) -1-methylpropyl (meth) acrylate, 1- (adamantan-1-yl) -1-ethylpropyl (meth) acrylate , (Meth) acrylic acid-5-oxo-4-oxa-tricyclo [4.2.1.03,7] non-2-yl, (meth) acrylic acid-5-oxo-4-oxa-tricyclo [5 .2.1.03,8] dec-2-yl, dihydro-α-terpinyl (meth) acrylate, (meth) acrylic acid-6-oxo-7-oxa-bicyclo [3.2.1] octa- 2-yl, (meth) acrylic acid-7-oxo-8-oxa-bicyclo [3.3.1] oct-2-yl, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl F 2- (meth) acryloyloxybutyl phthalate, 2- (meth) acryloyloxyhexyl phthalate, 2- (meth) acryloyloxyoctyl phthalate, 2- (meth) acryloyloxydecyl phthalate, 2- (meth) acryloyloxyethyl Hexahydrophthalate, (meth) acrylic acid (3,4-epoxycyclohexyl) methyl, (meth) acrylic acid-o-2-propenylphenyl, (meth) acrylic acid cyclohexyl glycidyl ether, (meth) acrylic acid phenylglycidyl ether, etc. (Meth) acrylic acid cyclic esters of

For example, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 3-propoxyethyl (meth) acrylate, 2-butoxy (meth) acrylate Alkoxy group-containing (meth) acrylic acid esters such as ethyl, 3-butoxyethyl (meth) acrylate, 4-butoxyethyl (meth) acrylate;

For example, alkylene oxide-containing (meth) acrylic acid derivatives such as poly (ethylene) ethene oxide methyl (meth) acrylate and polyethylene oxide ethyl (meth) acrylate;

For example, styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-methoxystyrene, 3-methoxystyrene, 4-methoxystyrene, 4-t-butoxystyrene, 4-t- Butoxy-α-methylstyrene, 4- (2-ethyl-2-propoxy) styrene, 4- (2-ethyl-2-propoxy) -α-methylstyrene, 4- (1-ethoxyethoxy) styrene, 4- ( Aromatic vinyl monomers such as 1-ethoxyethoxy) -α-methylstyrene, 1-butylstyrene, 1-chloro-4-isopropenylbenzene;

For example, (meth) acrylic acid (meth) allyl, (meth) acrylic acid 1-butenyl, (meth) acrylic acid 2-butenyl, (meth) acrylic acid 3-butenyl, (meth) acrylic acid 1,3-methyl- 3-butenyl, (meth) acrylic acid 2-chloro-2-propenyl, (meth) acrylic acid 3-chloro-2-propenyl, (meth) acrylic acid 2- (2-propenyloxy) ethyl, (meth) acrylic acid 2- Propenyl lactyl, 3,7-dimethyloct-6-en-1-yl (meth) acrylate, (meth) acrylic acid (E) -3,7-dimethyloct-2,6-dien-1-yl, (Meth) acrylic acid esters further containing an unsaturated group such as rosinyl (meth) acrylate, cinnamyl (meth) acrylate, vinyl (meth) acrylate;

For example, perfluoromethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoropropyl (meth) acrylate, perfluorobutyl (meth) acrylate, perfluorooctyl (meth) acrylate, (meth) Trifluoromethylmethyl acrylate, 2-trifluoromethylethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-par (meth) acrylate Fluoromethyl-2-perfluoroethylmethyl, triperfluoromethylmethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate , (Meth) acrylic propenoic acid 2-perf Orodeshiruechiru, (meth) (meth) acrylic acid perfluoroalkyl esters such as 2-perfluoro-hexadecyl acrylate;

For example, glycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, (3-methyl-3-oxetanyl) methyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ( (Meth) acrylic acid-2-oxotetrahydropyran-4-yl, (meth) acrylic acid-4-methyl-2-oxotetrahydropyran-4-yl, (meth) acrylic acid-4-ethyl-2-oxotetrahydropyran -4-yl, (meth) acrylic acid-4-propyl-2-oxotetrahydropyran-4-yl, (meth) acrylic acid-5-oxotetrahydrofuran-3-yl, (meth) acrylic acid-2,2- Dimethyl-5-oxotetrahydrofuran-3-yl, (meth) acrylic acid-4,4-dimethyl-5-oxoteto Hydrofuran-3-yl, (meth) acrylic acid-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-4,4-dimethyl-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-5, 5-dimethyl-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-5-oxotetrahydrofuran-2-ylmethyl, (meth) acrylic acid-3 , 3-Dimethyl-5-oxotetrahydrofuran-2-ylmethyl, (meth) acrylic acid-4,4-dimethyl-5-oxotetrahydrofuran-2-ylmethyl, and the like. ;

For example, N-methylaminoethyl (meth) acrylate, N-ethylaminoethyl (meth) acrylate, N-propylaminoethyl (meth) acrylate, N-butylaminoethyl (meth) acrylate, (meth) acryl (Meth) acrylic acid esters having primary and / or secondary amino groups such as acid N-tributylaminoethyl, tetramethylpiperidinyl (meth) acrylate, tetramethylpiperidinyl acrylate, etc .;

For example, (meth) acrylic acid hydrazide, 2- (2-furyl) -3- (5-nitro-2-furyl) (meth) acrylic acid hydrazide, β- (2-furanyl) (meth) acrylic acid N2, N2 -Bis (2-chloroethyl) hydrazide, p-vinylbenzhydrazide, N- (m-vinylphenyl) acrylohydrazide, 4-vinylbenzenesulfonic acid hydrazide, 2- [2- (5-nitro-2-furyl) vinyl ] -4-Methacrylic acid esters having a hydrazino group such as quinolinecarbohydrazide;

For example, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, pentamethylpiperidinyl (meth) acrylate, 4- (pyrimidine (2-yl) piperazin-1-yl (meth) acrylate (meth) acrylic acid esters having a tertiary amino group;

For example, imide (meth) acrylate, 2- (4-oxazolin-3-yl) ethyl (meth) acrylate, di (meth) acrylic acid ethoxylated isocyanuric acid, tri (meth) acrylic acid ethoxylated isocyanuric acid, ε-caprolactone Heterocyclic structures containing oxygen atoms in addition to nitrogen atoms such as modified tris- (2-acryloyloxyethyl) isocyanurate, di (meth) acrylic acid isocyanuric acid ethylene oxide modification, tri (meth) acrylic acid isocyanuric acid ethylene oxide modification Cyclic amino group-containing (meth) acrylic acid esters having;

For example, (meth) acrylic acid (methoxycarbonyl) methyl, (meth) acrylic acid (methoxycarbonyl) ethyl, (meth) acrylic acid (methoxycarbonyl) propyl, (meth) acrylic acid (methoxycarbonyl) butyl, (meth) acrylic Acid (methoxycarbonyl) decyl, (meth) acrylic acid (ethoxycarbonyl) methyl, (meth) acrylic acid (ethoxycarbonyl) ethyl, (meth) acrylic acid (ethoxycarbonyl) propyl, (meth) acrylic acid (ethoxycarbonyl) butyl , (Meth) acrylic acid (ethoxycarbonyl) hexyl, (meth) acrylic acid (ethoxycarbonyl) octyl, (meth) acrylic acid 2- (ethoxycarbonyloxy) ethyl, (meth) acrylic acid 2- (ethoxycarbonyloxy) propyl , (Meth) acrylic acid 2- (ethoxyca (Rubonyloxy) butyl, 2- (ethoxycarbonyloxy) hexyl (meth) acrylate, 2- (ethoxycarbonyloxy) octyl (meth) acrylate, 2- (propoxycarbonyloxy) ethyl (meth) acrylate, (meth) 2- (Butoxycarbonyloxy) ethyl acrylate, 2- (butoxycarbonyloxy) butyl (meth) acrylate, 2- (octyloxycarbonyloxy) ethyl (meth) acrylate, 2- (octyloxy) (meth) acrylate Aliphatic (meth) acrylic acid esters having one carbonyl group such as carbonyloxy) butyl;

For example, 2-oxobutanoylethyl (meth) acrylate, 2-oxobutanoylpropyl (meth) acrylate, 2-oxobutanoylbutyl (meth) acrylate, 2-oxobutanoylhexyl (meth) acrylate, (Meth) acrylic acid 2-oxobutanoyloctyl, (meth) acrylic acid 2-oxobutanoyldecyl, (meth) acrylic acid 2-oxobutanoyldodecyl, (meth) acrylic acid 3-oxobutanoylethyl, ) 3-oxobutanoylpropyl acrylate, 3-oxobutanoylbutyl (meth) acrylate, 3-oxobutanoylhexyl (meth) acrylate, 3-oxobutanoyloctyl (meth) acrylate, (meth) acrylic 3-oxobutanoyldecyl acid, 3-oxobutanoyldodecyl (meth) acrylate (Meth) acrylic acid 4-cyanooxobutanoylethyl, (meth) acrylic acid 4-cyanooxobutanoylpropyl, (meth) acrylic acid 4-cyanooxobutanoylbutyl, (meth) acrylic acid 4-cyanooxobutanoyl Ruhexyl, 4-cyanooxobutanoyloctyl (meth) acrylate, 2,3-di (oxobutanoyl) propyl (meth) acrylate, 2,3-di (oxobutanoyl) butyl (meth) acrylate, ( Aliphatic (meth) acrylic acid esters having two carbonyl groups such as 2,3-di (oxobutanoyl) hexyl (meth) acrylate and 2,3-di (oxobutanoyl) octyl (meth) acrylate Kind;

For example, (meth) acrylic acid-9-methoxycarbonyl-5-oxo-4-oxa-tricyclo [4.2.1.03,7] non-2-yl, (meth) acrylic acid-10-methoxycarbonyl- 5-oxo-4-oxa-tricyclo [5.2.1.03,8] non-2-yl, (meth) acrylic acid-4-methoxycarbonyl-6-oxo-7-oxa-bicyclo [3.2 .1] having a carbonyl group such as octa-2-yl, (meth) acrylic acid-4-methoxycarbonyl-7-oxo-8-oxa-bicyclo [3.3.1] oct-2-yl (meth) Acrylic acid cyclic esters;

For example, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N-propyl (Meth) acrylamide, N-tert-butyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-octyl (meth) acrylamide, N-nonyl (meth) acrylamide, N-tricosyl (meth) acrylamide, N-nonadecyl (Meth) acrylamide, N-docosyl (meth) acrylamide, N-methylene (meth) acrylamide, N-tridecyl (meth) acrylamide, N- (5,5-dimethylhexyl) (meth) acrylamide, crotonamide, maleami , Fumaramide, mesaconamide, citraconic amide, itaconic amide, 2-methylprop-2-enoylamine, N, N-dimethyl (meth) acrylamide, N, N-diethyl- (meth) acrylamide, N- [3- (N ′, N Aliphatic (meth) acrylamides such as' -dimethylamino) propyl]-(meth) acrylamide, N- (dibutylaminomethyl) (meth) acrylamide, N-vinylmethanamide, N-vinylacetamide;

For example, N-methoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-methoxypropyl (meth) acrylamide, N-methoxybutyl (meth) acrylamide, N-methoxyhexyl (meth) acrylamide, N-methoxy Octyl (meth) acrylamide, N-methoxydecyl (meth) acrylamide, N-methoxydodecyl (meth) acrylamide, N-methoxyoctadecyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-ethoxyethyl (meth) acrylamide N-ethoxypropyl (meth) acrylamide, N-ethoxybutyl (meth) acrylamide, N-ethoxyhexyl (meth) acrylamide, N-ethoxyoctyl (meth) acrylamide, N-iso Roxymethyl (meth) acrylamide, N-isopropoxyethyl (meth) acrylamide, N-isopropoxypropyl (meth) acrylamide, N-isopropoxybutyl (meth) acrylamide, N-isopropoxyhexyl (meth) acrylamide, N-isopropoxy Octyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-butoxyethyl (meth) acrylamide, N-butoxypropyl (meth) acrylamide, N-butoxybutyl (meth) acrylamide, N-butoxyhexyl (meth) acrylamide N-butoxyoctyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide, N-isobutoxyethyl (meth) acrylamide, N-isobutoxypropyl (meth) Acrylamide, N-isobutoxybutyl (meth) acrylamide, N-isobutoxyhexyl (meth) acrylamide, N-isobutoxyoctyl (meth) acrylamide, N- (pentoxymethyl) (meth) acrylamide, N-1-methyl- N-alkoxy group-containing (meth) acrylamides such as 2-methoxyethyl (meth) acrylamide, N, N-di (methoxymethyl) meth) acrylamide, N, N-di (ethoxymethyl) (meth) acrylamide;

For example, (meth) acrylamides having a tertiary amino group such as dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide;

For example, N- (4-carbamoylphenyl) (meth) acrylamide, β- (2-furyl) (meth) acrylamide, 2,3-bis (2-furyl) acrylamide, N- (9H-fluoren-2-yl) (Meth) acrylamide, N-[(R) -1-phenylethyl] (meth) acrylamide, N-[(S) -1-phenylethyl] (meth) acrylamide, (Z) -N-methyl-3- ( Phenyl) (meth) acrylamide, (Z) -3- (phenyl) (meth) acrylamide, N, N-diethyl-3-phenyl (meth) acrylamide, (Z) -N, N-dimethyl-3- (phenyl) (Meth) acrylamides containing cyclic structures such as (meth) acrylamide

For example, 4-acryloylmorpholine, N- [2- (1H-imidazol-5-yl) ethyl] (meth) acrylamide, N- (oxetane-3-ylmethoxymethyl) (meth) acrylamide, N- (oxetane-2 -Heterocyclic acrylamides such as (ylmethoxymethyl) (meth) acrylamide;

For example, vinylamine, methylvinylamine, ethylvinylamine, propylvinylamine, butylvinylamine, 2-vinylimidazole, 2-vinylpiperazine, 4-vinylpiperazine, 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 6-methyl-2-ethenylpyridine, 2-vinylpyrrole, 2-methyl-5-vinyl-1H-pyrrole, 2-vinylpyrazine, 2-methyl-5-vinylpyrazine, 2-methyl-6-vinylpyrazine, 2,5-dimethyl-3-vinylpyrazine, 2-vinylpyrimidine, 2-vinylpyridazine, 2-vinyl-1H-benzimidazole, 2-vinyl-5,6-dimethyl-1H-benzimidazole, 2-vinylindazole, 2-vinylquinoline, 4-vinylquinoline, 2-vinylisoquino Phosphorus, 2-vinylisoxaline, 2-vinylquinoxaline, 2-vinylquinazoline, 2-vinylcinnoline, 2,3-divinylpyridine, 2,4-divinylpyridine, 2,5-divinylpyridine, 2,6- Vinyl compounds having primary and / or secondary amino groups such as divinylpyridine;

For example, (meth) allylamine, 4- (meth) allyl-3,5-dimethyl-1H-pyrazole, 5- (1-methylpropyl) -5- (meth) allylpyrimidine, 5- (meth) allyl-5- (Meth) having primary and / or secondary amino groups such as isopropylpyrimidine, 2- (meth) allylpyridine, 4- (meth) allylpyridine, 3,6-dihydro-4- (meth) allylpyridine, etc. Allyl compounds;

For example, vinyl compounds containing tertiary amino groups such as N-ethyl-N-nitrosovinylamine;

For example, maleic derivatives of maleimide derivatives having both nitrogen and oxygen atoms, such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide, β-unsaturated double bond group-containing compounds;

For example, 2-vinyl oxazole, 2-phenyl-4-vinyl oxazole, 2-phenyl-5-vinyl oxazole, 5-ethoxy-2-vinyl oxazole, 3-vinyl-5-nitrosoxazole, 2-vinyl-4,5 -It has a heterocyclic structure containing an oxygen atom in addition to a nitrogen atom such as diphenyloxazole, 2-vinyl-2-oxazoline, 4,4-dimethyl-2-vinyl-2-oxazolin-5-one, 2-vinylbenzoxazole Vinyl group-containing compounds;

For example, 1-vinylpyrrole, 1-vinyl-2-imidazoline, 1-vinyl-2-methyl-2-imidazoline, 1-vinylimidazole, 1-vinyl-1H-pyrazole, 1-vinyl-3,5-dimethyl- 1H-pyrazole, 3-methyl-5-phenyl-1-vinylpyrazole, 1-vinylindole, 1-vinyl-2-methyl-1H-indole, 1-vinylisoindole, 1-vinyl-1H-benzimidazole, 1 -Vinylindazole, 1-vinylquinoline, 1-vinylisoxaline, 1-vinylquinazoline, 1-vinylcinnoline, 1-vinylcarbazole, 1,1'-divinyl-2,2'-bi (1H-imidazole) N-vinyl-2-pyrrolidone, N-vinyl-ε-caprolactam, 1-vinylpyridin-2 (1H) -one 1-vinyl -2 (IH) - cyclic amino group-containing compounds having a heterocyclic nitrogen-containing, such as pyridinethione;

For example, 1- (meth) allyl-1H-imidazole, 1- (meth) allyl-2-methyl-1H-imidazole, 1- (meth) allyl-3-methyl-1H-imidazol-3-ium, 1- ( (Meth) allyl-3-ethyl-1H-imidazol-3-ium, 5-bromo-1- (meth) allyl-1H-pyrazole, 1- (meth) allylpiperazine, 1- (meth) allyl-5,5- Diethylpyrimidine, N- (meth) allyl-s-triazine-2,4,6-triamine, N- (meth) allyl-4,6-dichloro-1,3-5-triazine-2-amine, 1-benzyl 2-vinylpiperazine, 1-benzyl-3-vinylpiperazine, 1,4-dimethyl-3-vinylpiperazine, 2-vinyl-4,6-diamino-1,3,5-triazine, 6-vinyl 1,3,5-dimethyl-2,4-diamine, 3-vinyl-1,2,4,5-cyclic amino group-containing compounds having a six-membered ring nitrogen-containing, such as tetrazine;

For example, 1-vinyl-1H-benzimidazole, 1-vinyl-5,6-dimethyl-1H-benzimidazole, 1-vinylindazole, 1-vinylquinoline, 1-vinylquinoline, 1-vinylisoquinoline, 1-vinyliso Xaline, 1-vinylquinoxaline, 1-vinylquinazoline, 1-vinylcinnoline, 1- (meth) allyl-1H-benzimidazole, 1- (meth) allyl-3-methyl-1H-indazole, 1- (meta ) Nitrogen atoms such as allyl-4-methyl-1H-indazole, N- (meth) allylquinolin-4-amine, di (meth) allylquinoline, 1,2-di (meth) allyl-1,2-dihydroisoquinoline Containing heteropolycyclic cyclic amino group-containing compounds;

For example, compounds having a nitrogen atom-containing heterocyclic structure and two or more cyclic amino groups, such as 1-methyl-4,5-divinyl-1H-imidazole;

For example, 1- (meth) allyl-3,5-dimethyl-1H-pyrazole, 1- (1-methylpropyl) -5- (meth) allylpyrimidine, 1- (meth) allyl-5-isopropylpyrimidine, 1- Cyclic amino group-containing (meth) allyl group-containing compounds having a nitrogen atom-containing heterocyclic structure such as (meth) allylpyridine, 1- (meth) allylpyridine, and 3,6-dihydro-1- (meth) allylpyridine ;

For example, 2- (meth) allyl-1H-indole, 3- (meth) allyl-1H-indole, 2- (meth) allylindazole, 3-phenyl-4- (meth) allylisoquinoline, 9- (meth) allyl Examples include cyclic amino group-containing (meth) allyl group-containing compounds having a nitrogen atom-containing heteropolycyclic structure such as -9H-carbazole, but are not particularly limited thereto. These may use only 1 type or may use multiple types together.

For example, (meth) acryloyloxyethyldimethylbenzylammonium-p-toluenesulfonate, (meth) acryloyloxyethyltrimethylammonium-p-toluenesulfonate, (meth) acryloylaminopropyltrimethylammonium-p-toluenesulfonate, phenyl-2- ( Metal salts and ammonium salts of (meth) acrylic acid cyclic esters containing a sulfonyl group such as (meth) acryloyloxyethyl phosphate;

For example, di (meth) acrylic acid tricyclodecane dihydroxymethyl, di (meth) acrylic acid tricyclodecane dihydroxymethyl dicaprolactonate, di (meth) acrylic acid 1,2-adamantanediol, di (meth) acrylic acid 1 , 3-adamantanediol, 1,4-adamantanediol di (meth) acrylate, tricyclodecanyl dimethylol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, di (meth) acrylate di Cyclopentenyl, dicyclopentenyloxyethyl di (meth) acrylate, 1,4-bis (2-hydroxypropyl) benzene di (meth) acrylate, 1,3-bis (2-hydroxypropyl) di (meth) acrylate ) Benzene, di (meth) acrylic acid-2,2-bis (hydroxyphenyl) propyl Tetraethylene oxide adduct of bread, tetraethylene oxide adduct of 2,2-bis (hydroxyphenyl) methane di (meth) acrylate, tetraethylene oxide of di (meth) acrylic acid-4,4′-sulfonyldiphenol Adduct, Tetraethylene oxide adduct of di (meth) acrylic acid-water-added 2,2-bis (hydroxyphenyl) propane, Tetra of di (meth) acrylic acid-water-added 2,2-bis (hydroxyphenyl) methane Ethylene oxide adduct, di (meth) acrylic acid-water-added 2,2-bis (hydroxyphenyl) propane, di (2-methyl) propenoic acid-water-added 2,2-bis (hydroxyphenyl) methane, di (meta ) Tetraethylene oxide adduct of acrylic acid-2,2-bis (hydroxyphenyl) propane-dicapro Bifunctional (meth) acrylic acid cyclic esters such as lactonate, tetraethylene oxide adduct of di (meth) acrylic acid-2,2-bis (hydroxyphenyl) methane-dicaprolactonate;

For example, 5-vinylbicyclo [2.2.1] hept-2-ene, 2,5-bis (allyloxy) norbornane, 5-vinyl-2,3-oxirane norbornane, 2- (2-propenyl) bicyclo [2 2.1] Heptane, 5-vinylbicyclo [2.2.1] hept-2-ene, 2-ethenylideneadamantane, 1-allyladamantane, cyclohexyl vinyl ether, cyclohexylmaleimide, vinylcyclohexene monooxirane and the like Cyclic compounds of

For example, cyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, cyclohexyl ethyl vinyl ether, menthyl vinyl ether, tetrahydrofurfuryl vinyl ether, norbornenyl vinyl ether, 1-adamantyl vinyl ether, 2-adamantyl vinyl ether, phenyl vinyl ether, benzyl vinyl ether, 1-naphthyl vinyl ether, 2- Cyclic vinyl ethers such as naphthyl vinyl ether;

For example, vinyl phenyl pentyl ether, vinyl phenyl hexyl ether, vinyl phenyl heptyl ether, vinyl phenyl octyl ether, vinyl phenyl nonyl ether, vinyl phenyl decyl ether, vinyl phenyl undecyl ether, vinyl phenyl dodecyl ether, vinyl phenyl tridecyl ether, vinyl Phenyl tetradecyl ether, vinyl phenyl pentadecyl ether, vinyl phenyl hexadecyl ether, vinyl phenyl heptadecyl ether, vinyl phenyl octadecyl ether, vinyl phenyl nonadecyl ether, vinyl phenyl eicosyl ether, vinyl phenyl henecosyl ether, vinyl phenyl doco Sil ether, vinyl phenyl methyl butyl ether, vinyl phenyl Rupentyl ether, vinyl phenyl methyl hexyl ether, vinyl phenyl methyl heptyl ether, vinyl phenyl methyl octyl ether, vinyl phenyl methyl nonyl ether, vinyl phenyl methyl decyl ether, vinyl phenyl methyl undecyl ether, vinyl phenyl methyl dodecyl ether, vinyl phenyl methyl Tridecyl ether, vinyl phenylmethyl tetradecyl ether, vinyl phenyl methyl pentadecyl ether, vinyl phenyl methyl hexadecyl ether, vinyl phenyl methyl heptadecyl ether, vinyl phenyl methyl octadecyl ether, vinyl phenyl methyl nonadecyl ether, vinyl phenyl methyl eicosyl Ether, vinyl phenyl methyl henecosyl ether, vinyl Aromatic vinyl ether compounds having a long chain alkyl group, such as E methylpropenylmethyl docosyl ether;

For example, hexyl 4-vinylbenzoate, octyl 4-vinylbenzoate, nonyl 4-vinylbenzoate, decyl 4-vinylbenzoate, dodecyl 4-vinylbenzoate, tetradecyl 4-vinylbenzoate, hexadecyl 4-vinylbenzoate , Octadecyl 4-vinylbenzoate, eicosyl 4-vinylbenzoate, docosyl 4-vinylbenzoate, hexyl 4-isopropenylbenzoate, octyl 4-isopropenylbenzoate, nonyl 4-isopropenylbenzoate, 4-isopropenyl Decyl benzoate, 4-isopropenylbenzoic acid dodecyl, 4-isopropenylbenzoic acid tetradecyl, 4-isopropenylbenzoic acid hexadecyl, 4-isopropenylbenzoic acid octadecyl, 4-isopropenylbenzoic acid eicosyl, 4-isopropenylbenzoic acid Docosil How long chain vinyl benzoic acid ester or isopropenyl benzoic acid ester compounds having an alkyl group;

For example, tetra (ethylene oxide) vinyl phenyl ether, methyl tetra (ethylene oxide) vinyl phenyl ether, ethyl tetra (ethylene oxide) vinyl phenyl ether, propyl tetra (ethylene oxide) vinyl phenyl ether, n-butyl tetra (ethylene oxide) vinyl phenyl ether , N-pentyltetra (ethylene oxide) vinyl phenyl ether, tetra (propylene oxide) vinyl phenyl ether, methyl tetra (propylene oxide) vinyl phenyl ether, ethyl tetra (propylene oxide) vinyl phenyl ether, propoxy tetra (propylene oxide) vinyl phenyl ether N-butyltetra (propylene oxide) vinyl phenyl ether, n Pentaxytetra (propylene oxide) vinyl phenyl ether, poly (ethylene oxide) vinyl phenyl ether, methyl poly (ethylene oxide) vinyl phenyl ether, ethyl poly (ethylene oxide) vinyl phenyl ether, poly (propylene oxide) vinyl phenyl ether, methyl poly (propene Oxide) vinyl phenyl ether, ethyl poly (propylene oxide) ethenyl phenyl ether, poly (ethylene oxide) vinyl benzyl ether, methyl poly (ethylene oxide) vinyl benzyl ether, ethyl poly (ethylene oxide) ethenyl benzyl ether, poly (propylene oxide) vinyl Benzyl ether, methyl vinyl poly (propylene oxide) vinyl benzyl Ether, ethyl poly (propylene oxide) vinyl benzyl ether, poly (ethylene oxide) vinyl phenyl ethyl ether, methyl poly (ethylene oxide) vinyl phenyl ethyl ether, ethyl poly (ethylene oxide) vinyl phenyl ethyl ether, poly (oxypropylene) vinyl phenyl ethyl ether Vinyl phenyl ether compounds having a long-chain polyalkylene oxide moiety such as methyl poly (propylene oxide) vinyl phenyl ethyl ether, ethyl poly (propylene oxide) vinyl phenyl ethyl ether;

For example, isopropenyl phenylmethyl butyl ether, isopropenyl phenyl methyl pentyl ether, isopropenyl phenyl methyl hexyl ether, isopropenyl phenyl methyl heptyl ether, isopropenyl phenyl methyl octyl ether, isopropenyl phenyl methyl nonyl ether, isopropenyl phenyl methyl decyl ether, Isopropenyl phenylmethyl undecyl ether, isopropenyl phenyl methyl dodecyl ether, isopropenyl phenyl methyl tridecyl ether, isopropenyl phenyl methyl tetradecyl ether, isopropenyl phenyl methyl pentadecyl ether, isopropenyl phenyl methyl hexadecyl ether, isopropenyl phenyl Methyl heptadecyl ether, Isopropenyl phenyl having a long chain alkyl group such as isopropenyl phenyl methyl octadecyl ether, isopropenyl phenyl methyl nonadecyl ether, isopropenyl phenyl methyl eicosyl ether, isopropenyl phenyl methyl heneicosyl ether, isopropenyl phenyl methyl docosyl ether Compounds,

For example, poly (ethylene oxide) isopropenyl phenyl ether, methyl poly (ethylene oxide) isopropenyl phenyl ether, ethyl poly (ethylene oxide) isopropenyl phenyl ether, poly (propylene oxide) isopropenyl phenyl ether, methyl poly (propylene oxide) isopropenyl phenyl Ether, ethyl poly (propene oxide) isopropenyl phenyl ether, poly (ethylene oxide) isopropenyl benzyl ether, methyl poly (ethylene oxide) isopropenyl benzyl ether, ethyl poly (ethylene oxide) isopropenyl benzyl ether, poly (propylene oxide) isopropenyl benzyl Ether, methyl poly (propylene oxide) Isopropenyl-based compounds having a polyalkylene oxide moiety, such as propenyl benzyl ether;

For example, mono-long chain alkyl ester cyclic compounds of dicarboxylic acid such as vinyl phenylnonyl succinate, vinyl phenyl methyl decyl hexahydrophthalate, vinyl phenyl ethyl dodecyl terephthalate;

For example, monopolyalkylene oxide esters of dicarboxylic acids such as vinyl phenyl poly (ethylene oxide) succinate, vinyl phenyl methyl poly (ethylene oxide) hexahydrophthalate, vinyl phenyl ethyl poly (ethylene oxide) terephthalate;
For example, poly such as methyl 4-vinylbenzoate poly (ethylene oxide), ethyl 4-vinylbenzoate poly (ethylene oxide), methyl 4-isopropenylbenzoate poly (propylene oxide), ethyl polyisopropenylbenzoate poly (propylene oxide), etc. Vinyl benzoate or isopropenyl benzoate compounds having an alkylene oxide moiety;

For example, glycidyl group-containing vinyl esters such as glycidyl cinnamate, allyl glycidyl ether, 1,3-butadiene monooxirane;

For example, 2-vinylthiazol, 4-methyl-5-vinylthiazole, 2-vinylbenzothiazole, 2- [2- (1-naphthyl) vinyl] benzothiazole, 2- [2- (dimethylamino) vinyl] benzo Vinyl group-containing compounds having a heterocyclic structure containing a sulfur atom in addition to a nitrogen atom, such as thiazole;

For example, N- (2-oxobutanoylethyl) (meth) acrylamide, N- (2-oxobutanoylpropyl) (meth) acrylamide, N- (2-oxobutanoylbutyl) (meth) acrylamide, N- ( (Meth) acrylamides having a carbonyl group such as 2-oxobutanoylhexyl) (meth) acrylamide, N- (2-oxobutanoyloctyl) (meth) acrylamide, diacetone (meth) acrylamide;

For example, vinyl acetoacetate, vinyl acetopropionate, vinyl acetoisobutyrate, vinyl acetobutyrate, vinyl acetovalerate, vinyl acetohexanoate, vinyl aceto-2-ethylhexanoate, vinyl aceto-n-octanoate, vinyl acetodecanoate, acetodecanoic acid Vinyl, vinyl acetooctadecanoate, vinyl acetopivalate, vinyl acetocaprate, vinyl acetocrotonate, vinyl acetosorbate, vinyl propanoyl acetate, vinyl butyryl acetate, vinyl isobutyryl acetate, vinyl palmitoyl acetate, vinyl stearoyl acetate, pyrboyl vinyl acetate, propa Vinyl noyl valerate, vinyl butyryl valerate, vinyl isobutyryl valerate, vinyl palmitoyl valerate, vinyl stearoyl valerate, vinyl pyruvyl valerate - acetoacetoxyethyl vinyl ether, 2-acetoacetoxyethyl butyl vinyl ether, 2-acetoacetoxyethyl hexyl vinyl ether, 2-acetoacetoxyethyl vinyl compounds of aliphatic having an acyl group such as octyl vinyl ether;

For example, vinyl benzoyl formate, vinyl benzoyl acetate, vinyl benzoyl propionate, vinyl benzoyl butyrate, vinyl benzoyl valerate, vinyl benzoyl hexanoate, vinyl benzoyl dodecanoate, vinyl 1-naphthoyl vinyl acetate, vinyl 1-naphthoyl propionate, 1- Vinyl naphthoyl butyrate, vinyl 1-naphthoyl valerate, vinyl 1-naphthoyl hexanoate, 2-naphthoyl vinyl acetate, vinyl 2-naphthoyl propionate, vinyl 2-naphthoyl butyrate, vinyl 2-naphthoyl valerate, 2-naphthoyl hexanoate Vinyl, nicotinoyl vinyl acetate, vinyl nicotinoyl propionate, vinyl nicotinoyl butyrate, vinyl nicotinoyl valerate, vinyl nicotinoyl hexanoate, vinyl nicotinoyl decanoate, nicotinoyl dodeca Vinyl acid, vinyl isonicotinoyl acetate, vinyl isonicotinoyl propionate, vinyl isonicotinoyl butyrate, vinyl isonicotinoyl valerate, vinyl isonicotinoyl hexanoate, vinyl isonicotinoyl decanoate, vinyl isonicotinoyl dodecanoate, 2-furoyl acetate Vinyl, vinyl 2-furoylpropionate, vinyl 2-furoyl butyrate, vinyl 2-furoyl valerate, vinyl 2-furoyl hexanoate, vinyl 2-furoyl decanoate, vinyl 2-furoyl dodecanoate, vinyl 3-furoyl vinyl acetate, 3-Furoyl vinyl propionate, 3-Furoyl butyrate, 3-Furoyl valerate, 3-Furoyl hexanoate, 3-Furoyl decanoate, 3-Furoyl dodecanoate, Anthraniloyl vinyl acetate, Anthrani Vinyl ilpropionate, vinyl anthraniloyl butyrate, vinyl anthraniloyl valerate, vinyl anthraniloyl hexanoate, vinyl anthraniloyl decanoate, vinyl anthraniloyl decanoate, 4- (2-t-ethoxycarbonylethyloxy) styrene , Aromatic vinyl compounds having an acyl group such as 4- (2-t-butoxycarbonylethyloxy) styrene and 4- (2-t-butoxycarbonylpropyloxy) styrene;

For example, acetoacetic acid (meth) allyl, acetopropionic acid (meth) allyl, acetoisobutyric acid (meth) allyl, acetobutyric acid (meth) allyl, acetovalerate (meth) allyl, acetohexanoic acid (meth) allyl, aceto-2-ethyl Hexanoic acid (meth) allyl, aceto-n-octanoic acid (meth) allyl, acetodecanoic acid (meth) allyl, acetodecanoic acid (meth) allyl, acetooctadecanoic acid (meth) allyl, acetopivalic acid (meth) allyl, acetocapric acid ( (Meth) allyl, acetocrotonic acid (meth) allyl, acetosorbic acid (meth) allyl, propanoyl acetate (meth) allyl, butyryl acetate (meth) allyl, isobutyryl acetate (meth) allyl, palmitoyl acetate (meth) allyl, stearoyl acetate (Meth) allyl, (meth) allylaldehyde Aliphatic (meth) allyl compounds having an acyl group;

For example, benzoyl formate (meth) allyl, benzoyl acetate (meth) allyl, benzoyl propionate (meth) allyl, benzoyl butyrate (meth) allyl, benzoylvalerate (meth) allyl, benzoylhexanoic acid (meth) allyl, benzoyldodecanoic acid (Meth) allyl, 1-naphthoylacetic acid (meth) allyl, 1-naphthoylpropionic acid (meth) allyl, 1-naphthoylbutyric acid (meth) allyl, 1-naphthoylvaleric acid (meth) allyl, 1-naphthoylhexanoic acid ( (Meth) allyl, 2-naphthoylacetic acid (meth) allyl, 2-naphthoylpropionic acid (meth) allyl, 2-naphthoylbutyric acid (meth) allyl, 2-naphthoylvalerate (meth) allyl, 2-naphthoylhexanoic acid (meta) ) Aromatic (meth) allyl compounds having an acyl group such as allyl Carbonyl group-containing alpha, beta-unsaturated double bond group-containing compounds and the like;

For example, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltripropoxysilane, 3- (meth) acryloyloxypropyltributoxysilane 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 3- (meth) acryloyloxypropylethyldimethoxysilane, 3- (meth) acryloyloxypropylbutyldimethoxysilane, 3- (meth) acryloyloxypropylethyldipropoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 3- (meth) acryloyloxypropyltrime Kishishiran, 3- (meth) acryloyloxy propyl triethoxysilane, 3- (meth) acryloyl alkoxysilyl group-containing (meth) acrylic acid esters such as propyl tripropoxysilane;

For example, metal salts and ammonium of (meth) acrylic acid esters containing sulfonyl groups such as (meth) acryloyloxydimethylethylammonium ethyl sulfate, (meth) acryloylaminopropyltrimethylammonium sulfate, (meth) acryloylaminopropyltriethylammonium sulfate salt;

For example, di (meth) acrylic acid ethylene oxide, di (meth) acrylic acid triethylene oxide, di (meth) acrylic acid tetraethylene oxide, di (meth) acrylic acid polyethylene oxide, di (meth) acrylic acid propylene oxide, di (Meth) acrylic acid dipropylene oxide, di (meth) acrylic acid tripropylene oxide, di (meth) acrylic acid polypropylene oxide, di (meth) acrylic acid butene oxide, di (meth) acrylic acid pentane oxide, di (meth) 2,2-dimethylpropyl acrylate, hydroxypivalylhydroxypivalate di (meth) acrylate, hydroxypivalylhydroxypivalate hydroxypivalate dicaprolactonate, 1,6-hexane di (meth) acrylate Gio Di (meth) acrylic acid 1,2-hexanediol, di (meth) acrylic acid 1,5-hexanediol, di (meth) acrylic acid 2,5-hexanediol, di (meth) acrylic acid 1,7- Heptanediol, 1,8-octanediol di (meth) acrylic acid, 1,2-octanediol di (meth) acrylic acid, 1,9-nonanediol di (meth) acrylic acid, 1, di (meth) acrylic acid 1, 2-decanediol, di (meth) acrylic acid 1,10-decanediol, di (meth) acrylic acid 1,2-decanediol, di (meth) acrylic acid 1,12-dodecanediol, di (meth) acrylic acid 1,2-dodecanediol, di (meth) acrylic acid 1,14-tetradecanediol, di (meth) acrylic acid 1,2-tetradecanediol, di (meth) a 1,16-hexadecanediol silylate, 1,2-hexadecanediol di (meth) acrylate, 2-methyl-2,4-pentanediol di (meth) acrylate, 3-methyl-1 di (meth) acrylate , 5-pentanediol, 2-methyl-2-propyl-1,3-propanediol di (meth) acrylate, 2,4-dimethyl-2,4-pentanediol di (meth) acrylate, di (meth) 2,2-diethyl-1,3-propanediol acrylate, 2,2,4-trimethyl-1,3-pentanediol di (meth) acrylate, dimethyloloctane di (meth) acrylate, di (meth) 2-ethyl-1,3-hexanediol acrylate, 2,5-dimethyl-2,5-hexanediol di (meth) acrylate, 2-methyl di (meth) acrylate , 8-octanediol, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, 2,4-diethyl-1,5-pentanediol di (meth) acrylate, di (meth) 2-methyl-2-propyl-1,3-propanediol acrylate, 2,4-dimethyl-2,4-pentanediol di (meth) acrylate, 2,2-diethyl-1, di (meth) acrylate 3-propanediol, 2,2,4-trimethyl-1,3-pentanediol di (meth) acrylate, dimethyloloctane di (meth) acrylate, 2-ethyl-1,3-di (meth) acrylate Hexanediol, 2,5-dimethyl-2,5-hexanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, di (meth) acrylate ) Bifunctional (meth) acrylic acid esters such as 2,4-diethyl-1,5-pentanediol acrylate, 1,1,1-trishydroxymethylethane di (meth) acrylate;

For example, 1,2,3-propanetriol tri (meth) acrylate, 2-methylpentane-2,4-diol tri (meth) acrylate, 2-methylpentane-2,4-diol tri (meth) acrylate Tricaprolactonate, 2,2-dimethylpropane-1,3-diol tri (meth) acrylate, trimethylolhexane tri (meth) acrylate, trimethyloloctane tri (meth) acrylate, tri (meth) acrylic acid 2,2-bis (hydroxymethyl) 1,3-propanediol, 1,1,1-trishydroxymethylethane tri (meth) acrylate, 1,1,1-trishydroxymethylpropane tri (meth) acrylate, Trifunctional (meth) acrylic esters such as pentaerythritol tri (meth) acrylate;

For example, tetra (meth) acrylic acid pentaerythritol, tetra (meth) acrylic acid ethoxylated pentaerythritol, tetra (meth) acrylic acid ditrimethylolpropane, hexa (meth) acrylic acid dipentaerythritol, tetra (meth) acrylic acid 2, 2-bis (hydroxymethyl) 1,3-propanediol, tetra (meth) acrylic acid 2,2-bis (hydroxymethyl) 1,3-propanediol tetracaprolactonate, tetra (meth) acrylic acid di1, 2,3-propanetriol, tetra (meth) acrylate di-2-methylpentane-2,4-diol, tetra (meth) acrylate di-2-methylpentane-2,4-diol tetracaprolactonate, tetra ( (Meth) acrylic acid di-2,2-dimethylpropane-1,3- All, tetra (meth) acrylate ditrimethylolbutane, tetra (meth) acrylate ditrimethylolhexane, tetra (meth) acrylate ditrimethyloloctane, tetra (meth) acrylate di-2,2-bis (hydroxymethyl) 1, 3-propanediol, hexa (meth) acrylate di-2,2-bis (hydroxymethyl) 1,3-propanediol, hexa (meth) acrylate tri-2,2-bis (hydroxymethyl) 1,3-propanediol , Hepta (meth) acrylic acid tri-2,2-bis (hydroxymethyl) 1,3-propanediol, octa (meth) acrylic acid tri-2,2-bis (hydroxymethyl) 1,3-propanediol, hepta (meta ) Di2,2-bis (hydroxymethyl) 1,3-propanediol acrylate Polyfunctional (meth) acrylic acid esters such as real sharp emission oxide;

For example, vinyl esters of carboxylic acids such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caprate, vinyl laurate, vinyl versatate, vinyl pivalate, vinyl palmitate, vinyl stearate;

For example, methyl vinyl ether, ethyl vinyl ether, 2-chlorovinyl ether, n-propyl vinyl ether, allyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, isopentyl vinyl ether, tert -Pentyl vinyl ether, n-hexyl vinyl ether, isohexyl vinyl ether, 2-ethylbutyl vinyl ether, 2-ethylhexyl vinyl ether, n-heptyl vinyl ether, n-octyl vinyl ether, isooctyl vinyl ether, nonyl vinyl ether, decyl vinyl ether, dodecyl vinyl ether, hexanedecyl vinyl ether , Octa Sil vinyl ether, ethoxymethyl vinyl ether, 2-methoxyethyl vinyl ether, 2-ethoxyethyl vinyl ether, 2-butoxyethyl vinyl ether, acetoxymethyl vinyl ether, 2-acetoxyethyl vinyl ether, 3-acetoxypropyl vinyl ether, 4-acetoxybutyl vinyl ether, 4-ethoxy Butyl vinyl ether, 2- (2-methoxyethoxy) ethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, diethylene glycol methyl vinyl ether, diethylene glycol ethyl vinyl ether, diethylene glycol butyl vinyl ether, etc. The aliphatic Vinyl ether compounds;

For example, ethylene glycol divinyl ether, diethylene glycol divinyl ether (DEGVE), triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, tripropylene glycol divinyl ether, polypropylene glycol Divinyl ether, butanediol divinyl ether, neopentyl glycol divinyl ether, hexanediol divinyl ether, nonanediol divinyl ether, hydroquinone divinyl ether, 1,4-cyclohexanediol divinyl ether (CHODVE), 1,4-cyclohexanedimethanol divinyl ether ( HDVE), trimethylolpropane trivinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether (TMPEOTVE), epentaerythritol tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, ditrimethylolpropane tetravinyl ether, dipentaerythritol hexavinyl ether, etc. Vinyl ethers of

For example, fluorine-containing vinyl compounds such as perfluorovinyl, perfluoropropene, perfluoro (propyl vinyl ether), vinylidene fluoride;

For example, (meth) allylchlorosilane, (meth) allyltrimethoxysilane, (meth) allyltriethoxysilane, (meth) allylaminotrimethylsilane, diethoxyethylvinylsilane, trichlorovinylsilane, trimethoxyvinylsilane, triethoxyvinylsilane, tripropoxy Alkoxysilyl group-containing α, β-unsaturated double bond group-containing compounds such as vinylsilane and vinyltris (2-methoxyethoxy) silane;

For example, nitrile group-containing α, such as (meth) acrylonitrile, α-chloroacrylonitrile, crotonnitrile, maleinnitrile, fumaronitrile, mesaconnitrile, citraconnitrile, itacononitrile, 2-propenenitrile, 2-methacrylic acid (meth) acrylate, etc. β-unsaturated double bond group-containing compounds;

For example, vinyl halides such as vinyl chloride, vinylidene chloride and allyl chloride;

For example, dienes such as allene, 1,2-butadiene, 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene;

For example, cis-diallyl succinate, diallyl 2-methylidene succinate, vinyl (E) -but-2-enoate, (Z) -octadeca-9-enoate, (9Z, 12Z, 15Z) -octadeca-9, Α, β-unsaturated double bond group-containing compounds containing polyfunctional unsaturated bonds such as vinyl 12,15-trienoate;

For example, ethylene, propylene, 1-butene, 2-butene, 2-methylpropene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene 1-docosene, 1-tetracocene, 1-hexacocene, 1-octacocene, 1-triacontene, 1-dotriacontene, 1-tetratoacontene, 1-hexatriacontene, 1-octatriacontene, 1-tetraconten And alkenes such as polybutene-1, polypentene-1, poly-4-methylpentene-1, and the like. In particular, it is not limited to these.

  Moreover, these may use only 1 type or may use multiple types together.

  As the other copolymerizable α, β-unsaturated compound (a3) having no hydroxyl group in the molecule, a compound having a (meth) acryloyl group is preferable from the viewpoint of reactivity, and the resin composition of the present invention is laminated. When used as a steel sheet, the α, β-ethylenically unsaturated double bond group preferably includes a compound having a methacryloyl group.

  In the other copolymerizable α, β-unsaturated compound (a3) of the present invention, polymerization reactivity, shrinkage in crosslinking and curing with a reactive compound (C) described later, heat resistance, moist heat resistance and water resistance From the viewpoint of durability such as, it is possible to obtain a good resin composition by blending in a timely manner so that both the compound (a1) and the compound (a3) are contained in a balanced manner.

The copolymer (A) is based on the balance between the adhesion to the film at the time of lamination and the wettability and cohesive force in the cured coating film after the curing reaction accompanying the crosslinking of the resin composition for bonding a metal substrate. It is preferable to adjust the glass temperature (Tg) of A) to a range of 10 ° C. or more and less than 100 ° C., more preferably 30 ° C. or more and less than 80 ° C., and further preferably 40 ° C. or more and less than 70 ° C. When Tg is less than 10 ° C., the cohesive force in the cured coating film of the resin composition for bonding a metal substrate may be insufficient, causing cohesive failure and reducing the adhesive strength. Since the wettability of the metal substrate bonding resin composition is lowered, the adhesion to the film during lamination may be lowered and peeled off.
If the Tg of a homopolymer that can be formed from each monomer that is a constituent component of the copolymer (A) is known, the copolymer is based on the Tg of each homopolymer and the constituent ratio of each monomer. The Tg of the polymer (A) can be determined theoretically.

The glass transition temperature (Tg) can be theoretically calculated by the following FOX equation.
<FOX type> 1 / Tg = W1 / Tg1 + W2 / Tg2 + ... + Wi / Tgi + ... + Wn / Tgn
[In the above FOX formula, the glass transition temperature of the homopolymer of each monomer constituting the polymer composed of n types of monomers is Tgi (K), the mass fraction of each monomer is Wi, and (W1 + W2 + ... + Wi +... Wn = 1). ]

In addition, the value described in literature can be used for Tg of a homopolymer. As such documents, for example, the following documents can be referred to: Mitsubishi Rayon Co., Ltd. acrylic ester catalog (2001 edition); Osaka Organic Chemical Industry Co., Ltd. catalog (2009 edition); Hitachi Chemical Co., Ltd. funkrill catalog ( 2007 edition); and "POLYMER HANDBOOK" 3rd edition, pages 209-277, John Wiley & Sons, Inc. 1989.
In the present specification, the glass transition temperature (° C.) of a homopolymer of the following monomers is as follows.
(A1) α, β-unsaturated compound containing hydroxyl group 2-hydroxyethyl methacrylate: 55 ° C.
4-hydroxybutyl acrylate: -60 ° C
(A3) Other α, β-unsaturated compound butyl acrylate: −48 ° C.
2-ethylhexyl acrylate: -50 ° C
N-Butyl methacrylate: 20 ° C
Isobornyl methacrylate: 110 ° C
Cyclohexyl methacrylate: 66 ° C
Styrene: 100 ° C
Methyl methacrylate: 105 ° C
Ethyl methacrylate: 65 ° C
2-methoxyethyl methacrylate: -2 ° C
Methacrylic acid: 144 ° C
Glycidyl methacrylate 46 ° C
Ethyl acrylate -24 ℃

  The weight average molecular weight of the copolymer (A) is preferably 50,000 to 1,000,000 in order to ensure the coating suitability of the metal base bonding resin composition and the cohesive strength of the cured coating film. 55,000 to 500,000, more preferably 60,000 to 200,000. When the weight average molecular weight is less than 50,000, the cohesive force of the cured coating film is insufficient, and cohesive failure may occur, resulting in a decrease in adhesive strength. When it is 1,000,000 or more, Viscosity is high, and coatability may be deteriorated. A weight average molecular weight in the range of 60,000 to 200,000 makes it easy to balance the wettability, cohesive force, and viscosity of the cured coating film with respect to the substrate, and exhibits stress relaxation.

  The molecular weight distribution (weight average molecular weight / number average molecular weight) of the copolymer (A) is preferably in the range of 1.5 to 8, more preferably 3 to 6. When the molecular weight distribution (weight average molecular weight / number average molecular weight) is less than 1.5, since there are few low molecular weight components, the leveling property at the time of lamination is lowered, and the initial adhesion to the film may be lowered. When the distribution (weight average molecular weight / number average molecular weight) exceeds 8, the thixotropy becomes too high, and unevenness may occur during coating, resulting in poor appearance of the coating film.

<Copolymer (B)>
The copolymer (B) of the present invention is an α, β-unsaturated compound (a2) having one or more functional groups selected from the group consisting of a carboxyl group, a phosphate group, and a sulfonyl group, and other copolymers are possible. It is a copolymer with an α, β-unsaturated compound (a3).

  Copolymer (B) is obtained by copolymerizing (a2) having an acidic functional group and mixing with copolymer (A), thereby strengthening the interaction with a highly polar substrate and improving the adhesive strength. You can expect In particular, excellent adhesion to metal-based substrates can be expected.

By incorporating (a2) having an acidic functional group into the copolymer (B), it is possible to change the nucleophilicity and electrophilicity of the resin composition for bonding a metal substrate, taking an isocyanate group as an example Then, the following effects are expected.
It is known that the isocyanate group exhibits a resonance structure as represented by the general formula (1).

Among them, the carboxyl group is considered to promote the curing reaction with active hydrogen by moving the resonance of the isocyanate group to N = C ⁺ —O ⁻ .

  In a total of 100 parts by weight of the copolymer (A) and the copolymer (B), the copolymer (A) preferably contains 30 to 99 parts by weight, more preferably 40 to 90 parts by weight, still more preferably. It is preferable to include 50 to 80 parts by weight. When it is less than 30 parts by weight, the curing reaction with the reactive compound (C) is difficult to proceed, the cohesive force in the cured coating film of the metal base joining resin composition is insufficient, and tends to cohesive failure at the time of peeling, Adhesive strength may be reduced, and when it is more than 99 parts by weight, the effect of adding an acidic functional group of the copolymer (B) is difficult to obtain, and adhesiveness may be reduced. In addition, 50 to 80 parts often provide a good balance between the wettability and cohesive force of the cured coating film and have high adhesive strength.

Α, β- having one or more functional groups selected from the group consisting of carboxyl group, phosphate group and sulfonyl group in 100 parts by weight of α, β-unsaturated compound used for copolymerization of copolymer (B) The unsaturated compound (a2) is preferably contained in an amount of 0.01 to 20 parts by weight, more preferably 0.1 to 15 parts by weight, and further preferably 0.5 to 10 parts by weight.
When the amount is less than 0.01 parts by weight, the interaction with the substrate is low and the adhesiveness may be low. When the amount is more than 20 parts by weight, the viscosity of the resin is high, and the coating property is deteriorated or the polarity is low. The compatibility with the copolymer (A) may deteriorate.
In addition, the range of 0.5 to 10 parts by weight is more preferable because it is easy to improve the interaction with the base material and to adjust the compatibility with the copolymer (A).

  Examples of the α, β-unsaturated compound (a2) having one or more functional groups selected from the group consisting of a carboxyl group, a phosphate group, and a sulfonyl group include:

For example, (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, 3-carboxypropyl (meth) acrylate, 4-carboxybutyl (meth) acrylate, (meth ) Acrylic acid dimer, monomethylmaleic acid, monomethylfumaric acid, sorbic acid, cinnamic acid, α-chlorosorbic acid, tiglic acid, angelic acid, senecioic acid, crotonic acid, isococrotonic acid, mucobromic acid, mucochloric acid, penicillic acid, Ring-opening addition of lactone ring such as gellanic acid, citronellic acid, 4-acrylamidobutanoic acid, 6-acrylamidohexanoic acid, 2- (meth) acryloyloxyethyl succinate, mono (meth) acrylic acid ω-carboxypolycaprolactone ester With a carboxyl group at the end , Polylactone-based (meth) acrylic acid esters, alkylene oxides such as ethylene oxide and propylene oxide repeatedly added, alkylene oxide-added succinic acid having a carboxyl group at the terminal, and (meth) acrylic acid esters, etc. A carboxyl group-containing aliphatic α, β-unsaturated double bond group-containing carboxylic acid;

For example, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxybutyl phthalate, 2- (meth) acryloyl Oxyhexyl phthalate, 2- (meth) acryloyloxyoctyl phthalate, 2- (meth) acryloyloxydecyl phthalate, 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, 4-isopropenylbenzenecarboxylic acid, Α, β-unsaturated double bond group-containing carboxylic acids having a carboxyl group-containing alicyclic ring or aromatic ring, such as cinnamic acid and 7-amino-3-vinyl-3-cephem-4-carboxylic acid;

For example, saturation of (meth) allyl acetate, (meth) allyl propionate, (meth) allyl butyrate, (meth) allyl caprate, (meth) allyl laurate, allyl octylate, coconut oil fatty acid, vinyl pivaphosphate, etc. (Meth) allyl esters of carboxylic acids;

For example, acid phosphooxyethyl (meth) acrylate, acid phosphooxypropyl (meth) acrylate, acid phosphooxypolyoxyethylene glycol mono (meth) acrylate, acid phosphooxypolyoxypropylene glycol mono (meth) acrylate, 2,2 ′ -Α, β-unsaturated compounds having a phosphate group such as di (meth) acryloyloxydiethyl phosphate, ethylene oxide-modified di (meth) acrylate phosphate, phosphate-modified epoxy (meth) acrylate, vinyl phosphate, etc. It is done.

It can also be obtained by reacting an α, β-unsaturated compound having a phosphate structure containing a hydroxyl group with anhydrous phosphoric acid. Specific examples include mono (2- (meth) acryloyloxyethyl) acid phosphate and di (2- (meth) acryloyloxyethyl) acid phosphate.

The structural formula of phosphoric acid is illustrated.
(General formula)

In the formula, R ¹ represents a (meth) acryloyl group, a vinyl group or an allyl group, R ² represents hydrogen or a methyl group, and a and b independently represent an integer of 1 to 8. In the formula, R ² and a may be the same as or different from each other.

For example, (meth) acrylamides containing sulfonic acids such as (meth) acrylamide sulfonic acid, tert-butyl- (meth) acrylamide sulfonic acid, (meth) acrylamide-2-methyl-1-propanesulfonic acid;

For example, (meth) acrylic acid cyclic esters containing a sulfonyl group, such as (meth) acrylic acid sulfophenoxyethyl, (meth) acrylic acid sulfocyclohexyl, (meth) acrylic acid sulfobenzyl;

For example, alkenyl group-containing cyclic sulfonic acids such as styrenesulfonic acid, 2-propenyloxybenzenesulfonic acid, 2-methyl-2-propenyloxybenzenesulfonic acid;

For example, ammonium styrene sulfonate, monomethyl ammonium styrene sulfonate, dimethyl ammonium styrene sulfonate, trimethyl ammonium styrene sulfonate, tetramethyl ammonium styrene sulfonate, ethyl ammonium styrene sulfonate, diethyl ammonium styrene sulfonate, triethyl styrene sulfonate Styrenesulfonic acid such as ammonium, tetraethylammonium styrenesulfonate, propylammonium styrenesulfonate, dipropylammonium styrenesulfonate, tripropylammonium styrenesulfonate, butylammonium styrenesulfonate, pentylammonium styrenesulfonate or hexylammonium styrenesulfonate Ammonium salts of
Metal salts of styrene sulfonic acid such as sodium styrene sulfonate, potassium styrene sulfonate, lithium styrene sulfonate, magnesium styrene sulfonate, zinc styrene sulfonate, iron styrene sulfonate;
Metal salts and ammonium salts of alkenyl group-containing vinyloxybenzenesulfonic acid such as ammonium vinyloxybenzenesulfonate, sodium vinyloxybenzenesulfonate, potassium vinyloxybenzenesulfonate, etc .;
2-methyl-2-propenyloxybenzenesulfonate ammonium, 2-methyl-2-propenyloxybenzenesulfonate sodium, 2-methyl-2-propenyloxybenzenesulfonate potassium and the like 2-methyl-2-propenyloxybenzenesulfonate Metal salts and ammonium salts of acids;

For example, (meth) acrylic acid phosphooxyethyl, (meth) acrylic acid phosphooxypropyl, (meth) acrylic acid phosphooxybutyl, (meth) acrylic acid-3-chloro-2-acid phosphooxyethyl, ( (Meth) acrylic acid-3-chloro-2-acid phosphooxypropyl, (meth) acrylic acid-3-chloro-2-acid phosphooxybutyl, (meth) acrylic acid phosphooxyethylene oxide (ethylene oxide addition moles: 4-10), (meth) acrylic acid phosphooxypropylene oxide (propylene oxide addition moles: 4-10) and other phosphonic acid group-containing (meth) acrylic acid esters;

For example, alkenyl group-containing sulfonic acids such as vinyl sulfonic acid, 2-propenyl sulfonic acid, 2-methyl-2-propenyl sulfonic acid, and vinyl sulfuric acid;

For example, metal salts and ammonium salts such as ammonium vinyl sulfonate, sodium vinyl sulfonate, potassium vinyl sulfonate, sodium vinyl alkyl sulfosuccinate;
For example, 2-methyl-2-propenyl sulfonate ammonium salt, ammonium 2-methyl-2-propenyl sulfonate, sodium 2-methyl-2-propenyl sulfonate, potassium 2-methyl-2-propenyl sulfonate, and ammonium salts;

  Moreover, these may use only 1 type or may use multiple types together.

  The weight average molecular weight of the copolymer (B) is 1,000 to 300 in order to ensure the coating suitability of the resin composition for joining a metal substrate and the compatibility of the copolymer (A) and the compound (C). 50,000, preferably 10,000 to 250,000, and more preferably 50,000 to 150,000. If the weight average molecular weight is less than 1,000, the cohesive force of the cured coating film may be insufficient, resulting in cohesive failure and a decrease in adhesive strength. If it is 300,000 or more, the phase with the copolymer (A) The solubility is low, which may cause the coating film to become cloudy or decrease in storage stability. The weight average molecular weight in the range of 50,000 to 150,000 is the expression of the effect of the polar group of the copolymer (B), the control of the cohesive force, and the compatibility with the copolymer (A) and the compound (C). Adjustment is easy and preferable.

  Next, the polymerization initiator used when producing a copolymer (A) and a copolymer (B) is demonstrated.

  The copolymer (A) in the present invention has a polymerization start of 0.001 to 20 parts by weight relative to a total of 100 parts by weight of the various α, β-unsaturated compounds (a1) and (a3) as described above. It is synthesized by a method such as bulk polymerization, solution polymerization, emulsion polymerization or suspension polymerization using an agent. Preferably, it is synthesized by solution polymerization.

  The copolymer (B) in the present invention also has a polymerization start of 0.001 to 20 parts by weight with respect to a total of 100 parts by weight of the various α, β-unsaturated compounds (a2) and (a3) as described above. It is synthesized in the same manner as the copolymer (A) using an agent.

  Examples of polymerization initiators include 2,2′-azobis (2-methylpropionitrile), 2,2′-azobis (2-methylbutanenitrile), 1,1′-azobis (cyclohexane 1-carbonitrile) 2,2′-azobis (2,4-dimethylpentalonitrile), 2,2′-azobis (2,4-dimethyl-4-methoxypentalonitrile) and dimethyl 2,2′-azobis (2-methyl) Propionate), 4,4'-azobis (4-cyanopentanoic acid), 2,2'-azobis (2-hydroxymethylpropionitrile), 2,2'-azobis [2- (2-imidazoline-2 And azo compounds such as -yl) propane].

  Dibenzoyldioxydan, tert-butyl perbenzoate, tert-butyl peroxypivalate, tert-hexyl peroxypivalate, octanoyl peroxide, lauroyl peroxide, cumene hydroperoxide, diisopropyl peroxydicarbonate, diisopropyl -N-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxydicarbonate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyneodecanoate and tert-butylperoxybiba And organic peroxides such as rate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide.

  In the synthesis, mercaptans such as lauryl mercaptan and n-dodecyl mercaptan, and chain transfer agents such as α-methylstyrene dimer and limonene may be used.

  Among these, from the viewpoint of molecular weight control and molecular weight distribution control, 2,2′-azobisisobutyronitrile, dimethyl 2,2′-azobis (2-methylpropionate), dibenzoyldioxidane and tert-butyl are used. Perbenzoate, tert-butyl peroxypivalate, tert-hexyl peroxypivalate, octanoyl peroxide, lauroyl peroxide, tert-butylperoxy-2-ethylhexanoate are preferred.

  When the copolymer (A) and the copolymer (B) are prepared by a solution polymerization method, examples of the solvent include aromatic solvents such as 1,2-dimethylbenzene; ethanol, propan-2-ol, 1- Alcohol solvents such as butanol; ether solvents such as 1-methoxy-2-propanol, (2-methoxymethylethoxy) -propanol 2-ethoxyethanol, 2-butoxyethanol; ethyl ethanoate, butyl ethanoate, 2-ethoxy Examples include ester solvents such as ethanol acetate; ketone solvents such as 2-propanone, 2-butanone, 4-methyl-2-pentanone, and 2,4-pentadione; and organic solvents such as amide solvents such as dimethylformamide. The present invention is not limited to such examples. These solvents may be used alone or in combination of two or more. The amount of the solvent is appropriately determined in consideration of the polymerization conditions, the composition of the α, β-unsaturated compounds (a-1) to (a-2), the viscosity and concentration of the resulting copolymer (A), and the like. However, it is preferable not to use a solvent having active hydrogen that may react with the reactive compound (C), for example, an alcohol solvent or an ether solvent.

  What is necessary is just to set suitably the polymerization conditions at the time of producing a copolymer (A) and a copolymer (B) according to a polymerization method, and it is not specifically limited. The polymerization temperature is preferably room temperature to 150 ° C, more preferably 40 to 120 ° C. What is necessary is just to set reaction time suitably so that the polymerization reaction of (alpha), (beta)-unsaturated compound (a1)-(a3) component may be completed.

<Compound (C)>
Next, the compound (C) will be described.
In the compound (C), the reactive functional group in the compound (C) undergoes a curing reaction with the active hydrogen group in the copolymer (A) and the copolymer (B), and the metal base bonding resin composition It has the role of improving the molecular weight of the cured coating and improving the internal cohesive force that develops energy elasticity.
The compound (C) can also be expected to improve the interaction with the substrate surface described later. Furthermore, for a base material subjected to physical treatment such as corona discharge treatment or chemical treatment modified with an acid or the like, the reactive functional group in the compound (C) is chemically reacted with the base material, It is also possible to develop a strong interaction between the copolymer (A) and the substrate.
Thus, by using the compound (C), it becomes possible to form a strong cured coating film, and the expansion and contraction movement of the base material accompanying a rapid environmental change is achieved by the compound (C) that expresses energy elasticity. It becomes possible to suppress.

Examples thereof include an isocyanate group-containing compound (c1), a high molecular weight polycarbodiimide compound, a polyfunctional aziridine compound, and a metal chelate compound.
Among these, in order for the curing reaction of the compound (C) to act effectively, a compound having two or more functional groups capable of reacting with a hydroxyl group in the copolymer (A) is preferably used. In particular, an isocyanate group-containing compound (c1) such as a polyisocyanate compound is preferably used because it has high reactivity with a hydroxyl group and is excellent in improving the adhesiveness of the resin composition for joining a metal substrate after the curing reaction.

  Of the compounds (C), the isocyanate group-containing compound (c1) is not particularly limited as long as it is a compound having at least one isocyanate group in the molecule.

  Examples of the isocyanate compound (c1) include monofunctional isocyanates and polyfunctional isocyanates, and examples thereof include aromatic isocyanates, aliphatic isocyanates, araliphatic isocyanates, and alicyclic isocyanates.

  More specifically, monofunctional isocyanates include, for example, methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, octyl isocyanate, decyl isocyanate, octadecyl isocyanate, stearyl isocyanate, cyclohexyl isocyanate, phenyl isocyanate, benzyl isocyanate, and p-chlorophenyl isocyanate. , P-nitrophenyl isocyanate, 2-chloroethyl isocyanate, 2,4-dichlorophenyl isocyanate, 3-chloro-4-methylphenyl isocyanate, trichloroacetyl isocyanate, chlorosulfonyl isocyanate, (R)-(+)-α-methylbenzyl Isocyanate, (S)-(−)-α-methylbenzyl isocyanate (R)-(-)-1- (1-naphthyl) ethyl isocyanate, (R)-(+)-1-phenylethyl isocyanate, (S)-(-)-1-phenylethyl isocyanate, p- And toluenesulfonyl isocyanate.

  More specifically, among polyfunctional isocyanates, aromatic polyisocyanates include, for example, 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate ( Alias: 4,4'-MDI), 2,4-tolylene diisocyanate (alias: 2,4-TDI), 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-tri Examples include isocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4′-diphenyl ether diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, and the like.

  Aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also known as HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodeca Examples include methylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate.

  In addition, as part of the component (c1), the above-described adducts of polyisocyanates with polyols such as 2-methylpentane-2,4-diol and trimethylolpropane, trimers having an isocyanurate ring, and the like are also used. be able to. Polyphenylmethane polyisocyanate (also known as PAPI), and these polyisocyanate-modified products can be used. As the polyisocyanate-modified product, a carbodiimide group, a uretdione group, a uretonimine group, a burette group reacted with water, a group of isocyanurate groups, or a modified product having two or more of these groups can be used. A reaction product of a polyol and a diisocyanate can also be used as a compound having at least two isocyanate groups.

  As the isocyanate compound (c1), a blocked isocyanate (c1-1) in which an isocyanate group is blocked using a blocking agent can also be used. By blocking the isocyanate group, storage stability can be improved and the reaction rate of the isocyanate group can be adjusted.

As the blocking agent to be used, a known compound such as an alcohol-based, lactam-based, oxime-based, or β-diketone-based blocking agent can be used. Generally, their dissociation temperatures are said to be about 180 ° C. or higher for alcohols, about 160 ° C. for lactams, about 140 ° C. for oximes, and about 100 ° C. for β-diketones. It is preferable to use an oxime type as the blocking agent.
Alcohol-based and lactam-based blocking agents generally seem to have good stability over time, but the preferred laminating temperature when using the adhesive composition for laminated sheets of the present invention is about 160-200 ° C. Considering that, since the temperature difference is small for complete dissociation at the laminating temperature, an oxime blocking agent is preferable from the viewpoint of dissociation temperature. On the other hand, the β-diketone system may have poor storage stability because the dissociation temperature is too low. From these points, it is preferable to use an oxime system, and in particular, methyl ethyl ketone oxime can be suitably used.

  When the isocyanate compound (c1) is used, a known catalyst can be used as necessary to accelerate the reaction. For example, a tertiary amine compound, an organometallic compound, etc. are mentioned, and it is possible to use a single compound or plural compounds.

  Examples of tertiary amine compounds include triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, diazabicycloundecene (also known as DBU), and may be used alone or in combination. You can also.

Examples of organometallic compounds include tin compounds and non-tin compounds.
Examples of tin compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (also known as DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyl Examples thereof include tin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, and tin 2-ethylhexanoate.
Examples of non-tin compounds include titanium compounds such as dibutyltitanium dichloride, tetrabutyltitanate and butoxytitanium trichloride, lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate and lead naphthenate, 2- Iron-based such as iron ethylhexanoate and iron 2,4-pentadionate, cobalt-based such as cobalt benzoate and cobalt 2-ethylhexanoate, zinc-based such as zinc naphthenate and zinc 2-ethylhexanoate, naphthene Examples thereof include zirconium acid.
Among the above catalysts, dibutyltin dilaurate (also known as DBTDL), tin 2-ethylhexanoate and the like are preferable in terms of reactivity and hygiene.

  As the high molecular weight polycarbodiimide compound, a compound having two or more carbodiimide groups (—N═C═N—) in the molecule is preferably used, and a known polycarbodiimide can be used. Moreover, as a carbodiimide compound (b4), the high molecular weight polycarbodiimide produced | generated by carrying out the decarboxylation condensation reaction of diisocyanate in presence of a carbodiimidization catalyst can also be used.

Examples of such compounds include those obtained by subjecting the following diisocyanates to a decarboxylation condensation reaction. As the diisocyanate, 4,4′-diphenylmethane diisocyanate, 3,3′-dimethoxy-4,4′-diphenylmethane diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, 4,4′-diphenyl ether diisocyanate, 3,3′-dimethyl-4,4′-diphenyl ether diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1-methoxyphenyl-2,4-diisocyanate, isophorone diisocyanate, 4,4′- One of dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, or a mixture thereof can be used.
As the carbodiimidization catalyst, 1-phenyl-2-phospholene-1-oxide, 3-methyl-2-phospholene-1-oxide, 1-ethyl-3-methyl-2-phospholene-1-oxide, 1-ethyl- Phosphorene oxides such as 2-phospholene-1-oxide or their 3-phospholene isomers can be used.

  Examples of such high molecular weight polycarbodiimides include Nisshinbo's Carbodilite series. Among these, Carbodilite V-01, 03, 05, 07, 09 is preferable because of its excellent compatibility with organic solvents.

  Examples of the polyfunctional aziridine compound include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxite), N, N′-toluene-2,4-bis (1-aziridinecarboxite), Bisisophthaloyl-1- (2-methylaziridine), tri-1-aziridinylphosphine oxide, N, N′-hexamethylene-1,6-bis (1-aziridinecarboxite), 2-methylpentane- 2,4-diol-tri-β-aziridinylpropionate, 2,2-bis (hydroxymethyl) 1,3-propanediol-tri-β-aziridinylpropionate, tris-2,4, 6- (1-aziridinyl) -1,3,5-triazine, 2-methylpentane-2,4-diol tris [3- (1-aziridinyl) propionate ], 2-methylpentane-2,4-diol tris [3- (1-aziridinyl) butyrate], 2-methylpentane-2,4-diol tris [3- (1- (2-methyl) aziridinyl) propionate] 2-methylpentane-2,4-diol tris [3- (1-aziridinyl) -2-methylpropionate], 2,2-bis (hydroxymethyl) 1,3-propanediol tetra [3- (1 -Aziridinyl) propionate], diphenylmethane-4,4-bis-N, N'-ethyleneurea, 1,6-hexamethylenebis-N, N'-ethyleneurea, 2,4,6- (triethyleneimino)- Syn-triazine, bis [1- (2-ethyl) aziridinyl] benzene-1,3-carboxylic acid amide, and the like.

  Examples of the metal chelate compound include aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium and zirconium, and 2,4-pentadione and ethyl-3-oxobuta And coordination compounds with noate.

  Compound (C) can be used alone or in combination.

The amount of the compound (C) added is that of the active hydrogen group (X) contained in the copolymer (A) and the copolymer (B) and the reactive functional group (Y) contained in the compound (C). It is determined by the equivalent ratio ([reactive functional group (Y) of compound (C)] / [active hydrogen group (X) in copolymer (A) and copolymer (B)]). 8 is preferable, 1.2 to 5 is more preferable, and 1.5 to 3 is more preferable.
When the equivalence ratio is less than 1, the amount of compound (C) added is small, the effect of improving the molecular weight due to the curing reaction cannot be obtained, the cohesive force is insufficient, and the adhesive strength may be lowered, and the equivalence ratio exceeds 8. And excess compound (C) may remain in the metal substrate bonding resin composition, resulting in a decrease in adhesive strength, and the remaining compound (C) during the durability test may cause a curing reaction, When the base material bonding resin composition is used for bonding two adherends, the metal base material bonding resin composition may be deteriorated such as being too hard. In addition, when the equivalence ratio is in the range of 1.5 to 3, it is easy to control the cohesive force of the laminated sheet resin composition, complete the reaction of the compound (C), or set the reactive functional group in excess to react. It is most preferable because a strong interaction is obtained between the copolymer (A) and the substrate by chemically reacting the functional functional group and the substrate.

<Silane coupling agent (D)>
Next, the silane coupling agent will be described.
In addition to the said component, the resin composition for metal base joining of this invention may contain a silane coupling agent (D). By using a silane coupling agent, interaction such as condensation reaction is developed between the hydroxyl group on the substrate surface and functional groups such as carboxyl groups, improving the adhesion of the resin composition for joining metal substrates. Can be made. In particular, since the interaction is high with respect to the surface of an inorganic material such as glass, metal foil, metal plate (or steel plate), or metal vapor deposited film, it is easy to improve the adhesive strength.

  As a silane coupling agent (D), a well-known silane compound can be used and it will not specifically limit if adhesiveness with the below-mentioned base material improves. For example, alkyl alkoxysilane, aryl alkoxysilane, vinyl alkoxysilane, amino alkoxysilane, epoxy alkoxysilane, halogen alkoxysilane, (meth) acryloyl alkoxysilane, mercapto alkoxysilane, cationic alkoxysilane, Examples thereof include alkoxysilanes having an alkoxyl group such as isocyanate-based alkoxysilanes, and / or organic silanes having reactivity by directly bonding a hydrogen atom to a silicon atom.

  More specifically, for example, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltriacetoxysilane, methyltris (methoxyethoxy) silane, methyltris ( Methoxypropoxy) silane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltriisopropoxysilane, butyltrimethoxysilane, butyltriethoxysilane, hexyltrimethoxy Silane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltrie Xysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiisopropoxysilane, dimethyldiacetoxysilane, dimethylbis (methoxyethoxy) silane, dimethylbis (methoxypropoxy) silane, diethyldimethoxy Silane, diethyldiethoxysilane, diethyldiisopropoxysilane, diethyldiacetoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methylethyldiisopropoxysilane, methylethyldiacetoxysilane, methylpropyldimethoxysilane, methylpropyldi Alkyl series such as ethoxysilane, methylpropyldiisopropoxysilane, methylpropyldiacetoxysilane, etc. Alkoxysilane compounds;

For example, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, phenyltriacetoxysilane, tolyltrimethoxysilane, tolyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiisopropoxysilane, diphenyldi Aryl alkoxysilanes such as acetoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, methylphenyldiisopropoxysilane, methylphenyldiacetoxysilane;

  For example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltriacetoxysilane, vinyltris (methoxyethoxy) silane, vinyltris (methoxypropoxy) silane, allyltrimethoxysilane, allyltriethoxysilane, divinyldimethoxysilane , Divinyldiethoxysilane, divinyldiisopropoxysilane, divinyldiacetoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, methylvinyldiisopropoxysilane, methylvinyldiacetoxysilane, diallyldimethoxysilane, diallyldiethoxysilane, Diallyldiisopropoxysilane, methylallyldimethoxysilane, methylallyldiethoxysilane, methylallyldiisopropoxy Vinyl alkoxysilanes such as silane and methylallyldiacetoxysilane;

  For example, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2-aminomethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane Amino acids such as N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- [2- (vinylbenzylamino) ethyl] -3-aminopropyltrimethoxysilane hydrochloride Alkoxysilanes;

  For example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- ( Epoxy-based alkoxysilanes such as 3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane;

  For example, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, 3-chloropropylmethyldiethoxysilane, 3,3,3-trifluoropropyltrimethoxy Halogen-based alkoxysilanes such as silane, 3,3,3-trifluoropropyltriethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, 3,3,3-trifluoropropylmethyldimethoxysilane Kind;

  For example, 3-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ- (Meth) acryloyl alkoxysilanes such as acryloxypropylmethyldimethoxysilane;

  For example, mercaptoalkoxysilanes such as 3-mercaptopropyltrimethoxylane, 3-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldiethoxysilane;

  For example, alkoxysilanes represented by isocyanate-based alkoxysilanes such as γ-isocyanatopropyltriethoxysilane are exemplified.

  For example, methylsilane, ethylsilane, dimethylsilane, diethylsilane, diethylmethylsilane, butyldimethylsilane, di-t-butylmethylsilane, triethylsilane, trihexylsilane, butyldimethylsilane, cyclohexyldimethylsilane, n-hexylsilane, n- Octylsilane, tri-n-octylsilane, tripropylsilane, triisopropylsilane, triisobutylsilane, trihexylsilane, n-octadecylsilane, phenylsilane, methylphenylsilane, dimethylphenylsilane, methylphenylvinylsilane, dimethylbenzylsilane, Diphenylsilane, triphenylsilane, (phenylethynyl) dimethylsilane, methyldichlorosilane, ethyldichlorosilane, dimethylchlorosilane, bis ( -Chloroethoxy) methylsilane, tris (2-chloroethoxy) silane, n-hexyldichlorosilane, diisopropylchlorosilane, dichlorosilane, di-t-butylchlorosilane, trichlorosilane, chloromethylsilane, methylphenylchlorosilane, phenyldichlorosilane, diphenyl Chlorosilane, chloroisopropylsilane, dichloromethylsilane, dichloroethylsilane, methyldimethoxysilane, dimethoxymethylsilane, methyldiethoxysilane, dimethylethoxysilane, diethoxysilane, trimethoxysilane, triethoxysilane, tripentyloxysilane, tris ( Trimethylsiloxy) silane, methylphenylethenylsilane, allyldimethylsilane, 1,1,2-trimethyldisilane, 1,1,2, -Tetraphenyldisilane, 1,1,3,3-tetramethyldisilazane, 1,4-bis (dimethylsilyl) benzene, methyltris (dimethylsiloxy) silane, tris (trimethylsiloxy) silane, phenyltris (dimethylsiloxy) silane , Tetrakis (dimethylsiloxy) silane, tetramethyldisilazane, dimethylsilyldimethylamine, bis (dimethylamino) methylsilane, tris (dimethylamino) silane, tris (dimethylsilyl) amine, N, N-dimethylaminomethylethoxysilane, di Acetoxymethylsilane, N, O-bis (dimethylsilyl) acetamide, 2- (dimethylsilyl) pyridine, tetrakis (dimethylsilyl) silane, allyldimethylsilane, mercaptodimethylsilane, cyclopropanesilane , Tris (trimethylsilyl) silane, 1,1,4,4-tetramethyldisilylethene, cyclohexanesilane, pentamethyldisiloxane, tetramethylcyclotetrasiloxane, 1,3-diphenyl-1,3-dimethyldisiloxane, penta Methyldisiloxane, 1,1,3,3-tetramethyldisiloxane, 1,1,3,3-tetraisopropyldisiloxane, 1,1,3,3-tetrakis (trimethylsiloxy) disiloxane, 1,1,3 3,3, -tetramethyldisilazane, 1,2-bis (dimethylsilyl) benzene, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,3,3,5,5 7,7-octamethyltetrasiloxane, 1,1,1,3,5,5,5-heptamethyltrisiloxane, 1,1,3,3,5,5 Heptamethyltrisiloxane, 1,1,1,3,5,7,7,7-octamethyltetrasiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9- Pentamethylcyclopentasiloxane, 1,2,3,4,5,6-hexamethylcyclotrisilazane, α, ω-bis (hydrodiene) polydimethylsiloxane and long-chain dimethylsiloxane oligomer with oily state Or waxy organic silanes etc. are mentioned.

  In addition, as the silane coupling agent (D), commercially available products can be used, and it is also possible to use an oligomeric silane obtained by oligomerizing a mixture of two or more silanes by hydrolysis and condensation. Included in ring agent (D). The silane coupling agent (D) can be used alone or as a mixture of two or more.

  The resin composition for bonding a metal substrate of the present invention preferably contains 0.1 to 5 parts by weight of the silane coupling agent (D) with respect to 100 parts by weight of the copolymer (A). It is more preferable to contain 0.5 to 2 parts by weight. If the amount is less than 0.1 parts by weight, the effect of improving heat resistance and moist heat resistance cannot be expected. On the other hand, when the amount exceeds 5 parts by weight, foaming of the coating film tends to occur during the lamination process, and therefore, the cohesive force is insufficient and the adhesion and adhesion to the substrate are lowered, which is not preferable.

<Other ingredients>
If the resin composition of this invention is a range which does not impair the effect by this invention, it is also possible to mix | blend various additives suitably. For example, from the viewpoint of curing shrinkage reduction, thermal expansion coefficient reduction, dimensional stability improvement, elastic modulus improvement, viscosity adjustment, thermal conductivity improvement, strength improvement, toughness improvement, and coloring improvement, an organic or inorganic filler is used. Can be blended. Such fillers may be composed of materials such as polymers, ceramics, metals, metal oxides, metal salts, and dyes and pigments. Moreover, about the shape, it is not specifically limited, For example, a particulate form, fibrous form, etc. may be sufficient. In addition, when blending the above polymer-based materials, tackifiers, flexibility-imparting agents, plasticizers, flame retardants, storage stabilizers, antioxidants, metal deactivators, ultraviolet absorbers, thixotropy In the resin composition, as a polymer blend or a polymer alloy, not as an independent filler, such as an imparting agent, a leveling agent, an antifoaming agent, a dispersion stabilizer, a fluidity imparting agent, and an antifoaming agent. It can also be dissolved or microdispersed.

  Examples of the leveling agent include polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, aralkyl-modified polymethylalkylsiloxane, polyester-modified hydroxyl group-containing polydimethylsiloxane, polyetherester-modified hydroxyl group-containing polydimethylsiloxane, and polyether-modified polymethyl. Examples include alkylsiloxane, (2-methyl) acrylic acid alkyl ester copolymer, lecithin, and mixtures thereof.

  As an antifoamer, well-known things, such as a silicone resin, the copolymer of an alkyl ethenyl ether and (2-methyl) propenoic acid alkyl ester, or mixtures thereof, are mentioned. When a leveling agent and an antifoaming agent are added, one type of compound may be used independently, or two or more types may be used in any combination.

Next, the metal substrate bonding resin composition will be described.
The resin composition for joining metal base materials of the present invention comprises the above copolymer (A), copolymer (B), and reactive compound (C) as essential components, and further, if necessary, silane coupling. It can manufacture by mixing uniformly after mixing other components, such as an agent (D) and a leveling agent. When stirring and mixing, it may be prepared by stirring and mixing using a general-purpose device such as a uniaxial or multiaxial extruder, a kneader, or a dissolver equipped with a decompression device. Usually, the temperature at the time of stirring and mixing is preferably set to 10 to 60 ° C. If the set temperature at the time of preparation is less than 10 ° C, the viscosity may be too high to make uniform stirring / mixing work difficult. Conversely, if the temperature at the time of preparation exceeds 60 ° C, a curing reaction due to heat occurs. In some cases, a normal resin composition may not be obtained.

The resin composition for joining metal substrates of the present invention can be used in any form of liquid, paste and film.
In addition, it is preferable that the resin composition for metal substrate joining in this invention contains an organic solvent, and a non volatile matter (henceforth also called solid content) is used in 10-60 weight%. As the organic solvent to be contained, an organic solvent used as a solvent during the polymerization reaction of the above copolymer (A) can be preferably used. However, in consideration of energy saving properties such as reduction in drying temperature, the boiling point temperature is 160 ° C. or lower. The use of organic solvents is preferred. For example, methanol, ethanol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, cyclohexane, toluene, xylene, ethylene glycol monoisopropyl ether, other hydrocarbons An organic solvent such as a solvent or water can be used to adjust the viscosity of the resin composition, or the resin composition can be heated to lower the viscosity.
These organic solvents may be used alone or in combination of two or more. The amount of the solvent used may be appropriately determined in consideration of the polymerization conditions of the copolymer (A), the composition of each component, the viscosity and concentration of the copolymer (A) to be obtained, etc. It is preferable not to use a solvent having an active hydrogen that may react with the solvent), such as an alcohol solvent or an ether solvent.

  The resin composition for joining metal base materials in the present invention is typically used by coating so that an adhesive layer having a film thickness of 10 μm or less is formed. Therefore, from the viewpoint of coating film formation, it is important that the resin composition has a viscosity of at least 25 ° C. of 1 to 5000 mPa · s, preferably 2 to 2500 mPa · s, and preferably 5 to 1000 mPa · s. It is more preferable that When the viscosity is higher than 5000 mPa · s, coating cannot be performed on the thin film, streaks or the like are generated, and adhesiveness is deteriorated. On the other hand, when the viscosity is lower than 1 mPa · s, it becomes difficult to control the film thickness of the resin composition.

When the resin composition contains a liquid medium such as an organic solvent or water, the liquid medium is removed by a method such as heating or the resin composition. When the product does not contain a liquid medium to be volatilized, the resin layer in the molten state can be cooled and solidified to form an adhesive layer on the surface of the substrate or adherend.
The thickness of the adhesive layer formed by coating is preferably from 0.1 to 10 μm, and more preferably from 0.1 to 6 μm. By setting the thickness of the adhesive layer to 0.1 μm or more, it is easy to obtain sufficient adhesion or adhesive force to the adhesive layer. On the other hand, when the thickness of the resin layer exceeds 10 μm, there is often no change in properties such as adhesion or adhesive strength.

The method for applying the metal base material bonding resin composition of the present invention to the base material is not particularly limited, and may be a Meyer bar, applicator, brush, spray, roller, gravure coater, die coater, lip coater, comma coater, Various coating methods such as a knife coater, a reverse coater, and a spin coater can be used.
There is no restriction | limiting in particular in a drying method, The thing using hot air drying, infrared rays, and the pressure reduction method is mentioned. As drying conditions, although it depends on the crosslinking and curing form of the resin composition, the film thickness, and the selected organic solvent, heating with hot air at about 60 to 180 ° C. is usually sufficient.

Next, a laminated body is demonstrated.
The resin composition for joining metal base materials of the present invention can be used as an adhesive for joining the first base material and the second base material. However, at least one of the first substrate (K1) and the second substrate (K2) is a metal substrate.
The substrate may be plate-shaped, film-shaped, sheet-shaped, or tape-shaped. Moreover, adhesion | attachment of metal base materials may be sufficient, and one side may be base materials other than a metal base material, for example, a plastic film, or a glass plate. In particular, it is used in applications such as laminated steel sheets, food packaging films, automotive interior sheets, solar cell backsheets, and the like. In this embodiment, the film thickness, viscosity, or non-volatile content of the adhesive layer is set according to the use of the laminate.
Examples of the metal substrate include metal substrates such as metal plates and metal foils. Further, a part or all of the adhesion surface of a substrate other than metal such as a plastic film or a glass plate may be subjected to metal vapor deposition or a metal-containing coupling agent treatment. When both substrates to be bonded are metal substrates, the same metal substrate or different metal substrates may be used.

  As the base material used in the laminate of the present invention, a plastic film, a metal plate, or a glass plate is used. Examples of the plastic film include transparency, coloring stability, mechanical strength, thermal stability, moisture Various films composed of a thermoplastic resin excellent in properties such as barrier properties, isotropic properties, and design properties are used, which are also referred to as various plastic sheets and are not particularly limited. Specific examples include, for example, polyvinyl alcohol films, polytriacetyl cellulose films, polyolefin films such as polypropylene, polyethylene, polycycloolefin, and ethylene-vinyl acetate copolymers, polyester films such as polyethylene terephthalate and polybutylene terephthalate, Polycarbonate film, polynorbornene film, polyarylate film, polyacrylic film, polyphenylene sulfide film, polystyrene film, polyvinyl chloride film, polyamide film, polyimide film, polyfluorine film and polyoxirane film A film etc. are mentioned. The thickness of the plastic film that can be laminated is not particularly limited. For example, a film having a thickness of 500 μm can be used.

  In addition, plastic film has a surface with physical treatment such as corona discharge, plasma treatment, flame treatment, etc., chemical treatment that modifies the film surface with acid or alkali, etc. Film with increased surface area, or plastic film with deposited metal oxide such as silicon, aluminum, magnesium, calcium, potassium, tin, sodium, boron, titanium, lead, zirconium, yttrium, or non-metallic inorganic oxide For example, those that have been subjected to an easy adhesion treatment or those that have been provided with functionality for each application can be suitably used.

Moreover, as a metal plate, the plate-shaped metal plate which has iron as a main component, what is called a steel plate is used preferably. Although a steel plate is not specifically limited, For example, common steel plate base materials, such as a stainless steel base material or a galvanized steel base material, can be used. The galvanization on the surface of the galvanized steel base material may be, for example, a steel plate as a base material, which has been subjected to any treatment of pure galvanization or zinc alloy plating. It may be plated in multiple layers.
If necessary, these steel plate base materials can be subjected to a ground treatment for rust prevention. The stainless steel plate does not particularly require a base treatment, but the adhesion with the resin composition can be further improved by the chromic acid treatment. In a galvanized steel sheet, it may be necessary to perform either or both of phosphate treatment and chromic acid treatment. About a phosphate process and a chromic acid process, it can be based on the conventional general method without a restriction | limiting in particular.
Besides the steel plate, a metal plate such as an aluminum plate, a copper plate, a titanium plate, brass, an aluminum alloy plate, or a galbarium plate can also be used. Furthermore, it is also possible to use a coated steel sheet that has been coated for rust prevention and design.

In one embodiment of the laminate according to the present invention, a laminated steel sheet is preferably used by using a plastic film and a steel sheet as the base material, and bonding the metal base material bonding resin composition of the present application.
Laminated steel sheets are manufactured in the following two stages. First, in the first step, the resin composition is applied to a plastic film or a steel plate, dried at a temperature in an arbitrary range of 50 to 200 ° C., the solvent is removed, and a dry adhesive layer is formed. In this case, it is preferable to apply on the steel plate side in order to facilitate drying and to maintain the design of the film. Next, in the second stage, although the steel sheet on which the plastic film and the resin composition are laminated is different from the type of the plastic film or the resin composition, for example, the pressure is 1.0 to 5.0 kg / cm ² , the lamination temperature is 200 to Heat lamination is performed using a heating roll at 220 ° C. and a line speed of 5 to 20 m / min. Lamination is preferably performed immediately after drying without cooling. At this time, heat curing occurs instantaneously due to heat at the time of laminating, and adhesion force appears.
For example, when a blocked polyisocyanate is used as the compound (C), the blocking agent is dissociated and volatilized when the heat lamination is carried out, the isocyanate group is activated, and the hydroxyl group of the copolymer (A) It reacts, causes a chemical reaction with the base material, reacts with moisture in the air, or reacts with isocyanate groups to ensure the adhesive strength between the film and the steel plate. The laminated steel sheet thus obtained is excellent in design, corrosion resistance, and work adhesion, and can be used for various applications.

The resin composition for joining metal base materials of the present invention is characterized by having excellent adhesion and durability. Therefore, the present invention is not limited to laminated steel sheets, and can be used for beverage cans and flexible packaging materials in which metal cans and films are laminated. It can also be used for coating agents such as decorative sheets.

  Hereinafter, the present invention will be described with reference to specific examples. However, the present invention is not limited to the following examples. Further, “parts” and “%” described in the following Examples and Comparative Examples represent “parts by weight” and “% by weight”, respectively.

<Production of copolymer (A)>
[Synthesis Examples 1 to 7]
In a polymerization reactor equipped with a reaction vessel, a dropping device, a stirrer, a thermometer, a reflux condenser, and an air introduction tube, 100 parts of ethyl acetate, which is a solvent, is charged, and one or more hydroxyl groups are added in the molecule below. An α, β-unsaturated double bond group-containing compound (a-1) to be contained, an α, β-unsaturated double bond group-containing compound (a-3) not containing a hydroxyl group in the molecule, and a polymerization initiator, respectively The dropping device was charged at the ratio of parts shown in Table 1.
Next, after the air in the reaction vessel was replaced with nitrogen gas, the temperature was raised to 80 ° C. in a nitrogen atmosphere while stirring, and dropping of the mixture described in Table 1 was started from the dropping device. After dropwise addition over 2 hours, the mixture was further aged with stirring for 6 hours, and then cooled by adding ethyl acetate so as to have the ratio shown in Table 1, and the copolymers (A-1) to (A-7) A resin solution containing was obtained.

  About the obtained resin solution, an external appearance, molecular weight, and glass transition temperature were calculated | required in accordance with the following method, and Table 1 showed the result. For reference, methods for measuring acid value, hydroxyl value, and acid anhydride value are also shown below.

《Molecular weight》
The number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured using Showa Denko GPC (gel permeation chromatography) “Shodex GPC System-21”. GPC is liquid chromatography that separates and quantifies substances dissolved in a solvent based on the difference in molecular size. The sample was dissolved in tetrahydrofuran, and measurement was carried out using tetrahydrofuran as a developing solvent at a flow rate of 0.6 ml / min and a column temperature of 40 ° C. A calibration curve using monodispersed polystyrene as a standard substance is prepared, and the molecular weight of the copolymer (A) and the copolymer (B) is the number average molecular weight (Mn) in terms of polystyrene and the weight average molecular weight (Mw). Was measured.

<< Glass transition temperature (Tg) >>
An “SSC5200 disk station” (manufactured by Seiko Instruments Inc.) was connected to a robot DSC (differential scanning calorimeter, “RDC220” manufactured by Seiko Instruments Inc.) and used for measurement.
Applying the resin solution to the peeled polyester film, irradiating active energy rays, scraping about 10 mg of polymerized and cured, putting it in an aluminum pan as a sample, weighing it, and setting it in a differential scanning calorimeter, The aluminum pan of the same type without a sample was used as a reference, heated at a temperature of 100 ° C. for 5 minutes, and then rapidly cooled to −120 ° C. using liquid nitrogen. Thereafter, the temperature was raised at 10 ° C./min, and the glass transition temperature (Tg, unit: ° C.) was determined from the DSC chart obtained during the temperature elevation.

<< Hydroxyl value (OHV) >>
About 1 g of a sample is accurately weighed in a stoppered Erlenmeyer flask and dissolved by adding 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixed solution. Further, exactly 5 ml of an acetylating agent (a solution in which 25 g of acetic anhydride was dissolved in pyridine to make a volume of 100 ml) was added and stirred for about 1 hour. To this, phenolphthalein reagent is added as an indicator and lasts for 30 seconds. Thereafter, the solution is titrated with a 0.1N alcoholic potassium hydroxide solution until the solution becomes light red.
The hydroxyl value was determined by the following formula. The hydroxyl value was a numerical value in the dry state of the resin (unit: mgKOH / g).
Hydroxyl value (mgKOH / g) = [{(ba) × F × 28.25} / S] / (Non-volatile content concentration / 100) + D
Where S: Amount of sample collected (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
b: Consumption of 0.1N alcoholic potassium hydroxide solution in the empty experiment (ml)
F: Potency of 0.1N alcoholic potassium hydroxide solution
D: Acid value (mgKOH / g)

《Acid value (AV)》
About 1 g of a sample was precisely weighed in a stoppered Erlenmeyer flask and dissolved by adding 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixed solution. To this was added a phenolphthalein test solution as an indicator, which was held for 30 seconds, and then titrated with a 0.1N alcoholic potassium hydroxide solution until the solution turned light red.
The acid value (mgKOH / g) was determined by the following equation as the value of the resin in the dry state.
Acid value (mgKOH / g) = {(5.611 × a × F) / S} / (Nonvolatile content concentration / 100)
Where S: Amount of sample collected (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
F: Potency of 0.1N alcoholic potassium hydroxide solution

Illustrative compounds are specifically shown in Table 1 below, but are not limited thereto. The blank in Table 1 means no blending.

Abbreviations in Table 1 are as follows.
(A-1-1) 2-hydroxyethyl methacrylate (a-1-2) 4-hydroxybutyl acrylate (a-3-1) n-butyl acrylate (a-3-2) acrylic 2-ethylhexyl acid, (a-3-3) n-butyl methacrylate, (a-3-4) iso-bornyl methacrylate, (a-3-5) cyclohexyl methacrylate, (a-3-6) styrene (A-3-7) methyl methacrylate (a-3-8) ethyl methacrylate (a-3-9) ethoxymethyl methacrylate polymerization initiator 1 azoisobutyronitrile polymerization initiator 2 tert -Butylperoxy-2-ethylhexanoate / solvent: ethyl acetate.

<Production of copolymer (B)>
[Synthesis Examples 8 to 13]
(Synthesis Example B-1 to 6)
Synthesis was carried out in the same manner as in Synthesis Example 1 except that the raw materials and preparation parts listed in Table 2 were used, and the resin solutions of Synthesis Examples (B-1) to (B-6) were obtained.

Abbreviations in Table 2 are as follows.
(A-2-1) acrylic acid (a-2-2) acryloyloxyethyl hexahydrophthalate (a-2-3) mono (2-methacryloyloxyethyl) acid phosphate (a-2-4) ) Tert-Butyl-methacrylamide sulfonic acid (a-2-5) 2-sulfoethyl methacrylate

Comparative Production Examples 1-5
(Synthesis Example Comparative A-1 to 5)
The synthesis was carried out in the same manner as in Synthesis Example 1 except that the raw materials and preparation parts listed in Table 3 were used, and the resin solutions of Comparative Synthesis Examples (Comparative A-1) to (Comparative A-5) were obtained.

Abbreviations in Table 3 are as follows.
(A-3-10) glycidyl methacrylate (a-3-11) allyl methacrylate (a-3-12) ethyl acrylate

(Synthesis Example Comparative A-6)
Transesterification of 194 g of dimethyl phthalate, 124 g of ethylene glycol, 104 g of neopentyl glycol and 0.1 g of tetrabutyl titanate was carried out at 160 to 220 ° C. in a N ₂ gas stream. After distilling a predetermined amount of methanol, 202 g of sebacic acid and 73 g of adipic acid are added, esterification is performed at 220 to 230 ° C, and the pressure is gradually reduced, and polycondensation reaction is performed at 230 to 260 ° C under 1 mmHg for 3 hours. went. A polyester polyol having a number average molecular weight of about 6,000 was obtained. Dibutyltin dilaurate (0.15 g), isophorone diisocyanate (100 g), and ethyl oxalate (100 g) were added thereto, and the mixture was reacted at 70 ° C. under a N ₂ gas stream for 7 hours. A polyurethane polyol having a number average molecular weight of about 10,000 and an OH number of 10 was obtained. To this, 102 g of SMA 1,000 (styrene / maleic anhydride = 1/1 copolymer, molecular weight 1,600) and 102 g of ethyl oxalate were added and reacted at 70 ° C. for 60 minutes. % To obtain a modified polyester polyurethane resin (Comparative A-6). This corresponds to the resin used in Patent Document 5.

(Example of urethane compound synthesis)
After synthesizing polyester by a conventional method using itaconic acid as the acid component and neopentyl glycol as the alcohol component, isophorone diisocyanate (IPDI) is used as the isocyanate, and has a solid content of 40% with an acid value of 2 and a hydroxyl group equivalent of 2300. A polyurethane resin (urethane-1) was obtained. This corresponds to the urethane compound used in Patent Document 3.

<Metal substrate bonding resin composition>
[Examples 1 to 13]
Each is a 450 cc glass bottle with a copolymer solution (A), a copolymer solution (B), and a reactive compound (C) as essential components in the molecule, and a silane coupling agent as required. (D) was added, ethyl acetate was added as a solvent, the non-volatile content was adjusted to 20%, the mixture was sufficiently stirred and sufficiently defoamed, and then a metal base bonding resin composition was obtained. The formulation was charged at the ratio shown in Table 4 in terms of nonvolatile content.

《Pot life》
About the obtained resin composition for joining a metal substrate, the viscosity at 25 ° C. is rotated at 20 rpm for 2 minutes using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) until after 1 hour, 4 hours, 8 hours, and 24 hours. The pot life (pot life) was evaluated in three stages. In the case of “△” evaluation or higher, there is no problem in actual use.
○: No change in viscosity. The increase in viscosity up to 24 hours is less than 2 times. Very good.
Δ: A slight increase in viscosity is observed, and the rate of increase in viscosity up to 8 hours is less than twice. It can be used.
X: Viscosity increase rate is 2 times or more in 1 hour of addition. There are practical problems.

<Laminate>
About the resin composition for joining metal base materials shown in Table 4, various physical properties (initial workability, low temperature workability, boiling water workability, heat resistance workability, and adhesiveness) are measured by the following methods, and the results are shown. .

<Creation of laminate>
The resin composition for joining metal base materials was applied to a galvanized steel sheet (thickness = 0.5 mm) with a bar coater so that the dried coating film was 2 μm. Immediately after completion of the process of heating in an oven (infrared oven with conveyor) for 100 seconds and setting the temperature of the steel sheet to 160 ° C., a plastic film (thickness = 150 μm) is laminated with a laminator at a pressure of 5 kg / cm ^2. Immediately after that, it was put into a water tank and rapidly cooled to obtain a laminate.

<Initial workability>
In order to stabilize a laminated body, it was left to stand overnight, and using the obtained laminated body, the peeling degree of the sample which performed the Eriksen test prescribed | regulated to JISK6744 was evaluated visually. Further, peeling was forcibly performed with tweezers, and the presence or absence of peeling was observed with the naked eye and evaluated in four stages. In the case of “△” evaluation or higher, there is no problem in actual use.
A: There is no visual peeling at all, and forced peeling with tweezers is difficult. No problem at all.
○: No peeling is visually observed, but some forced peeling with tweezers is possible, but there is no problem.
Δ: No peeling is visually observed, but partial peeling is possible by forced peeling with tweezers. It is a usable level.
X: Peeling can be observed visually. Practical use is difficult.

<Low temperature workability>
The laminate is cut into a length: 3 cm / width: 5 cm, and cut into a plastic film in a cross-cut shape. This sample was left in the atmosphere at 0 ° C for 6 hours, and in the atmosphere at 0 ° C, the sample was set so that the crosscut was at the center, and a 12mm iron ball was placed on the steel plate surface, and 50cm on the iron ball. A weight of 500 g was dropped from the height and the state where the plastic film was naturally peeled was observed with the naked eye, and was evaluated in four stages based on the same criteria as the initial processability. In the case of “△” evaluation or higher, there is no problem in actual use.
A: There is no visual peeling at all, and forced peeling with tweezers is difficult. No problem at all.
○: No peeling is visually observed, but some forced peeling with tweezers is possible, but there is no problem.
Δ: No peeling is visually observed, but partial peeling is possible by forced peeling with tweezers. It is a usable level.
X: Peeling can be observed visually. Practical use is difficult.

<Boiling water resistance>
The laminate is subjected to the Erichsen test in the same manner as the initial workability evaluation test, and the test sample is further immersed in boiling water for 3 hours, then dried and evaluated in four stages according to the same criteria as the initial workability. did. In the case of “△” evaluation or higher, there is no problem in actual use.
A: There is no visual peeling at all, and forced peeling with tweezers is difficult. No problem at all.
○: No peeling is visually observed, but some forced peeling with tweezers is possible, but there is no problem.
Δ: No peeling is visually observed, but partial peeling is possible by forced peeling with tweezers. It is a usable level.
X: Peeling can be observed visually. Practical use is difficult.

《Heat resistance processability》
The laminate was subjected to an Erichsen test in the same manner as the initial workability evaluation test, and the sample after the test was further allowed to stand in an atmosphere of 150 ° C. for 1 hour, then cooled to room temperature, and on the same basis as the initial workability. Evaluation was made on a four-point scale. In the case of “△” evaluation or higher, there is no problem in actual use.
A: There is no visual peeling at all, and forced peeling with tweezers is difficult. No problem at all.
○: No peeling is visually observed, but some forced peeling with tweezers is possible, but there is no problem.
Δ: No peeling is visually observed, but partial peeling is possible by forced peeling with tweezers. It is a usable level.
X: Peeling can be observed visually. Practical use is difficult.

"Adhesiveness"
Each of the laminates was cut into a size of 200 mm × 30 mm, and allowed to stand for 6 hours in an environment of 25 ° C. and a humidity of 65%. Then, using a tensile tester according to the test method of ASTM-D1876-61, In an environment of 25 ° C. and humidity of 65%, a 180 ° peel test was performed at a load speed of 300 mm / min, and adhesion was evaluated in four stages. In the case of “△” evaluation or higher, there is no problem in actual use.
A: Unreleasable Adhesiveness is very excellent. no problem.
○: Peel strength 50 N / 30 mm or more Excellent adhesion. no problem.
(Triangle | delta): Peel strength 20N / 30mm or more and less than 50N / 30mm Although adhesiveness is a little insufficient, it is the range which can be used practically.
X: Peel strength is less than 20 N / 30 mm, and adhesion is poor. Practical problem

In the present invention, as representative examples of the substrate (steel plate and plastic film), exemplary compounds are specifically shown in Table 4 below, but are not limited thereto. In addition, the structure of the laminated body of Table 4 is as follows.
Laminate 1: Galvanized steel sheet (thickness = 0.5 mm) / resin composition for joining metal substrates / PVC: vinyl chloride film (thickness = 150 μm)
Laminate 2: Galvanized steel sheet (thickness = 0.5 mm) / resin composition for joining metal substrates / PET: Corona-treated polyester film (thickness = 150 μm)

(Examples 1 to 13)

Abbreviations in Table 4 are as follows.
Compound (C)
-(C1-1-1) 1,6-hexamethylene diisocyanate isocyanurate trimer-MEK oxime block ("Sumijour BL3175" manufactured by Sumika Bayer Urethane Co., Ltd., NCO group content 11.2%, solid content 75%)
-(C1-1-2) Trimethylolpropane adduct of tolylene diisocyanate-MEK oxime block ("Takenate B-830" manufactured by Mitsui Chemicals, NCO group content 7%, solid content 55.5%)
(C1-2) Isocyanurate trimer of 1,6-hexamethylene diisocyanate “Sumijour N3300” manufactured by Sumika Bayer Urethane Co., Ltd., NCO group content 21.8%, solid content 100%)
(C1-3) Prepolymer of polymethylene polyphenyl isocyanate (“Sumijour E22” NCO group content 8.6%, manufactured by Sumika Bayer Urethane Co., Ltd.)
(D-1) 3-glycidoxypropyltrimethoxysilane (d-2) 3-glycidoxypropyltriethoxysilane

(Comparative Example 1) to (Comparative Example 9)
In the same manner as in Example 1 using the raw materials and preparation amounts shown in Table 5, metal base bonding resin compositions (Comparative Example 1) to (Comparative Example 9) were obtained. The result of having implemented evaluation similar to Example 1 is shown.

(C2-1) Epoxy group-containing compound: N, N, N ′, N′-tetraglycidyl-m-xylenediamineamine compound: (amine-1) 3,9-bis (3-aminopropyl) 2,4, 8,10-Tetrooxaspiro [5,5] undecanimine compound: (Imine-1) Polyethyleneimine

  As shown in Table 4, the resin compositions for joining metal substrates of Examples 1 to 13 are excellent in workability after lamination and peel strength, excellent in boiling water resistance, heat resistance, and low temperature workability, and are long-term. It was found that the adhesive strength can be maintained over a wide range. This is to control the resin Tg of the copolymer (A), to achieve both high cohesive strength and wettability during coating, and interaction with the base material by the acid-containing resin of the copolymer (B), This is considered to be an effect of enhancing the interaction with the metal surface centering on the steel plate. Further, it is presumed that the effect of improving the cohesive force due to the curing reaction of the reactive compound (C) with the hydroxyl group in the copolymer (A) and the active hydrogen group in the copolymer (B) and the reactive compound (C) is presumed. In addition, the copolymer (A) has a high molecular weight, the copolymer (B) has a low molecular weight, and the blending ratio is optimized to improve compatibility and form an interface inside the adhesive. By suppressing it, it is considered that high adhesive strength is obtained without causing cohesive failure.

  As shown in Table 5, Comparative Example 1 is an example in which the copolymer (B) is not used together, and the curing reaction by which the effect of the curing catalyst by the copolymer (B) is obtained does not proceed and the cohesive force. As a result, the interaction with the metal surface was low, and sufficient workability was not obtained.

  Comparative Example 2 is an example in which the copolymer (A) is not used, the curing reaction with the reactive compound (C) does not proceed, and the effect of improving the cohesive strength of the metal base joining resin composition is obtained. Therefore, the adhesive strength is reduced and the processability is not sufficient. Resin composition for joining metal substrates

  Comparative Example 3 is an example in which the copolymer (A) is not copolymerized with an α, β-unsaturated double bond group-containing compound (a1) containing one or more hydroxyl groups in the molecule. In that case, not only did the curing reaction not proceed, but also the interaction with the substrate interface could not be obtained, and sufficient adhesion and workability could not be obtained.

  Comparative Example 4 is an example in which the compound (B) is not used, but is an example in which a plurality of types of copolymers (A) are used and the improvement of adhesive properties and workability is achieved by controlling the cohesive force. However, since the effect of the interaction with the interface due to the acid cannot be obtained, the adhesive strength is lowered, and sufficient workability cannot be obtained.

  Comparative Example 5 is an example in which the glass transition temperature of the copolymer (A) is lower than this right range. If the glass transition temperature of the copolymer (A) is too low, the cohesive strength is insufficient and the adhesive strength cannot be obtained.

  Comparative Example 6 is an example of Patent Document 1, but since the copolymer (A) does not contain a hydroxyl group, the epoxy group remains, the boiling water resistance deteriorates, and the crosslinking is sufficient. As a result, the curing reaction does not proceed and the cohesive strength of the coating film becomes low, resulting in failure to obtain adhesive strength.

  Comparative Example 7 is an example of Patent Document 2, which is a resin composition for joining a metal base material using a reaction between allyl and polyethyleneimine, but the curing reaction site is alkylimine and is flexible. Therefore, the effect of improving the cohesive force is difficult to obtain, resulting in poor boiling water resistance and low-temperature adhesiveness.

Although the comparative example 8 is an Example of patent document 3, the resin Tg of a copolymer (A) is low, and although the urethane resin is mixed and used, the resin composition for metal base-material joining after hardening reaction is used. The cohesive strength of the product was low, resulting in poor boiling water resistance, heat resistance and low temperature adhesion.

Although the comparative example 9 is an Example of patent document 5, since the main component of comparative A-7 resin is polyester and it is a low molecular weight body, cohesion force is insufficient. In addition, hydrolysis occurred during the boiling water resistance test, resulting in a decrease in cohesive force, resulting in particularly poor boiling water resistance.

By changing the ratio of (A), (B), and (C) in the resin composition for joining a metal base material according to the same or different materials, the resin composition for joining a metal base material according to the present invention is used. It is used for joining various films.
For example, it is suitably used for joining a multilayer laminate of a plastic material and a metal material. In addition, since it has excellent adhesive strength, it is in the construction field (eg, exterior, interior, equipment, etc.), electrical equipment field (eg, home appliances, kitchen equipment, air conditioning, etc.), and transport equipment field (eg, ships, automobiles, etc.). Used in various industrial fields such as furniture and miscellaneous fields, such as wall materials, door materials, outer panels, panels, decorative panels, cases, covers, etc. In order to give, it can use suitably. In addition, even at a low temperature of 160 ° C., there is a possibility that the adhesive strength can be secured with a thin film. Therefore, a plastic film having a high design property such as embossing can be applied without impairing the embossing. It can be adhered to the kimono. In addition, the laminated steel sheet produced using the composition of the present invention is 0 ° C.
Even at a low temperature of around 0 ° C., the end face is not peeled off by bending, and the processability is excellent.
The resin composition for joining a metal substrate according to the present invention exhibits high adhesive strength particularly between laminates including a surface-treated layer of a plastic film, but is a surface untreated film (including a surface untreated plastic film). It can be suitably applied to.

Claims (9)

A metal base-bonding resin composition comprising a first copolymer (A), a second copolymer (B), and a reactive compound (C), the following (1) and (2 The resin composition for joining metal base materials, wherein
(1) The first copolymer (A) has a glass transition temperature (Tg) of 10 ° C. or higher and lower than 100 ° C., and
Copolymerized α, β-unsaturated compound (a1) containing one or more hydroxyl groups in the molecule and other copolymerizable α, β-unsaturated compound (a3) (excluding (a2) below) Do it.
(2) an α, β-unsaturated compound (a2) in which the second copolymer (B) has one or more functional groups selected from the group consisting of a carboxyl group, a phosphate group, and a sulfonyl group; Other copolymerized α, β-unsaturated compounds (a3) (excluding the above (a1)) are copolymerized. The metal substrate bonding according to claim 1, wherein the copolymer (A) contains 30 to 99 parts by weight with respect to a total of 100 parts by weight of the copolymer (A) and the copolymer (B). Resin composition. The copolymer (A) is
In 100 parts by weight of all α, β-unsaturated compounds used for copolymerization,
0.01-20 parts by weight of α, β-unsaturated compound (a1);
The resin composition for bonding a metal substrate according to claim 1 or 2, wherein 80 to 99.99 parts by weight of another copolymerizable α, β-unsaturated compound (a3) is copolymerized. The weight average molecular weight of the copolymer (A) is 50,000 to 1,000,000, and the weight average molecular weight of the copolymer (B) is 1,000 to 300,000. The resin composition for joining metal base materials according to any one of claims 1 to 3. Reactive compound (C) is an isocyanate group containing compound (c1), The resin composition for metal base joining in any one of Claims 1-4 characterized by the above-mentioned. The resin composition for joining metal base materials according to claim 5, wherein the isocyanate group-containing compound (c1) contains a blocked isocyanate (c1-1). Furthermore, a silane coupling agent (D) is contained,
The metal substrate bonding resin according to any one of claims 1 to 6, comprising 0.1 to 5 parts by weight of the silane coupling agent (D) with respect to 100 parts by weight of the copolymer (A). Composition. The laminated body formed by joining the 1st base material (K1) and the 2nd base material (K2) with the resin composition for metal base material joining in any one of Claims 1-7.
However, at least one of the first substrate (K1) and the second substrate (K2) is a metal substrate. The laminate according to claim 8, wherein the metal substrate is a steel plate.