JP6432265B2 - Adhesive composition for laminated sheet - Google Patents

Description

  The present invention relates to an adhesive composition for laminated sheets used for bonding plastic films, metal plates, metal foils and the like.

  In recent years, for outdoor industrial applications, for example, as barrier sheets, roofing materials, solar cell panel materials, window materials, outdoor flooring materials, lighting protection materials, automobile members, signboards, stickers, etc., laminated sheets such as aluminum, copper, Alternatively, a metal foil such as a steel plate, a metal plate, or a metal vapor-deposited film and a plastic film such as a polypropylene resin, a polyvinyl chloride resin, a polyester resin, a fluorine resin, or a polyacrylic resin are laminated together. (Laminated) has been used. In these laminated sheets, polyepoxy resin, polyester resin, or polyurethane resin is used as an adhesive composition for laminated sheets that bonds a metal foil, a metal plate, or a metal vapor-deposited film, and a plastic film. Known adhesive compositions for laminated sheets are known.

  As such an adhesive composition, an adhesive composition for a laminated sheet using a polyurethane-based resin containing a polyester-based resin in consideration of balance, which can give excellent initial cohesive force and adhesive force, etc. is disclosed. (Patent Document 1). Moreover, the adhesive composition for laminated sheets using the polyurethane-type resin excellent in the hot water resistance at the time of the retort sterilization in food packaging is disclosed (patent document 2). Moreover, the adhesive composition for laminated sheets which uses the polyurethane-type resin using the tin catalyst in the automotive use is disclosed (patent document 3). Moreover, in the solar cell back surface protection sheet, an adhesive composition for a laminated sheet (Patent Document 4) using a polyurethane resin having hydrolysis resistance, a polyester resin, or an adhesive for a laminated sheet using a polyester polyurethane resin. The solar cell back surface protection sheet (patent document 5) provided with the adhesion improvement layer comprised by the agent composition is disclosed.

However, when the adhesive composition using the polyester resin or the polyurethane resin adhesive composition containing the polyester resin is used, the adhesive layer after the curing reaction is aggregated by hydrolysis of the ester skeleton. The force is reduced, and a problem that a plurality of constituting films are peeled off in retort sterilization applications in food packaging, interior sheets in automobile applications, solar cell back surface protection sheet applications, and the like has become apparent.
In addition, when an adhesive composition using a polyepoxy resin is used, cracking or peeling occurs during processing such as punching or bending, or when a polyurethane resin adhesive composition is used, In some cases, the pot life was short and could not withstand practical use.

On the other hand, a film laminated metal plate in which a plastic film with printing or embossing on the surface is laminated on a metal plate, also called a laminated steel plate, is mainly used for home appliances, heating equipment, building materials, equipment, etc. Compared to metal coating, it is used as a material with improved design and luxury. These laminated steel plates are manufactured by being laminated on a metal plate by providing an adhesive layer on a metal plate, or providing an adhesive layer on a plastic film, or melting a plastic film. Moreover, the metal plate used for a laminated steel plate is also called a steel plate.
Thus, a typical example of a laminated steel sheet in which a plastic film is laminated on a metal plate is a vinyl chloride (hereinafter sometimes abbreviated as PVC) laminated steel sheet. Conventionally, a PVC laminated steel sheet is used as a solvent on the steel sheet. Immediately after applying the dissolved adhesive composition and drying at a high temperature of 200 ° C. or higher, a vinyl chloride film is bonded by roll pressing. Also, due to recent environmental problems, there is a tendency to replace vinyl chloride with other plastic films. As such plastic films, polyolefin-based films, fluororesin-based films, polyester-based films and the like are used.

  The adhesive composition for laminated sheets used for such laminated steel sheets is required to have high adhesiveness, heat resistance, hot water resistance, or boiling water resistance, and further, there is a need for an adhesive composition that greatly reduces the price. Since it is increasing, many studies have been made on the adhesive composition corresponding thereto. For example, a polyacrylic resin and a polyepoxy resin are blended (Patent Document 6), a polyacrylic resin and ethyleneimine are blended (Patent Document 7), or contain a carboxyl group, a hydroxyl group, and a glycidyl group. Use polyacrylic resin such as adhesive composition using polyacrylic resin (Patent Document 8) or adhesive composition containing carboxyl group-containing macropolyol and carbodiimide group-containing compound (Patent Document 9) An adhesive composition for laminated sheets is disclosed.

  However, in Patent Document 6, in the polyacrylic resin and the polyepoxy resin, the functional group capable of cross-linking reaction with the epoxy group is not incorporated in the polyacrylic resin, and the cross-linking curing reactivity of the epoxy group is poor. There is a concern that the resin may remain. When the remaining polyepoxy resin is hydrolyzed, two hydroxyl groups are generated, and the water resistance may be lowered. In Patent Document 7, ethyleneimine has a high water solubility, and a decrease in water resistance may occur. In addition, ethyleneimine has poor storage stability and may cause poor adhesion. In Patent Document 8, two or more kinds of functional groups capable of crosslinking reaction are copolymerized in the polyacrylic resin, and the pot life and storage stability may be lowered by the self-crosslinking reaction. Moreover, in patent document 9, although it is a system which utilized reaction of a carboxyl group and a carbodiimide group, the curing reactivity of a carboxyl group and a carbodiimide group is high, and storage stability may deteriorate, and the amount of carbodiimide is reduced. In some cases, the cohesive force after the curing reaction is insufficient, and the balance of the adhesive strength cannot be ensured.

In order to solve these disadvantages, by bonding the plastic film and the steel plate at a high temperature via the adhesive composition, by applying a high temperature laminate, the affinity between the plastic film and the steel plate and the adhesive composition is increased. It is possible to increase the adhesive strength.
However, there is a case where the thermal energy increases and the cost is increased. In addition, when a plastic film with high design that is embossed on a vinyl chloride film is used, the embossing process may be crushed or lost due to high-temperature lamination at 200 ° C or higher. A problem that the appearance is impaired such as occurring. In addition, when a polyester plastic film is used, the adhesive composition using a conventional polyacrylic resin is inferior in initial adhesiveness, boiling water resistance, and adhesiveness at low temperatures. When laminated with a laminate, the melting point of the plastic film is about 200 to 250 ° C., so when treated at a high temperature of 200 ° C. or higher using a conventional adhesive composition, the plastic film melts and the appearance May be greatly impaired. Therefore, it has become necessary to lower the manufacturing temperature (bonding temperature) of these laminated laminate steel sheets for plastic films to below 200 ° C.

  As described above, a conventional adhesive composition for laminated steel sheets is desired to be an inexpensive adhesive composition excellent in reducing the drying temperature, boiling water resistance, and low-temperature adhesiveness.

JP-A-10-218978 Japanese Patent Laid-Open No. 06-116542 Special table 2007-536422 gazette JP 2008-4691 A JP 2007-136911 A Japanese Patent Publication No.59-37034 Japanese Patent Laid-Open No. 5-287250 Japanese Patent No. 3660477 JP 2010-159339 A

  The present invention has been made in order to solve such problems, and the problems are excellent in curing reactivity, excellent in adhesion after curing reaction and durability after curing reaction, and good in various plastic films. An object of the present invention is to provide an adhesive composition for laminated sheets that has excellent adhesiveness and excellent boiling water resistance and low-temperature adhesiveness, and a laminated steel sheet using the adhesive composition for laminated sheets.

  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 resin composition for bonding laminated sheets shown below, and further completed the present invention by using an adhesive composition for laminated sheets. It came to do.

That is, the present invention relates to an α, β-unsaturated double bond group-containing compound (a1) containing at least one hydroxyl group in the molecule and an α, β-unsaturated double bond group not containing a hydroxyl group in the molecule. A copolymer (A) formed by polymerizing containing compound (a2) and a vinyl chloride copolymer resin (B);
It is related with the adhesive composition for laminated sheets containing the reactive compound (C) which can react with the hydroxyl group which a copolymer (A) has.

Furthermore, the present invention provides
In the total amount of the adhesive composition for laminated sheets,
40 to 95% by weight of copolymer (A),
0.5-30 wt% of vinyl chloride copolymer resin (B),
4.5-30% by weight of compound (C)
It contains, It is related with the adhesive composition for laminated sheets of Claim 1 characterized by the above-mentioned.

The copolymer (A) is
The number average molecular weight is 1,000 to 500,000,
And,
It has a hydroxyl value of 5 to 50 mgKOH / g.

  Further, the present invention provides the adhesive composition for laminated sheets, wherein the component derived from the vinyl chloride compound (b1) is 60 to 99% by weight in the total amount of the vinyl chloride copolymer resin (B). Related to things.

  Furthermore, the present invention relates to the above adhesive composition for laminated sheets, wherein the vinyl chloride copolymer resin (B) is a vinyl chloride vinyl acetate copolymer resin (B-1).

  Furthermore, the present invention provides the above adhesive composition for laminated sheets, wherein the reactive compound (C) is an isocyanate group-containing compound (c1).

  Furthermore, this invention relates to the said adhesive composition for laminated sheets characterized by the isocyanate group containing compound (c1) containing block isocyanate (c1-1).

Furthermore, in the case where the adhesive composition for laminated sheets further contains a silane coupling agent (D),
It is related with the adhesive composition for laminated sheets characterized by including 0.1-5 weight part of silane coupling agents (D) with respect to 100 weight part of copolymers (A).

It is related with the laminated body using the said adhesive composition for laminated sheets.

  According to the present invention, it is possible to provide a laminated sheet having excellent adhesion strength and high durability even in various plastic films. In particular, the present invention provides an adhesive composition for laminated sheets that is excellent in peel strength, workability, and water resistance at a laminating temperature of less than 200 ° C. in bonding with a steel plate.

Hereinafter, embodiments of the present invention will be described.

  The adhesive composition for laminated sheets of the present invention (hereinafter referred to as “adhesive composition”) is an α, β-unsaturated double bond group-containing compound (a1) containing one or more hydroxyl groups in the molecule. And a copolymer (A) and a vinyl chloride copolymer resin (B) formed by polymerizing the α, β-unsaturated double bond group-containing compound (a2) not containing a hydroxyl group in the molecule, It contains the reactive compound (C) which can react with the functional group which a copolymer (A) has, It is the characteristics.

<Copolymer (A)>
The copolymer (A) of the present invention comprises an α, β-unsaturated double bond group-containing compound (a1) containing one or more hydroxyl groups in the molecule and an α, β-uncontaining compound containing no hydroxyl groups in the molecule. It is a copolymer formed by copolymerization with a saturated double bond group-containing compound (a2).
By having a hydroxyl group in the copolymer (A), through addition or substitution reaction with a reactive compound (C) described later, polarity is imparted or a crosslinked structure is taken, so that a plastic film or glass as a substrate is obtained. It is possible to improve the adhesion to the plate or the steel plate and further increase the cohesive force of the adhesive layer.

  The hydroxyl group contained in the copolymer (A) of the present invention is derived from the α, β-unsaturated double bond group-containing compound (a1) containing one or more hydroxyl groups in the molecule as the constituent component. Yes, a compound having at least one hydroxyl group in the molecule and containing at least one α, β-unsaturated double bond group. The hydroxyl group in the compound (a1) is preferable from the viewpoint of improving the reaction rate in the polymerization reaction. The compound (a1) is divided into a compound (a1-1) having a hydroxyl group and not having a cyclic structure and a compound (a1-2) having a hydroxyl group and having a cyclic structure, both of which have a hydroxyl group. As a result, it has a great effect on the speed improvement accompanying the polymerization reaction.

  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 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. Although not particularly limited, specific examples include the following compounds:

  Of the α, β-unsaturated double bond group-containing compound (a1) containing one or more hydroxyl groups, the compound (a1-1) having a hydroxyl group and not having a cyclic structure includes a hydroxyl group in the structure. Is not particularly limited as long as it does not have a cyclic structure. For example, 2-hydroxyethyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate , 3-hydroxypropyl (meth) acrylate, 1-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate , 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, cyclohexanedimethanol mono (meth) ) Acrylic acid ester, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, ethyl (meth) acrylate-α- (hydroxymethyl), monofunctional (meth) acrylate glycerol, or ( Fatty acid ester-based (meth) acrylic acid esters such as (meth) acrylic acid glycidyl laurate, (meth) acrylic acid glycidyl oleate, (meth) acrylic acid glycidyl stearate, or 2- (acryloyloxy) ethyl 6 -(Meth) acrylic acid ester having a hydroxyl group at the terminal by ring-opening addition of ε-caprolactone lactone to the hydroxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound such as hydroxyhexanonate, Hydroxyl-containing α, β-ethylenically unsaturated double bonds Ethylene oxide to the base-containing compounds, propylene oxide, alkylene oxide adduct (meth) aliphatic hydroxyl group-containing acrylic acid ester obtained by repeatedly adding an alkylene oxide such as butylene oxide (meth) acrylate;

  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, triethylene glycol Hydroxyl-containing aliphatic vinyl ethers such as methylolpropane monovinyl ether, pentaerythritol monovinyl ether, or 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.
As the compound (a1-1), from the viewpoint of adhesion to the substrate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, ε -Caprolactone 1-2 mol addition (meth) acrylic acid 2-hydroxyethyl etc., C2-C18 alpha, beta-unsaturated double bond group containing compound is especially preferable.

  Among the compounds (a1), the compound (a2-2) having a hydroxyl group and having a cyclic structure can be used without particular limitation as long as it has both a hydroxyl group and a cyclic structure. Since the compound (a2-2) has one or more ring structures in the molecule, it is preferable from the viewpoint of water resistance in addition to durability such as heat resistance and moist heat resistance even if it has a hydroxyl group. .

  The compound (a2-2) is not particularly limited as long as it has both a hydroxyl group and a cyclic structure in its structure. For example, (meth) acrylic acid 1,2-cyclohexanedimethanol, (meth) acrylic acid 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol (meth) acrylate, 2-hydroxy-3-phenoxymethyl (meth) acrylate, 2-hydroxy-3-phenoxyethyl (meth) acrylate, ( 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3-phenoxybutyl (meth) acrylate, 2-hydroxy-3-phenoxydecyl (meth) acrylate, 2-hydroxy- (meth) acrylate 3-phenoxyoctadecyl, (meth) acrylic acid monohydroxyethyl phthalate, (meth ) Having a cyclic structure other than a hydroxyl group and a hetero ring such as acrylic acid 2- (4-benzoyl-3-hydroxyphenoxy) ethyl (meth) acrylate;

  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.

  As the compound (a2-2), (meth) acrylic acid 1,2-cyclohexanedimethanol, (meth) acrylic, from the viewpoint of compatibility with the compound (C) described later and durability such as heat resistance and water resistance Particularly preferred are acid 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol (meth) acrylic acid, 2-hydroxy-3-phenoxypropyl (meth) acrylic acid and the like.

  Thus, by using the compound (a1), it is easy to obtain a preferable polymerization rate and control the crosslinking density. Accordingly, when the adhesive composition is used as an adhesive composition for laminated laminates, the laminate comprising the adhesive composition is not only excellent in heat resistance, moist heat resistance, water resistance, etc., but also sufficiently processed. It becomes easy to impart the property.

In the adhesive composition of the present invention, the α, β-unsaturated double bond group-containing compound (a2) that does not have a hydroxyl group in the molecule and constitutes the copolymer (A) will be described. In the present invention, the compound (a2) is a compound containing an α, β-unsaturated double bond group having no hydroxyl group in the molecule, and the adhesive composition contains the component (a2). Therefore, it is easy to increase the efficiency and sensitivity of the copolymerization reaction with the compound (a1). In addition, the viscosity of the adhesive composition can be easily reduced, and the workability during coating can be easily improved. In addition, it is possible to improve the glass transition point (Tg) of the coated product to express a high cohesive force, or to form an adhesive layer having good resistance such as heat resistance and water resistance. Although it does not specifically limit, it is preferable to contain the (alpha), (beta)-unsaturated double bond group containing compound (a2-1) which has an amino group. The interaction between the boric acid derivative (B) described later and the compound (a2-1) improves the glass transition point (Tg) of the coating film to develop a high cohesive force, and has resistance to heat and water. It is possible to form a good coating film.
Therefore, the compound (a2) includes an α, β-unsaturated double bond group-containing compound (a2-1) having an amino group and an α, β-unsaturated double bond group-containing compound (a2-) having no amino group. The compounds that can be roughly classified into 2) and can be used as the component (a2) include the following. Note that amide bonds and amide groups are also included in the range of amino groups.

  As the α, β-unsaturated double bond group-containing compound (a2-1) having an amino group, if it is an α, β-ethylenically unsaturated double bond group-containing compound having an amino group in its structure, There is no restriction in particular, for example, N-methylaminoethyl (meth) acrylate, N-ethylaminoethyl (meth) acrylate, N-propylaminoethyl (meth) acrylate, N-butylaminoethyl (meth) acrylate (Meth) acrylic acid ester having primary and / or secondary amino groups such as N-tributylaminoethyl (meth) acrylate, tetramethylpiperidinyl (meth) acrylate, tetramethylpiperidinyl acrylate, etc. Kind;

  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- (Meth) acrylic 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) 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, (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, 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, heterocyclic α, maleimide derivatives having both nitrogen and oxygen atoms, such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide, etc. 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, -Cyclic amino group-containing compounds having a nitrogen atom-containing heterocycle such as vinyl-2 (1H) -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.

  Among the compounds (a2-2) having an amino group of the present invention, those that promote the interaction with the reactive compound (C) described later are more industrially (meth) acrylamide, monomethylaminoethyl (meta). ) Amino group-containing α, such as acrylamide, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl acrylate, pentamethylpiperidinyl (meth) acrylate, 2-vinylpyridine, 4-vinylpyridine, acryloylmorpholine, etc. A β-unsaturated double bond group-containing compound is particularly preferred.

  Examples of the compound (a2-2) include (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, 3-carboxypropyl (meth) acrylate, (meth) 4-carboxybutyl acrylate, (meth) acrylic acid dimer, maleic acid, fumaric acid, monomethylmaleic acid, monomethylfumaric acid, aconitic acid, sorbic acid, cinnamic acid, α-chlorosorbic acid, glutaconic acid, citraconic acid, Mesaconic acid, itaconic acid, tiglic acid, angelic acid, senetic acid, crotonic acid, isoccrotonic acid, mucobromic acid, mucochloric acid, sorbic acid, muconic acid, aconitic acid, penicillic acid, gellanic acid, citronellic acid, 4-acrylamidobutanoic acid , 6-acrylamidohexanoic acid, 2- (meth) acrylo Polylactone-based (meth) acrylic acid ester, ethylene oxide, propylene oxide, etc. having a carboxyl group at the terminal by ring-opening addition of lactone ring, such as ruoxyethyl succinate, mono (meth) acrylic acid ω-carboxypolycaprolactone ester An alkylene oxide-added succinic acid having a carboxyl group at the terminal, and an aliphatic α, β-unsaturated double bond containing a carboxyl group such as an ester of (meth) acrylic acid. Group-containing carboxylic acids and acid anhydrides thereof;

  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, Carboxylic acids such as cinnamic acid, 7-amino-3-vinyl-3-cephem-4-carboxylic acid and the like, and carboxylic acids containing alicyclic and aromatic rings containing aromatic groups and aromatic rings, and acid anhydrides thereof Etc .;

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 [4.2.1.0 ^3,7 ] non-2-yl, (meth) acrylic acid-5-oxo-4-oxa-tricyclo [ 5.2.1.0 ^3,8 ] dec-2-yl, dihydro-α-terpinyl (meth) acrylate, (meth) acrylic acid-6-oxo-7-oxa-bicyclo [3.2.1] Oct-2-yl, (meth) acrylic acid-7-oxo-8-oxa-bicyclo [3.3.1] oct-2-yl, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyl Oxypropylphthalate 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, (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, (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, 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinyl Cyclic compounds containing alkenyl groups such as benzoic acid, 4-isopropenylbenzenecarboxylic acid, cinnamic acid, 7-amino-3-vinyl-3-cephem-4-carboxylic acid, cyclohexyl vinyl ether, cyclohexylmaleimide, vinylcyclohexene monooxirane ;

  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, 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 acids 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;
Polyalkylene oxides such as methyl 4-vinylbenzoate poly (ethylene oxide), ethyl polyvinylbenzoate poly (ethylene oxide), methyl 4-isopropenylbenzoate poly (propylene oxide), ethyl polyisopropylenylbenzoate poly (propylene oxide) Vinyl benzoate or isopropenyl benzoate compounds having a moiety;

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, 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, 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, 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, (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, 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 an alkylene oxide adduct of (meth) acrylic acid;

  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 [4.2.1.0 ^3,7 ] non-2-yl, (meth) acrylic acid-10-methoxycarbonyl -5-oxo-4-oxa-tricyclo [5.2.1.0 ^3,8 ] 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, 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, pyrvoyl 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, (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, 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, 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;
Metal salts and ammonium salts of 2-methyl-2-propenylsulfonic acid such as ammonium 2-methyl-2-propenylsulfonate, sodium 2-methyl-2-propenylsulfonate, and potassium 2-methyl-2-propenylsulfonate;

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

  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, 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.

  Further, for example, o-di (meth) allylbisphenol A, hydrogenated bisphenol A in which an aromatic ring structure is hydrogenated, and the like are included in the compound (a2) if they have an α, β-unsaturated double bond group. . These may use only 1 type or may use multiple types together.

  The α, β-ethylenically unsaturated double bond group-containing compound (a2) having no hydroxyl group in the molecule is preferably a compound having a (meth) acryloyl group from the viewpoint of reactivity, and the adhesive composition of the present invention. When the product is used as a laminated steel sheet, it is particularly preferable that the α, β-ethylenically unsaturated double bond group includes a compound having a methacryloyl group.

  In the α, β-unsaturated double bond group-containing compound (a2) having no hydroxyl group in the molecule of the present invention, polymerization reactivity, shrinkage in crosslinking and curing with a reactive compound (C) described later, and heat resistance From the viewpoint of durability, such as heat resistance, moist heat resistance and water resistance, a good adhesive composition can be obtained by blending in a timely manner so that both the compound (a1) and the compound (a2) are contained in a balanced manner. it can.

  The copolymer (A) of the present invention is a copolymer obtained by copolymerizing the above compound (a1) and the compound (a2), and the number average molecular weight (denoted as Mn) of the copolymer (A). .) Is preferably 1,000 to 500,000, and more preferably 5,000 to 200,000, in order to achieve both the coating suitability of the adhesive composition for laminated sheets and the cohesive strength of the resin. More preferably, it is 10,000-100,000. If Mn is less than 1,000, the cohesive strength of the resin may be insufficient and the adhesive strength may be reduced. If it is 500,000 or more, the viscosity of the copolymer (A) is high and the coating property is deteriorated. May end up.

  Further, the hydroxyl value (also referred to as OHV) of the copolymer (A) is determined by the content of the compound (a1), but is preferably in the range of 5 to 50 mgKOH / g, more preferably 10 to 30 mgKOH / g. . When the OHV is less than 5 mgKOH / g, the compatibility with the vinyl chloride copolymer resin (B) described later is not sufficient, and sufficient adhesion to the substrate or adherend cannot be obtained. Furthermore, the crosslinking with the compound (C) described later is not sufficient and the heat and humidity resistance is lowered. On the other hand, if it exceeds 50 mgKOH / g, the crosslinking density with the compound (C) described later becomes too high, and in the difficult-to-adhere base material, the adhesive strength is lowered or the water resistance is lowered due to the presence of excess hydroxyl groups. Therefore, it is not preferable.

Copolymer (A) is wet in the adhesive layer, which is a cured coating film after the curing reaction associated with the crosslinking of the adhesive composition, and the adhesion to the plastic film, glass plate, or steel plate that is the substrate during lamination. It is preferable to adjust the glass transition temperature (hereinafter referred to as Tg) of the copolymer (A) to a range of 55 ° C. or more and less than 120 ° C. from the balance of the property and cohesive force, More preferably, it is 60 ° C. or more and less than 90 ° C. When the Tg is less than 50 ° C., the cohesive force in the cured coating film of the adhesive composition may be insufficient and the adhesive strength may be reduced. When the Tg exceeds 120 ° C., the wettability of the adhesive composition is reduced. In some cases, the adhesiveness to the substrate during lamination is lowered and peeled off.
If the Tg of a homopolymer that can be formed from each α, β-unsaturated double bond group-containing compound that is a constituent component of the copolymer (A) is known, the Tg of each homopolymer and each α , Β-unsaturated double bond group-containing compound, and Tg of the copolymer (A) can be theoretically determined.

The glass transition temperature (Tg) is measured using a differential scanning calorimeter (DSC) described later, but can also 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 a homopolymer of each compound constituting a polymer composed of n kinds of α, β-unsaturated double bond group-containing compounds is Tgi (K), and the mass of each compound The fraction is Wi, (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.

Next, the polymerization initiator used when producing a copolymer (A) is demonstrated.
The copolymer (A) in the present invention is 0.001 to 100 parts by weight based on a total of 100 parts by weight of the various α, β-unsaturated double bond group-containing compounds (a1) and to (a2) as described above. It is synthesized by a method such as bulk polymerization, solution polymerization, emulsion polymerization, or suspension polymerization using 20 parts by weight of a polymerization initiator. Preferably, it is synthesized by solution polymerization.

  Examples of the polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile) and 2 , 2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile) and dimethyl 2,2'-azobis (2-methylpropionate) 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), 2,2′-azobis [2- (2-imidazolin-2-yl) An azo compound such as propane].

  Also, benzoyl peroxide, tert-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxydicarbonate, tert-butyl peroxy Organic such as 2-ethylhexanoate, tert-butylperoxyneodecanoate, tert-butylperoxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide A peroxide is mentioned.

  In the polymerization reaction, mercaptans such as lauryl mercaptan and n-dodecyl mercaptan, 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) is prepared by a solution polymerization method, examples of the solvent include alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, and n-butyl alcohol, acetone, methyl ethyl ketone, and methyl-n. -Propyl ketone, methyl isopropyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, methyl isoamyl ketone, diethyl ketone, ethyl n-propyl ketone, ethyl isopropyl ketone, ethyl n-butyl ketone, ethyl isobutyl Ketones such as ketones, di-n-propyl ketone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, isophorone, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate Isobutyl acetate, hexyl acetate, octyl acetate, methyl lactate, propyl lactate, butyl lactate esters, ethylene glycol, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether , Diethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol Glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dipropyl ether, tripropylene glycol monomethyl ether and other glycols and glycol ethers, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, Ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether Glycol acetates such as acetate and dipropylene glycol monomethyl ether acetate, saturated hydrocarbons such as n-hexane, isohexane, n-nonane, isononane, dodecane and isododecane, 1-hexene, 1-heptene, 1-octene, etc. Saturated hydrocarbons, cyclic saturated hydrocarbons such as cyclohexane, cycloheptane, cyclooctane, cyclodecane, decalin, etc., cyclic such as cyclohexene, cycloheptene, cyclooctene, 1,1,3,5,7-cyclooctatetraene, cyclododecene, etc. Examples thereof include unsaturated hydrocarbons and aromatic hydrocarbons such as benzene, toluene and xylene. These organic solvents may be used alone or in combination of two or more. The amount of the solvent may be appropriately determined in consideration of the polymerization conditions, the composition of each component of the α, β-unsaturated double bond-containing compound, the viscosity and concentration of the resulting copolymer (A), etc. It is preferable not to use a solvent having active hydrogen that may react with the active compound (C), for example, an alcohol solvent.

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

<Vinyl chloride copolymer resin (B)>
Next, the vinyl chloride copolymer resin (B) will be described.
The vinyl chloride copolymer resin (B) of the present invention is a copolymer comprising a vinyl chloride compound (b1) as a main component and another α, β-unsaturated double bond group-containing compound (b2). Resin. In the present application, when the vinyl chloride compound is used as a constituent of the vinyl chloride copolymer resin (B), it is referred to as a vinyl chloride compound (b1). Further, an α, β-unsaturated double bond group-containing compound (a1) containing one or more hydroxyl groups in the molecule and an α, β-unsaturated double bond group-containing compound (a2) not containing a hydroxyl group in the molecule ) Including all of the α, β-unsaturated double bond group-containing compounds including both of the above compounds), other than the vinyl chloride compound (b1), other α, β-unsaturated double bond group-containing compounds (b2) Called.

  The vinyl chloride compound (b1) used in the present invention is not particularly limited as long as it is an α, β-unsaturated double bond group-containing compound having one or more chlorine atoms. For example, vinyl chloride monomer or vinylidene chloride monomer is preferably used because of compatibility with A) and industrial availability. When the plastic film used as a substrate is a polyvinyl chloride film described later, From the viewpoint of improving the adhesiveness of the adhesive composition of the present invention, it is preferable to use only one of vinyl chloride and vinylidene chloride, and it is more preferable to use vinyl chloride.

  In the total amount of the vinyl chloride copolymer resin (B) of the present invention, the component derived from the vinyl chloride compound (b1) is preferably 60 to 99% by weight, and more preferably 70 to 95% by weight. When the vinyl chloride compound (b1) is in this range, the compatibility with the copolymer (A) becomes good, and thus the transparency is excellent. In addition, when a polyvinyl chloride film is used as the plastic film of the base material, not only the effects of improving heat resistance and thermal stability can be balanced, but also the adhesive strength is remarkably improved.

  The other α, β-unsaturated double bond group-containing compound (b2) contained in the vinyl chloride copolymer resin (B) of the present invention can be used without particular limitation, and vinyl chloride compounds ( From the viewpoint of copolymerization reactivity with b1), for example, α-olefins such as ethylene and propylene, vinyl esters such as vinyl acetate and vinyl propionate, or these compounds may include a carboxyl group, a hydroxyl group, an amino group or Examples include α, β-unsaturated double bond group-containing compounds having a cyano group, and these components may be used alone or in combination of two or more. As the compound (b2) of the present invention, it is particularly preferable to use vinyl acetate from the viewpoint of improving the compatibility between the copolymer (A) and the vinyl chloride copolymer resin (B). As (B), it is more preferable to use vinyl chloride vinyl acetate copolymer resin (B-1). Copolymer resin (B-2) other than vinyl chloride vinyl acetate copolymer resin (B-1) can be used, but the heat resistance of the laminate using the adhesive composition of the present invention In view of durability such as water resistance, it is particularly preferable to use the vinyl chloride / vinyl acetate copolymer resin (B-1). Further, the vinyl chloride / vinyl acetate copolymer resin (B-1) may contain a slight amount of hydroxyl group or carboxyl group. Moreover, you may use a commercial item.

  The vinyl chloride copolymer resin (B) of the present invention is a copolymer obtained by copolymerizing the vinyl chloride compound (b1) and another α, β-unsaturated double bond group-containing compound (b2). The number average molecular weight (denoted as Mn) of the copolymer resin (B) is a polymer, in addition to the coating suitability of the adhesive composition for laminated sheets, the adhesion to the substrate and the cohesive strength of the resin Therefore, it is preferably 1,000 to 200,000, and more preferably 5,000 to 100,000. If Mn is less than 1,000, the cohesive strength of the resin may be insufficient, and the adhesive strength may be reduced. If it is 500,000 or more, the adhesiveness of the copolymer (A) to the substrate is reduced. Further, the viscosity is further increased, and the coatability may be deteriorated.

  The vinyl chloride copolymer resin (B) in the present invention is synthesized using the same polymerization method as that for the copolymer (A) described above. For example, a vinyl chloride compound (b1), another α, β-unsaturated double bond group-containing compound (b2), and a polymerization initiator are charged into a polymerization reactor equipped with a jacket, After the air is removed, the inside of the reactor is heated by the jacket to carry out the polymerization reaction. At this time, solution polymerization using a solvent may be used, or bulk polymerization without using a solvent may be used. Further, suspension polymerization may be performed by adding water and a dispersant, or emulsion polymerization may be performed by adding water and a surfactant.

<Reactive compound (C)>
Next, the reactive compound (C) will be described.
In the reactive compound (C), the reactive functional group in the compound (C) undergoes a curing reaction with the hydroxyl group of the copolymer (A), thereby improving the cross-linking molecular weight of the laminated sheet adhesive composition and increasing the cohesive force. Have a role to improve. Further, the compound (C) can be expected to improve the interaction with the substrate surface described later. Furthermore, for a base material subjected to a physical treatment such as corona discharge treatment or a chemical treatment modified with an acid or the like, a 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.

Examples of the reactive compound (C) include a polyisocyanate compound (c1), a high molecular weight polycarbodiimide compound (c2), a polyfunctional aziridine compound (c3), and a metal chelate compound (c4).
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, polyisocyanate compounds are preferably used because they have high reactivity with hydroxyl groups and are excellent in improving the adhesiveness of the adhesive composition for laminated sheets after the curing reaction.

Of the reactive compounds (C), the polyisocyanate 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 polyisocyanate compound (c1) include monofunctional polyisocyanates and polyfunctional isocyanates, and examples thereof include aromatic polyisocyanates, aliphatic polyisocyanates, araliphatic polyisocyanates, and alicyclic polyisocyanates. More specifically, as monofunctional polyisocyanate, for example, methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, octyl isocyanate, decyl isocyanate, octadecyl isocyanate, stearyl isocyanate, cyclohexyl isocyanate, phenyl isocyanate, benzyl isocyanate, p-chlorophenyl Isocyanate, p-nitrophenyl isocyanate, 2-chloroethyl isocyanate, 2,4-dichlorophenyl isocyanate, 3-chloro-4-methylphenyl isocyanate, trichloroacetyl isocyanate, chlorosulfonyl isocyanate, (R)-(+)-α-methyl Benzyl isocyanate, (S)-(−)-α-methylbenzyl isocyan Nate, (R)-(-)-1- (1-naphthyl) ethyl isocyanate, (R)-(+)-1-phenylethyl isocyanate, (S)-(-)-1-phenylethyl isocyanate, p- And toluenesulfonyl isocyanate.

  Among polyfunctional isocyanates, the aromatic polyisocyanate is more specifically, 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.

  As the aromatic aliphatic polyisocyanate, 2,4-diisocyanate-1-methyl-benzene (alias: 2,4-TDI), 2,6-diisocyanate-1-methyl-benzene (alias: 2,6-TDI), 1,3-phenylene bismethylene diisocyanate (alias: m-XDI), 1,4-phenylene bismethylene diisocyanate (alias: p-XDI), 2,2′-diphenylmethane diisocyanate (alias: 2,2- MDI), 4,4'-diphenylmethane diisocyanate (alias: 4,4-MDI), 1,3-naphthalenediyl diisocyanate (alias: 1,3-NDI), 1,5-naphthalenediyl diisocyanate (alias: 1,5) -NDI) and the like.

  As alicyclic polyisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (also known as IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, Mention may be made of methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatomethyl) cyclohexane, norbornene diisocyanate and the like.

  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 polyisocyanate 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 polyisocyanate compound (c1) is used, a known catalyst can be used as necessary for promoting 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 the tertiary amine compound include triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, diazabicycloundecene (also known as DBU), etc. 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 (c2), a compound having two or more carbodiimide groups (—N═C═N—) in the molecule is preferably used, and known polycarbodiimides can be used. Moreover, as a carbodiimide compound (c2), 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.

  As such a high molecular weight polycarbodiimide, a carbodilite series manufactured by Nisshinbo Industries, Ltd. may be mentioned. 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 (c3) include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxite), N, N′-toluene-2,4-bis (1-aziridinecarboxyl). Site), 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) propiyl Onate], 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 (c4) include polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium and zirconium, 2,4-pentadione and ethyl-3. -Coordination compounds with oxobutanoate and the like.

  The reactive compound (C) can be used alone or in combination, but as described above, the polyisocyanate compound (c1) is preferably used.

  When considering the hydroxyl value of the copolymer (A) described above, the adhesive composition for a laminated sheet of the present invention contains 40 to 95% by weight of the copolymer (A) in the total amount of the adhesive composition. The vinyl copolymer resin (B) is preferably contained in an amount of 0.5 to 30% by weight, and the compound (C) is preferably contained in an amount of 4.5 to 30% by weight. The copolymer (A) is preferably contained in an amount of 45 to 90% by weight. %, 1 to 20% by weight of the vinyl chloride copolymer resin (B), and 10 to 20% by weight of the compound (C).

When the copolymer (A) and the compound (C) are 40% by weight or more and 5% by weight or more in the total amount of the adhesive composition, sufficient cohesive force can be easily obtained, and the effect of improving heat resistance and moist heat resistance is improved. Can be expected. Further, when the vinyl chloride copolymer resin (B) is 0.5% by weight or more, sufficient adhesion to the substrate can be exhibited.
On the other hand, when the copolymer (A) and the compound (C) are 90% by weight or less and 59.5% by weight or less in the total amount of 100% by weight, curing shrinkage of the adhesive composition can be reduced,・ It is preferable because “peeling” is eliminated. Further, when the boric acid derivative (B) is 25% by weight or less, corrosion can be prevented when a steel plate is used as the substrate.

<Silane coupling agent (D)>
Next, the silane coupling agent will be described.
In addition to the above components, the adhesive composition for laminated sheets of the present invention may contain a silane coupling agent (D). By using a silane coupling agent, an interaction such as a condensation reaction is expressed between the hydroxyl group on the substrate surface and a functional group such as a carboxyl group, thereby improving the adhesive strength of the adhesive composition for laminated sheets. be able to. 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.

  More preferably, the laminated sheet adhesive composition of the present invention 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). If it is 0.1 parts by weight or more, the heat resistance and heat-and-moisture resistance are improved, and if it is less than 5 parts by weight, foaming of the coating film at the time of laminating can be suppressed, and adhesion and adhesion to the substrate can be suppressed. Is preferred.

Next, the three-membered cyclic oxirane compound will be described.
<Three-membered cyclic oxirane compound (E)>
Next, the three-membered cyclic oxirane compound will be described.
In addition to the said component, the adhesive composition for laminated sheets of this invention can contain a 3-membered cyclic oxirane compound (E). By using the three-membered cyclic oxirane compound (E), it becomes possible to improve the cohesive strength of the cured coating film, and the heat resistance, moist heat resistance, water resistance, etc. of the laminated sheet using the general adhesive composition It becomes easy to improve the durability.

The three-membered oxirane compound (E) is a compound having at least one three-membered cyclic ether group in the molecule as a reactive functional group, and can be used without any particular limitation.
Examples of the three-membered cyclic ether group in the molecule include oxirane, methyloxirane, phenyloxirane, 1,2-diphenyloxirane, methylideneoxirane, oxiranylmethyl, oxiranylmethanol, oxiranecarboxylic acid, (chloro Aliphatic cyclic ether groups such as methyl) oxirane, (bromomethyl) oxirane, and oxiranylacetonitrile;

  For example, 3,4-oxiranecyclohexylmethyl 3,4-oxiranecyclohexanecarboxylate, 3,4-oxirane-6-methylcyclohexylmethyl 3,4-oxirane-6-methylcyclohexanecarboxylate, ethylenebis (3,4-oxirane Cyclohexanecarboxylate), bis (3,4-oxiranecyclohexylmethyl) adipate, bis (3,4-oxirane-6-methylcyclohexylmethyl) adipate, diethylene glycol bis (3,4-oxiranecyclohexyl methyl ether), ethylene glycol bis ( 3,4-oxiranecyclohexyl methyl ether), 2,3,4,15-dioxirane-7,11,18,21-tetraoxatrispiro- [5.2.2.5.2.2] heny Cosane (also a compound that can be named 3,4-oxiranecyclospiro-2 ′, 6′-dioxanespiro-3 ″, 5 ″ -dioxanespiro-3 ′ ″, 4 ′ ″-oxiranecyclohexane), 4- (3,4-oxiranecyclohexyl) -2,6-dioxa-8,9-oxiranespiro [5.5] undecane, 4-vinylcyclohexene dioxide, bis-2,3-oxiranecyclopentyl ether, and dicyclo Examples include three-membered cyclic ether groups bonded to alicyclic rings such as pentadiene dioxide, and other groups in which one or more hydrogen atoms are removed from these three-membered cyclic ether group-containing compounds. A compound bonded to the chemical structure can be a three-membered cyclic oxirane compound (E).

  The oxirane compounds exemplified here may be used alone or in combination with a plurality of oxirane compounds.

  The oxirane equivalent of such a three-membered cyclic oxirane compound (E) is usually 3 to 3000 g / eq, preferably 5 to 1500 g / eq. When the oxirane equivalent is less than 3 g / eq, the flexibility of the cured optical film may be lowered, or the adhesive strength may be lowered. On the other hand, if it exceeds 3000 g / eq, the compatibility with other components may decrease, which is not preferable.

  The three-membered cyclic oxirane compound (E) of the present invention preferably further contains an oxirane compound (e1) having an aromatic ring in addition to the three-membered cyclic ether group in order to improve heat resistance and heat and moisture resistance. . Preferable aromatic ring substituents are more specifically, for example, phenyl, phenylene, tolyl, tolreno, benzyl, benzylidene, benzylidine, xylyl, xylylene, phthalylidene, isophthalylidene, terephthalylidene, phenethylidene, phenethylidine, styryl, styrylidene, as- Pseudocumyl, v-pseudocumyl, s-pseudocumyl, mesityl, cumenyl, α-cumyl, hydrocinnamyl, cinnamyl, cinnamilidene, cinnamiridin, duryl, jurylene, thymyl, carvacryl, cuminyl, cuminylidene, neophyll, xenyl, benzhydryl, benzhydrylden, etc. Substituents represented by benzene, toluene, xylene, styrene, hemimeritene, pseudocumene, mesitylene, Emissions, planing, isodurene, durene, cymene, an aromatic ring can be mentioned one or more forms of group obtained by removing a hydrogen atom in the benzene derivatives such as Meriten can bind to other chemical structures.

  In addition, for example, cycloalkenes such as cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclobutadiene, cyclopentadiene, cyclohexadiene, cycloheptadiene, cyclooctadiene;

  For example, [4n + 2] annulene having a carbon number other than benzene and having 3 or more carbon atoms constituting the ring can be mentioned.

  For example, aromatic polycyclic compounds such as biphenyl, diphenylmethane, triphenylmethane;

  For example, pentalene, indene, indane, ninhydrin, naphthalene, tetralin, decalin, sapotalene, cadalene, eudarene, naphthol, menadiol, gossypol, naphthoquinone, lauson, juglone, menadione, plumbagin, futhiocol, echinochrome A, alkanenin, shikonin, acetonaphthone Carbon condensed bicyclic systems such as acid, naphthoyl, naphthalic acid, naphthalate, acetomenaphton, naphthionic acid, naphthionate, naphthionyl, dansyl, crocenic acid, flavianic acid, chromotropic acid, neocuperone, azulene, camazulene, guaiazulene, heptalene, octalene, pulprogaline

  For example, as-indacene, s-indacene, as-hydroindacene, s-hydroindacene, biphenylene, acenaphthylene, acenaphthene, acenaphthoquinone, fluorene, phenalene, perinaphthene, phenanthrene, phenanthryl, phenanthryllium, phenanthryllidene, Phenanthrylene, phenanthrol, molhole, phenanthrone, phenanthraquinone, pimantrene, reten, anthracene, anthryl, anthryllium, anthrylidene, anthrylene, anthrol, anthranol, anthrobin, anthraline, ditranol, anthroyl, anthrone, bianthrone, anthraquinone , Anthraquinonyl, anthraquinonylene, alizarin, quinizarin, anthralphine, chrysazine, anthragalo Le, purpurin, flavonol pull pudding, Anne tiger pull pudding, quinalizarin, Tekutokinon, chrysophanol, chrysolite fan acid, emodin, rain, Kermes acid, carmine acid, Jiantorimido, Antorimido, Kurisanmin acid, carbon fused tricyclic ring system, such as colchicine;

  For example, trindene, trindane, fluoranthene, acephenanthrylene, acephenanthrene, acanthrylene, aceanthrene, triphenylene, pyrene, chrysene, tetraphen, tetracene, naphthacene, rubrene, tetracycline, chlortetracycline, oxytetracycline, pleiadene, benzo Carbon-fused tetracyclic systems such as anthrone;

  For example, a carbon condensed pentacyclic system such as picene, perylene, pentaphen, pentacene, tetraphenylene, coranthrylene, coranthrene;

For example, corannulene, fluorene, anthanthrene, zetrene, hexahelicene, hexaphen, hexacene, rubicene, coronene, trinaphthylene, heptaphene, heptacene, pyranthrene, octaphene, octacene, terylene, naphthacenonaphthacene, nonaphene, nonacene, violanthrene, violanthrene, isolan A carbon condensed ring system having 6 or more rings such as violanthrene, isoviolanthrone, obalene, decaphene, decacene, decacyclene, pentasenopentacene, quaterrylene, hexasenohexacene;
An aromatic ring in which a group in which one or a plurality of hydrogen atoms in a cyclic compound are removed can be bonded to another chemical structure.

These three-membered cyclic oxirane compounds (E) may contain a linking group such as N, S, or P atom.
The three-membered cyclic oxirane compound (E) of the present invention preferably contains a compound (f2) having two or more three-membered cyclic oxirane rings. By containing a plurality of three-membered oxirane rings, the crosslinkability of the adhesive composition to be described later is improved, and it becomes possible to maintain effective adhesive force, heat resistance, and moist heat resistance. The compound (e2) having two or more three-membered oxirane rings also includes a so-called phenoxy resin obtained by a condensation reaction between a diol having a diphenylmethane skeleton and epichlorohydrin.

Here, even if (e1) and (e2) are the same compound, that is, a compound (e12) having an aromatic ring and having two or more three-membered oxirane rings, it can be used without any problem. . These contents in the three-membered cyclic oxirane compound (E) are such that any of (e1), (e2) and (e12) is 0.1 to 100 parts by weight of the copolymer (A). It is preferable to contain the range of 50 weight part from durability points, such as heat resistance, heat-and-moisture resistance, or water resistance.
Further, (e3) which does not belong to any of (e1), (e2) and (e12) can be used without any problem. These may use only 1 type or may use multiple types together.

  The three-membered cyclic oxirane compound (E) is not particularly limited as long as it is a compound having a three-membered cyclic oxirane ring in the molecule, and in particular, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether. 1,6-hexanediol diglycidyl ether, bisphenol A / epichlorohydrin type phenoxy resin, bisphenol F / epichlorohydrin type phenoxy resin, N, N, N ′, N′-tetraglycidyl-m-xylenediamine 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N-diglycidylaniline, N, N-diglycidyltoluidine and the like are preferably used industrially.

  The laminated sheet adhesive composition of the present invention preferably contains 0.1 to 20 parts by weight of the three-membered cyclic oxirane compound (E) with respect to 100 parts by weight of the copolymer (A). A range of 0.5 to 10 parts by weight is particularly preferable. If it is 0.1 weight part or more, it is suitable for the cohesion force of a cured coating film, and the improvement of heat resistance and heat-and-moisture resistance can be expected. On the other hand, when the amount is 20 parts by weight or less, the reactive compound (C) hardly remains in the adhesive composition for laminated sheets, and the adhesive strength is hardly lowered. In addition, after the durability test, the remaining reactive compound (C) may cause a curing reaction and may cause alteration such as the adhesive layer becoming too hard.

<Other components (Q)>
In the adhesive composition of the present invention, various additives (Q) can be appropriately blended as other components as long as the effects of the present invention are not impaired. 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 polymer-based material, titanate coupling agent, tackifier, flexibility imparting agent, plasticizer, flame retardant, storage stabilizer, antioxidant, metal deactivator, It is possible to use independent fillers such as ultraviolet absorbers, thixotropy imparting agents, leveling agents, antifoaming agents, dispersion stabilizers, fluidity imparting agents, antifoaming agents and coloring materials. Further, it can be dissolved, semi-dissolved or micro-dispersed in the adhesive composition as a polymer blend or polymer alloy.

Next, the adhesive composition for laminated sheets will be described.
The adhesive composition for laminated sheets of the present invention comprises the above copolymer (A), vinyl chloride copolymer resin (B), and reactive compound (C) as essential components, and further, if necessary. , A silane coupling agent (D), a three-membered cyclic oxirane compound (E) and other components (Q) can be mixed and then mixed uniformly. 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 adhesive composition for laminated sheets of the present invention can be used in any form of liquid, paste, and film.
In addition, it is preferable that the adhesive composition for laminated sheets in this invention contains an organic solvent, and the 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 is preferably used, and the viscosity of the adhesive composition can be adjusted, or the adhesive 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 is the polymerization conditions of the copolymer (A) or vinyl chloride copolymer resin (B) described above, the composition of each component, the resulting copolymer (A) or vinyl chloride copolymer. It may be appropriately determined in consideration of the viscosity and concentration of the resin (B), but a solvent having active hydrogen that may react with the reactive compound (C), for example, an alcohol solvent or an ether solvent is used. It is better not to.

  The adhesive composition for laminated sheets in the present invention is typically applied and used 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 adhesive composition has a viscosity of at least 25 ° C. of 1 to 2000 mPa · s, preferably 2 to 1500 mPa · s, and preferably 5 to 1000 mPa · s. More preferably, it is s. When the viscosity is higher than 2000 mPa · s, thin film coating cannot be performed, and the hardness 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 adhesive composition.

When the adhesive composition contains a liquid medium such as an organic solvent or water by an appropriate method in accordance with a conventional method, the liquid medium is removed by a method such as heating, When the adhesive composition does not contain a liquid medium to be volatilized, the adhesive layer can be formed on the surface of the substrate or adherend by cooling and solidifying the resin layer in a molten state. .
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 adhesive composition for laminated sheets of the present invention to a substrate is not particularly limited and may be a Mayer bar, applicator, brush, spray, roller, gravure coater, die coater, lip coater, comma coater, knife. Various coating methods such as a coater, reverse coater, spin coater and the like can be mentioned.
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 adhesive 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 adhesive composition for laminated sheets of the present invention is applied to a base material such as a plastic film, a metal plate, or a glass plate, and is adhered to another plastic film, a metal plate, or a glass plate and used as a laminate. 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.

  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, but a polyvinyl chloride film is preferably used. Moreover, the thing of thickness of 500 micrometers can also 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 and 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 adhesive composition can be further improved by the chromic acid treatment. In the case of a galvanized steel sheet, it may be necessary to perform either or both of phosphate treatment and chromic acid treatment. The phosphating treatment and the rurumic acid treatment can be performed by a conventional general method without any particular limitation.
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 laminated body according to the present invention, a laminated steel sheet is preferably used by using a plastic film and a steel sheet as the substrate, and bonding the laminated sheet adhesive composition of the present application.
Laminated steel sheets are manufactured in the following two stages. First, the first step is to apply the adhesive composition to a plastic film or steel plate, dry it at a temperature in the range of 50 to 200 ° C., remove the solvent, and then form a dry adhesive layer Let 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, the steel sheet on which the plastic film and the adhesive composition are laminated differs depending on the type of the plastic film and the adhesive composition, for example, a pressure of 1.0 to 5.0 kg / cm ² , a lamination temperature. Heat lamination is performed using a heating roll so that the temperature is 200 to 220 ° C. and the line speed is 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, the blocking agent is dissociated and volatilized during the thermal lamination, and the isocyanate group is activated to react with the hydroxyl group of the copolymer (A). Cause a chemical reaction, 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 adhesive composition for laminated sheets of the present invention is characterized by having excellent adhesiveness 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 14]
Α, β-unsaturated double containing one or more hydroxyl groups in the molecule in the reaction vessel of the polymerization reaction device equipped with a reaction vessel, a dropping device, a stirrer, a thermometer, a reflux condenser, and an air introduction tube. A bonding group-containing compound (a1), an α, β-unsaturated double bond group-containing compound (a2) not containing a hydroxyl group in the molecule, a catalyst and an organic solvent were charged in the ratios shown in Table 1, respectively.
Next, after the air in the reaction vessel was replaced with nitrogen gas, the temperature was raised to 80 ° C. in an air atmosphere while stirring, and the mixture described in Table 1 was started to be dropped 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 to obtain a resin solution containing the copolymer (A1).

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

"appearance"
The liquid appearance of the resin solution obtained in each synthesis example was visually evaluated.

<< Measurement of nonvolatile content (NV) >>
About 1 g of each resin solution was weighed in a metal container, dried in an oven at 150 ° C. for 20 minutes, the residue was weighed, and the remaining rate was calculated to obtain a nonvolatile content concentration (solid content) (unit:%).

"viscosity"
Using resin type solution in an E-type viscometer (TV-22 manufactured by Toki Sangyo Co., Ltd.) in an atmosphere at 23 ° C., about 1.2 ml is used as a measurement sample, and rotation speed is 0.5 to 100 rpm, and rotation conditions are 1 minute The solution viscosity (mPa · s) was measured.

《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 was prepared, and the number average molecular weight (Mn) and weight average molecular weight (Mw) in terms of polystyrene were measured for the molecular weight of the copolymer (A).

<< 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.

《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

<< 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)

Illustrative compounds are specifically shown in Table 1 below, but are not limited thereto. In Table 1, a blank means no blending.
・ Ingredient (a1-1)
HEA: 2-hydroxyethyl acrylate, HEMA: 2-hydroxyethyl methacrylate / component (a1-2)
CHDMA: 1,4-cyclohexanedimethanol acrylic acid component (a2-1)
AAm: acrylamide, DE: dimethylaminoethyl methacrylate / component (a2-2)
AA: acrylic acid, BA: butyl acrylate, PhA phenoxyethyl acrylate, MMA: methyl methacrylate, EMA: ethyl methacrylate, BMA: butyl methacrylate, VAc: vinyl acetate / initiator AIBN: azoisobutyronitrile / Solvent EAc: ethyl acetate.

<Production of vinyl chloride copolymer resin (B)>
[Synthesis Examples 31-35]
In the pressure-resistant reaction tank of the reaction apparatus equipped with a pressure-resistant reaction tank, an introduction device, a stirrer, a thermometer, and a nitrogen introduction tube, the following other α, β-unsaturated double bond group-containing compound (b2), an initiator, and Each solvent was charged in the ratio shown in Table 2. After sealing and pressurizing with nitrogen, the pressure was reduced and the vinyl chloride compound (b1) was charged. This was kept warm for 40 hours while stirring in a 60 ° C. water bath to carry out a polymerization reaction. A solvent was added to the obtained vinyl chloride copolymer resin (B) to obtain a resin solution having a nonvolatile content concentration of about 30% containing the vinyl chloride copolymer resin (B).
About the obtained resin solution, an external appearance, a non-volatile content, and a viscosity were calculated | required according to said method, and the result was shown in Table 2.

・ Ingredient (b1)
VC: vinyl chloride, VDC: vinylidene chloride, component (b2)
VAc: Vinyl acetate, AN: Acrylonitrile, MA: Maleic acid / initiator PBO: Peroxide-based initiator (“Perbutyl O” manufactured by NOF Corporation)
-Solvent EAc: Ethyl acetate, Tol: Toluene is shown.

<Adhesive composition for laminated sheet>
[Composition Examples 1-46]
In a 300 ml mayonnaise bottle, the resin solution of copolymer (A), vinyl chloride copolymer resin (B), and reactive compound (C) are essential components in the molecule, and if necessary, a silane cup A ring agent (D), a three-membered cyclic oxirane compound (E), other components (Q), and ethyl acetate as an organic solvent are prepared, adjusted to a non-volatile content of about 20%, and sufficiently stirred. After defoaming, an adhesive composition for laminated sheets was obtained. The formulation was charged at the ratio shown in Table 3 (nonvolatile content conversion).

  The appearance of each laminated sheet adhesive composition was evaluated as shown in Table 2.

Illustrative compounds are specifically shown in Table 3 below, but are not limited thereto. In Table 3, a blank means no blending.
・ Ingredient (A)
Each synthesis example is shown.
・ Ingredient (B)
Synthesis examples: Synthesis examples 31 to 34 (vinyl chloride-vinyl acetate copolymer resin), C: vinyl chloride-vinyl acetate copolymer resin (“Solvine C” manufactured by Nisshin Chemical Co., Ltd.), 1008: vinyl chloride-vinyl acetate Copolymer resin (“Kane Vinyl MA1008” manufactured by Kaneka Corporation), Synthesis Example 35: Vinyl chloride-acrylonitrile copolymer resin / component (C)
N3300: Isocyanurate trimer of 1,6-hexamethylene diisocyanate (“SUMIDU N3300” manufactured by Sumika Bayer Urethane Co., Ltd.), E21-1: Prepolymer of polymethylene polyphenyl isocyanate (“SUMI” manufactured by Sumika Bayer Urethane Co., Ltd.) Joule E21-1 "), BL3175: 1,6-hexamethylene diisocyanate isocyanurate trimer-MEK oxime block (" Sumijoule BL3175 "manufactured by Sumika Bayer Urethane Co., Ltd.), V-05: high molecular weight polycarbodiimide compound ( “Carbodilite V-05” manufactured by Nisshinbo Co., Ltd.), HBAP: polyfunctional aziridine compound: 2,2′-bishydroxymethylbutanol tris [3- (1-aziridinyl) propionate], Alc: metal chelate compound: aluminum Squirrel (acetylacetonate)
・ Ingredient (D)
EpS: γ-glycidoxypropyltrimethoxysilane component (E)
FEXO: phenoxymethyl oxolane, HGMDO: (1,6-hexyleneglycoxymethyl)) dioxirane, TED: N, N, N ′, N′-tetraglycidyl-m-xylenediamine, JER1002: bisphenol A type oxirane resin ("JER1002" manufactured by Mitsubishi Chemical Corporation), EHXO: 2-ethylhexinoylmethyloxirane, component (Q)
AO50: An antioxidant manufactured by Adeka Company.

<Laminate>
[Examples 1 to 50] [Comparative Examples 1 to 5]
With respect to the adhesive composition for laminated sheets shown in Table 3, various physical properties (initial workability, low temperature workability, boiling water workability, heat resistance workability, and adhesiveness) were measured by the following methods, and the results are shown in Table 4. Shown in However, Examples 1-27, 33-34 and 42-47 are reference examples.

<Initial workability>
The adhesive composition for laminated sheets was applied to a galvanized steel sheet (thickness = 0.5 mm) with a bar coater so that the dried coating film was 2 μm. Place in an oven (infrared oven with conveyor at 200 ° C) and heat for 100 seconds. Immediately after the heating process is completed, a plastic film (thickness = 150 µm) is laminated at a pressure of 5 kg / cm ² with a laminator. Then, it was put in a water tank and rapidly cooled to obtain a laminate.
In addition, in order to stabilize a laminated body, it was left 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 in which 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, as description of an example base material, Zn plating: Zinc plating steel plate (thickness = 0.5 mm), Cr processing: Chromic acid processing steel plate (thickness = 0.5 mm), PVC: Vinyl chloride film (thickness = 150 μm), PET: Corona-treated polyester film (thickness = 150 μm).

  As shown in Table 4, the adhesive composition for laminated sheets of the present invention is not particularly problematic in Examples 1 to 16, 18, 19, 27 to 42, 45, 48, and 49. In Examples 17, 26, 20-26, 43, 44, 46, 47, and 50, any level of initial workability, low temperature workability, boiling water workability, heat resistance workability, adhesiveness, etc. Low but can be used. On the other hand, in Comparative Examples 1-5, it turns out that boiling-water resistance workability is especially low, there exists difficulty in other workability and adhesiveness, and it is inferior.

The adhesive fat composition for laminated sheets according to the present invention is used for bonding base materials (steel plates or plastic films) of the same or different materials, for example, a multilayer of plastic materials and metal materials. It is suitably used for adhesion of a laminate. Of course, it is also suitable for bonding between plastic films and between metal-based materials.
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.), 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 excellent in workability because the end face is not peeled off by bending even at a low temperature around 0 ° C.
The adhesive composition for laminated sheets according to the present invention exhibits high adhesive strength particularly between laminates including a surface-treated layer of a plastic film, but it is suitable for a surface untreated film (including a surface untreated plastic film). Can also be suitably applied.

Claims (9)

An α, β-unsaturated double bond group-containing compound (a1) containing at least one hydroxyl group in the molecule and an α, β-unsaturated double bond group-containing compound (a2) not containing a hydroxyl group in the molecule; A copolymer (A) formed by polymerizing and vinyl chloride copolymer resin (B),
A reactive compound (C) capable of reacting with the hydroxyl group of the copolymer (A) ;
A three-membered cyclic oxirane compound (E), and an adhesive composition for laminated sheets ,
Three-membered cyclic oxirane compound (E)
An oxirane compound having an aromatic ring in addition to a three-membered cyclic ether group (except for the case of having two or more three-membered oxirane rings) (e1),
A compound having two or more three-membered oxirane rings (excluding cases having an aromatic ring) (e2) and
An adhesive for laminated sheets comprising at least one selected from the group consisting of a compound (e12) having an aromatic ring and having two or more three-membered cyclic oxirane rings or 2-ethylhexinoylmethyloxirane Composition. In the total amount of the adhesive composition for laminated sheets,
40 to 95% by weight of copolymer (A),
0.5-30 wt% of vinyl chloride copolymer resin (B),
4.5-30% by weight of compound (C)
It contains, The adhesive composition for laminated sheets of Claim 1 characterized by the above-mentioned. The copolymer (A) is
The number average molecular weight is 1,000 to 500,000,
And,
The adhesive composition for laminated sheets according to claim 1 or 2, wherein the hydroxyl value is 5 to 50 mgKOH / g.   The adhesive for laminated sheets according to any one of claims 1 to 3, wherein the component derived from the vinyl chloride compound (b1) is 60 to 99 wt% in the total amount of the vinyl chloride copolymer resin (B). Agent composition.   The adhesive composition for laminated sheets according to any one of claims 1 to 4, wherein the vinyl chloride copolymer resin (B) is a vinyl chloride vinyl acetate copolymer resin (B-1).   Reactive compound (C) is an isocyanate group containing compound (c1), The adhesive composition for laminated sheets in any one of Claims 1-5 characterized by the above-mentioned.   The adhesive composition for laminated sheets according to claim 6, wherein the isocyanate group-containing compound (c1) contains a blocked isocyanate (c1-1). In the case where the adhesive composition for laminated sheets according to claim 1 further contains a silane coupling agent (D),
The adhesive composition for laminated sheets, 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). The laminated body using the adhesive composition for laminated sheets in any one of Claims 1-8.