JP2014025046A - Aqueous resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous resin composition and an adhesive resin composition, having excellent adhesiveness and blocking resistance and being environmentally friendly.SOLUTION: Provided is a composition containing a polymer and an aqueous medium, wherein the polymer contains a heteroatom-containing ring structure in a main chain and is obtained by cyclopolymerization of a monomer component containing at least one diene structure-containing monomer selected from the group consisting of 1,5-diene structure-containing monomers containing a heteroatom and 1,6-diene structure-containing monomers containing a heteroatom.

Description

  The present invention relates to an aqueous resin composition. More specifically, the present invention relates to an aqueous resin composition useful for an adhesive, a pressure-sensitive adhesive, a paint, a top coat for building materials, a back coat for building materials, a sealer for building materials, an in-mold material, an optical film, and the like. And a base material having a coating film formed by applying the aqueous resin composition to the base material.

  Conventionally, since an adhesive resin composition has weather resistance and flame retardancy, an ethylene-vinyl acetate copolymer (hereinafter referred to as EVA) is used as a filler (for example, Patent Document 1 and Patent). Reference 2). However, these adhesive resin compositions have a drawback that the adhesiveness decreases with time.

  Therefore, in recent years, development of an aqueous resin composition has been desired from the viewpoint of environmental friendliness as well as excellent adhesion and blocking resistance.

Japanese National Patent Publication No. 08-500214 Japanese translation of PCT publication No. 2002-520820

  This invention is made | formed in view of the said prior art, and it aims at providing the water-based resin composition which is excellent in adhesiveness, is excellent also in blocking resistance, and is kind to an environment.

The present invention
(1) at least one diene structure-containing monomer selected from the group consisting of a 1,5-diene structure-containing monomer containing a heteroatom and a 1,6-diene structure-containing monomer containing a heteroatom An aqueous resin composition comprising a polymer having a ring structure containing a heteroatom in a main chain formed by cyclopolymerization of a monomer component to be contained, and an aqueous medium;
(2) The polymer is of formula (I):

(Wherein R ¹ is a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, R ² is a methylene group, R ³ is a direct bond or a methylene group, R ⁴ is a hydrogen atom, an alkyl having 1 to 4 carbon atoms) Group, phenyl group, carboxyl group, ester group or cyano group, R ⁵ is a direct bond or methylene group, X and Y are each independently a methylene group optionally having an alkyl group of 1 to 4 carbon atoms, imino A group, a carbonyl group, an oxygen atom or a sulfur atom, Z represents a direct bond, a methylene group which may have an alkyl group having 1 to 4 carbon atoms, an imino group, a carbonyl group, an oxygen atom or a sulfur atom; At least one group of Y and Z is an oxygen atom, a sulfur atom or an imino group which are not adjacent to each other)
The aqueous resin composition according to the above (1) having a ring structure-containing unit represented by:
(3) Further described in (1) or (2), further comprising at least one crosslinking agent selected from oxazoline group-containing compounds, carbodiimide group-containing compounds, aminoplast resins, epoxy group-containing compounds and block polyisocyanate compounds. Aqueous resin composition,
(4) The adhesive resin composition comprising the aqueous resin composition according to any one of (1) to (3), and (5) The description according to any one of (1) to (3) The present invention relates to a substrate characterized by having a coating film formed by coating an aqueous resin composition on the substrate.

  The aqueous resin composition of the present invention is excellent in adhesiveness and anti-blocking property and is environmentally friendly because it is aqueous. Since the aqueous resin composition of the present invention contains the adhesive resin composition, it is excellent in adhesiveness, excellent in blocking resistance, and is environmentally friendly because it is aqueous. Since the base material of this invention has the coating film formed from the said aqueous resin composition, while being excellent in the adhesiveness of a base material and a coating film, it is excellent also in the blocking resistance of a coating film.

  The aqueous resin composition of the present invention comprises at least one diene selected from the group consisting of a 1,5-diene structure-containing monomer containing a heteroatom and a 1,6-diene structure-containing monomer containing a heteroatom. It comprises a polymer having a ring structure containing a hetero atom obtained by cyclopolymerizing a monomer component containing a structure-containing monomer in the main chain, and an aqueous medium.

  From the viewpoint of improving adhesion and blocking resistance, the polymer having a ring structure containing a heteroatom in the main chain is represented by formula (I):

(Wherein R ¹ is a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, R ² is a methylene group, R ³ is a direct bond or a methylene group, R ⁴ is a hydrogen atom, an alkyl having 1 to 4 carbon atoms) Group, phenyl group, carboxyl group, ester group or cyano group, R ⁵ is a direct bond or methylene group, X and Y are each independently a methylene group optionally having an alkyl group of 1 to 4 carbon atoms, imino Group, carbonyl group, oxygen atom or sulfur atom, Z is a direct bond, methylene group optionally having an alkyl group having 1 to 4 carbon atoms, imino group, carbonyl group, oxygen atom or sulfur atom, X, Y and At least one group of Z is an oxygen atom, sulfur atom or imino group which is not adjacent to each other)
It is preferable to have a ring structure-containing unit represented by

In the formula (I), R ¹ is a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms. Suitable monovalent organic groups having 1 to 30 carbon atoms include, for example, a chain saturated hydrocarbon group having 1 to 30 carbon atoms, a chain unsaturated hydrocarbon group having 2 to 30 carbon atoms, and 3 to 30 carbon atoms. Alicyclic hydrocarbon groups, aromatic hydrocarbon groups having 6 to 30 carbon atoms, cyclic ether groups having 2 to 30 carbon atoms, and the like. Some or all of the hydrogen atoms of these organic groups may be substituted with at least one substituent selected from the group consisting of an alkoxy group having 1 to 30 carbon atoms, a hydroxyl group and a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Specific examples of R ¹ include, for example, hydrogen atom; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-amyl group, sec-amyl. Group, tert-amyl group, n-hexyl group, sec-hexyl group, n-heptyl group, n-octyl group, sec-octyl group, tert-octyl group, 2-ethylhexyl group, capryl group, nonyl group, decyl group Chain saturated hydrocarbons having 1 to 30 carbon atoms such as a group, undecyl group, lauryl group, tridecyl group, myristyl group, pentadecyl group, cetyl group, heptadecyl group, stearyl group, nonadecyl group, eicosyl group, ceryl group, mesyl group Groups: methoxyethyl group, methoxyethoxyethyl group, methoxyethoxyethoxyethyl group, 3-methoxybutyl group, ethoxy group Alkoxy in which a part of hydrogen atoms of a chain saturated hydrocarbon group having 1 to 30 carbon atoms such as ethyl group, ethoxyethoxyethyl group, phenoxyethyl group, and phenoxyethoxyethyl group is substituted with an alkoxy group having 1 to 30 carbon atoms Group-containing chain saturated hydrocarbon group; a hydroxyl group-containing chain in which a part of hydrogen atoms of a chain saturated hydrocarbon group having 1 to 30 carbon atoms such as hydroxyethyl group, hydroxypropyl group, hydroxybutyl group and the like are substituted with a hydroxyl group A saturated hydrocarbon group; a part of hydrogen atoms of a chain saturated hydrocarbon group having 1 to 30 carbon atoms such as a fluoroethyl group, a difluoroethyl group, a chloroethyl group, a dichloroethyl group, a bromoethyl group and a dibromoethyl group are halogen atoms Substituted halogen-containing chain saturated hydrocarbon group; such as vinyl group, allyl group, methallyl group, crotyl group, propargyl group, etc. A chain unsaturated hydrocarbon group having 12 to 30 carbon atoms and a chain unsaturated hydrocarbon group in which part of the hydrogen atoms thereof is substituted with an alkoxy group, hydroxyl group or halogen atom having 1 to 30 carbon atoms; a cyclopropyl group; C3-C20 alicyclic carbonization such as cyclopentyl group, cyclohexyl group, 4-methylcyclohexyl group, 4-tert-butylcyclohexyl group, tricyclodecanyl group, isobornyl group, adamantyl group, dicyclopentadienyl group A hydrogen group and an alicyclic hydrocarbon group in which part of the hydrogen atom is substituted with an alkoxy group having 1 to 30 carbon atoms, a hydroxyl group or a halogen atom; a phenyl group, a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, 4 -Tert-butylphenyl group, benzyl group, diphenylmethyl group, diphenylethyl group, triphenyl An aromatic hydrocarbon group having 6 to 30 carbon atoms such as a til group, cinnamyl group, naphthyl group, and anthranyl group, and an aromatic group in which part of the hydrogen atoms is substituted with an alkoxy group, hydroxyl group, or halogen atom having 1 to 30 carbon atoms Group hydrocarbon group; carbon such as glycidyl group, β-methylglycidyl group, 3,4-epoxycyclohexylmethyl group, tetrahydrofurfuryl group, 3-methyl-3-oxetanylmethyl group, 3-ethyl-3-oxetanylmethyl group, etc. Examples of the cyclic ether group having 2 to 30 carbon atoms and a cyclic ether group in which a part of the hydrogen atom thereof is substituted with an alkoxy group having 1 to 30 carbon atoms, a hydroxyl group, or a halogen atom are included in the present invention. It is not limited. It is preferable that the said substituent is a C1-C30 alkoxy group, such as a methoxy group, an ethoxy group, a phenoxy group, for example.

Among R ¹ , a chain saturated hydrocarbon group having 1 to 20 carbon atoms and a chain saturated hydrocarbon group in which some of the hydrogen atoms are substituted with an alkoxy group having 1 to 30 carbon atoms; 4 to 20 carbon atoms Of the alicyclic hydrocarbon group and a part of the hydrogen atom thereof substituted with an alkoxy group having 1 to 30 carbon atoms; an aromatic hydrocarbon group having 6 to 20 carbon atoms and a hydrogen atom thereof An aromatic hydrocarbon group partially substituted with an alkoxy group having 1 to 30 carbon atoms; and a cyclic ether group having 4 to 20 carbon atoms and a part of the hydrogen atoms thereof being substituted with an alkoxy group having 1 to 30 carbon atoms. A cyclic ether group, a chain saturated hydrocarbon group having 1 to 20 carbon atoms and a chain saturated hydrocarbon group in which part of the hydrogen atoms are substituted with an alkoxy group having 1 to 30 carbon atoms; 20 alicyclic hydrocarbon groups; 6-20 carbon atoms An aromatic hydrocarbon group; and a cyclic ether group having 4 to 20 carbon atoms, more preferably a methyl group, an ethyl group, an isopropyl group, a phenoxyethyl group, a cyclohexyl group, an isobornyl group, a benzyl group, and a tetrahydrofurfuryl group, A methyl group and a cyclohexyl group are even more preferred.

R ² is a methylene group.
R ³ is a direct bond or a methylene group.
R ⁴ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, a carboxyl group, an ester group or a cyano group. Of the alkyl groups having 1 to 4 carbon atoms, a methyl group is preferable. Examples of the ester group include a group represented by the formula: —COOR ⁶ (wherein R ⁶ represents a monovalent organic group having 1 to 30 carbon atoms). Examples of the monovalent organic group having 1 to 30 carbon atoms include the same monovalent organic groups having 1 to 30 carbon atoms as described above. Among monovalent organic groups having 1 to 30 carbon atoms, chain saturated hydrocarbon groups having 1 to 20 carbon atoms and a portion of the hydrogen atoms substituted with alkoxy groups having 1 to 30 carbon atoms. A hydrocarbon group; an alicyclic hydrocarbon group having 4 to 20 carbon atoms and an alicyclic hydrocarbon group in which some of the hydrogen atoms are substituted with an alkoxy group having 1 to 30 carbon atoms; an aromatic having 6 to 20 carbon atoms Aromatic hydrocarbon group and aromatic hydrocarbon group in which part of its hydrogen atoms are substituted with alkoxy group having 1 to 30 carbon atoms; and cyclic ether group of 4 to 20 carbon atoms and part of its hydrogen atoms having carbon number A cyclic ether group substituted with an alkoxy group having 1 to 30 carbon atoms is preferred, and a chain saturated hydrocarbon group having 1 to 20 carbon atoms and a chain in which some of the hydrogen atoms are substituted with alkoxy groups having 1 to 30 carbon atoms. Saturated hydrocarbon group; alicyclic carbon having 4 to 20 carbon atoms A hydrogen group; an aromatic hydrocarbon group having 6 to 20 carbon atoms; and a cyclic ether group having 4 to 20 carbon atoms, more preferably a methyl group, an ethyl group, an isopropyl group, a phenoxyethyl group, a cyclohexyl group, an isobornyl group, and a phenyl group. Further, a benzyl group and a tetrahydrofurfuryl group are more preferable, and a methyl group and a cyclohexyl group are still more preferable.
R ⁵ is a direct bond or a methylene group.

X and Y are each independently a methylene group, imino group, carbonyl group, oxygen atom or sulfur atom which may have an alkyl group having 1 to 4 carbon atoms. Z is a direct bond, a methylene group optionally having an alkyl group having 1 to 4 carbon atoms, an imino group, a carbonyl group, an oxygen atom or a sulfur atom. At least one group of X, Y and Z is an oxygen atom, a sulfur atom or an imino group which are not adjacent to each other. Examples of the imino group include a —NR ⁷ — group (wherein R ⁷ represents a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms). The above-mentioned “oxygen atom, sulfur atom or imino group not adjacent to each other” means that heteroatoms are not adjacent to each other, for example, —O—O—, —O—NR ⁷ — and the like. In the R ⁷ group, examples of the monovalent organic group having 1 to 30 carbon atoms include the same monovalent organic groups having 1 to 30 carbon atoms as described above. Among monovalent organic groups having 1 to 30 carbon atoms, chain saturated hydrocarbon groups having 1 to 20 carbon atoms and a portion of the hydrogen atoms substituted with alkoxy groups having 1 to 30 carbon atoms. A hydrocarbon group; an alicyclic hydrocarbon group having 4 to 20 carbon atoms and an alicyclic hydrocarbon group in which some of the hydrogen atoms are substituted with an alkoxy group having 1 to 30 carbon atoms; an aromatic having 6 to 20 carbon atoms Aromatic hydrocarbon group and aromatic hydrocarbon group in which part of its hydrogen atoms are substituted with alkoxy group having 1 to 30 carbon atoms; and cyclic ether group of 4 to 20 carbon atoms and part of its hydrogen atoms having carbon number A cyclic ether group substituted with an alkoxy group having 1 to 30 carbon atoms is preferred, and a chain saturated hydrocarbon group having 1 to 20 carbon atoms and a chain in which some of the hydrogen atoms are substituted with alkoxy groups having 1 to 30 carbon atoms. Saturated hydrocarbon group; alicyclic carbon having 4 to 20 carbon atoms A hydrogen group; an aromatic hydrocarbon group having 6 to 20 carbon atoms; and a cyclic ether group having 4 to 20 carbon atoms, more preferably a methyl group, an ethyl group, an isopropyl group, a phenoxyethyl group, a cyclohexyl group, an isobornyl group, and a phenyl group. Further, a benzyl group and a tetrahydrofurfuryl group are more preferable, and a methyl group and a cyclohexyl group are still more preferable.

  1,5-diene structure-containing monomer containing a hetero atom and 1,6-diene structure-containing monomer containing a hetero atom as a diene structure-containing monomer giving a ring structure-containing unit represented by the formula (I) At least one diene structure-containing monomer selected from the group consisting of: Among the diene structure-containing monomers that give the ring structure-containing unit represented by the formula (I), preferred monomers include the formula (II):

(Wherein R ¹ , X, Y and Z are the same as above, R ⁸ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, a carboxyl group, an ester group or a cyano group)
The diene structure containing monomer represented by these is mentioned. Of the alkyl groups having 1 to 4 carbon atoms, a methyl group is preferable. Examples of the ester group include a group represented by the formula: —COOR ⁶ (wherein R ⁶ is the same as described above).

  Specific examples of the diene structure-containing monomer represented by the formula (II) include the formula (IIa):

(Wherein R ¹ is the same as above)
1,6-diene structure-containing monomer represented by the formula (IIb):

(Wherein R ¹ is the same as above)
1,6-diene structure-containing monomer represented by the formula (IIc):

(Wherein, R ¹ is the same as above, and each R ¹ may be the same or different)
1,6-diene structure-containing monomer represented by the formula (IId):

(Wherein R ¹ and R ⁷ are the same as above)
1,6-diene structure-containing monomer represented by the formula (IIe):

(Wherein R ¹ is the same as above)
1,6-diene structure-containing monomer represented by the formula (IIf):

(Wherein R ¹ and R ⁷ are the same as above)
1,6-diene structure-containing monomer represented by the formula (IIg):

(Wherein R ¹ is the same as above)
1,6-diene structure-containing monomer represented by the formula (IIh):

(Wherein R ¹ is the same as above)
1,5-diene structure-containing monomer represented by the formula (IIi):

(Wherein R ¹ is the same as above)
1,5-diene structure containing monomers represented by these. Among these, from the viewpoint of improving the cyclopolymerization activity, the adhesion and blocking resistance of the resulting polymer, a 1,6-diene structure-containing monomer represented by the formula (IIa), represented by the formula (IIb) The 1,6-diene structure-containing monomer represented by formula (IIc) and the 1,6-diene structure-containing monomer represented by formula (IIc) are preferred. From the viewpoint of improving adhesiveness and anti-blocking property, The represented 1,6-diene structure-containing monomer is more preferred. These monomers can be prepared, for example, by the method described in JP-A-10-226669.

  Examples of the 1,6-diene structure-containing monomer represented by the formula (IIa) include α-allyloxymethyl acrylic acid, α-allyloxymethyl acrylate methyl, α-allyloxymethyl ethyl acrylate, α- Propyl allyloxymethyl acrylate, isopropyl α-allyloxymethyl acrylate, butyl α-allyloxymethyl acrylate, tert-butyl α-allyloxymethyl acrylate, phenoxyethyl α-allyloxymethyl acrylate, α-allyloxy Cyclohexyl methyl acrylate, α-allyloxymethyl acrylate dicyclopentadienyl, α-allyloxymethyl acrylate isobornyl, α-allyloxymethyl acrylate adamantyl, α-allyloxymethyl acrylate benzyl, α-allyloxymethyl Acrylic acid Although such allyloxymethylacrylate esters such as tigers tetrahydrofurfuryl and the like, and the present invention is not limited only to those exemplified. These monomers may be used alone or in combination of two or more. Among these, from the viewpoint of improving adhesion and blocking resistance, methyl α-allyloxymethyl acrylate, ethyl α-allyloxymethyl acrylate, isopropyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylic Phenoxyethyl acid, cyclohexyl α-allyloxymethyl acrylate, isobornyl α-allyloxymethyl acrylate, benzyl α-allyloxymethyl acrylate and tetrahydrofurfuryl α-allyloxymethyl acrylate are preferred, α-allyloxymethyl acrylic Methyl acid and cyclohexyl α-allyloxymethyl acrylate are more preferred. Further, while the aqueous resin composition of the present invention is aqueous, the water resistance of the coating film formed from the aqueous resin composition is improved, and the glass transition temperature of the polymer used in the aqueous resin composition is improved. In particular, methyl α-allyloxymethyl acrylate is particularly preferable because the film can be formed at a low temperature and the scratch resistance can be improved even if the glass transition temperature is low.

  Examples of the 1,6-diene structure-containing monomer represented by the formula (IIb) include, for example, α-methallyloxymethyl acrylic acid, α-methallyloxymethyl acrylate methyl, α-methallyloxymethyl acrylate ethyl , Α-methallyloxymethyl propyl acrylate, α-methallyloxymethyl acrylate isopropyl, α-methallyloxymethyl acrylate butyl, α-methallyloxymethyl acrylate tert-butyl, α-methallyloxymethyl acrylate Phenoxyethyl acid, cyclohexyl α-methallyloxymethyl acrylate, dicyclopentadienyl α-methallyloxymethyl acrylate, isobornyl α-methallyloxymethyl acrylate, adamantyl α-methallyloxymethyl acrylate, α- Benzyl methallyloxymethyl acrylate, α-me Although such methallyl oxymethyl acrylate esters such as Lil oxymethyl tetrahydrofurfuryl acrylate and the like, and the present invention is not limited only to those exemplified. These monomers may be used alone or in combination of two or more. Among these, from the viewpoint of improving adhesion and blocking resistance, methyl α-methallyloxymethyl acrylate, ethyl α-methallyloxymethyl acrylate, isopropyl α-methallyloxymethyl acrylate, α-meta Phenoxyethyl ryloxymethyl acrylate, cyclohexyl α-methallyloxymethyl acrylate, isobornyl α-methallyloxymethyl acrylate, and benzyl α-methallyloxymethyl acrylate and tetrahydrofurfuryl α-methallyloxymethyl acrylate Are preferable, and methyl α-methallyloxymethyl acrylate and cyclohexyl α-methallyloxymethyl acrylate are more preferable.

  Examples of the 1,6-diene structure-containing monomer represented by the formula (IIc) include bis (α-hydroxymethylacrylic acid) ether, bis (α-hydroxymethylacrylic acid methyl) ether, and bis (α-hydroxy). Methyl acrylate) ether, bis (α-hydroxymethyl acrylate) ether, bis (α-hydroxymethyl acrylate) ether, bis (α-hydroxymethyl butyl) ether, bis (α-hydroxymethyl acryl) Acid tert-butyl) ether, bis (α-hydroxymethyl acrylate phenoxyethyl) ether, bis (α-hydroxymethyl acrylate) ether, bis (α-hydroxymethyl acrylate dicyclopentadienyl) ether, bis ( α-Hydroxymethyl Α-hydroxymethyl acryl such as isobornyl acrylate) ether, bis (α-hydroxymethyl acrylate adamantyl) ether, bis (α-hydroxymethyl acrylate benzyl) ether, bis (α-hydroxymethyl acrylate tetrahydrofurfuryl) ether Examples include ethers of acid monomers, but the present invention is not limited to such examples. These monomers may be used alone or in combination of two or more. Among these, from the viewpoint of improving adhesion and blocking resistance, bis (α-hydroxymethyl methyl acrylate) ether, bis (α-hydroxymethyl ethyl acrylate) ether, bis (α-hydroxymethyl acrylate) ) Ether, bis (α-hydroxymethyl acrylate) ether, bis (α-hydroxymethyl acrylate) ether, bis (α-hydroxymethyl acrylate) ether, bis (α-hydroxymethyl benzyl) Ethers and bis (α-hydroxymethyl acrylate tetrahydrofurfuryl) ether are preferred, bis (α-hydroxymethyl acrylate methyl) ether and bis (α-hydroxymethyl acrylate acrylate) Ether is preferred.

  The content of the ring structure-containing unit represented by the formula (I) in the polymer having a ring structure containing a hetero atom in the main chain is preferably 5% by mass or more from the viewpoint of improving adhesiveness and blocking resistance. Preferably, it is 10% by mass or more, more preferably 15% by mass or more, and from the viewpoint of improving adhesiveness and blocking resistance, it is 100% by mass or less, preferably 99% by mass or less, more preferably 95% by mass or less, Preferably it is 90 mass% or less.

  The content of the ring structure-containing unit represented by the formula (I) in the polymer having a ring structure containing a hetero atom in the main chain is used as a raw material for the polymer having a ring structure containing a hetero atom in the main chain. It is calculated | required as a content rate of the diene structure containing monomer which gives the ring structure containing unit represented by Formula (I) in a monomer component.

  The content of the diene structure-containing monomer in the monomer component is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more from the viewpoint of improving adhesiveness and blocking resistance. From the viewpoint of improving adhesiveness and blocking resistance, it is 100% by mass or less, preferably 99% by mass or less, more preferably 95% by mass or less, and further preferably 90% by mass or less.

  The polymer may contain a unit other than the unit having a ring structure containing a hetero atom within a range in which the object of the present invention is not inhibited. In other words, the monomer component may contain a monomer other than the diene structure-containing monomer. Examples of the monomer other than the diene structure-containing monomer include, for example, a monomer having a carboxyl group, an acidic phosphate ester monomer, a monomer having a group having an active hydrogen, and a (meth) acrylic ester. A monomer having an epoxy group, a monomer having a nitrogen atom, a monomer having two or more polymerizable double bonds, an aromatic monomer, a monomer having a halogen atom, a vinyl ester Monomers, vinyl ether monomers, and the like that do not have a ring structure containing a hetero atom can be mentioned, but the present invention is not limited to such examples. These monomers may be used alone or in combination of two or more.

  Examples of the monomer having a carboxyl group include aliphatic monocarboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, and maleic anhydride, but the present invention is not limited to such examples. Absent. These monomers having a carboxyl group may be used alone or in combination of two or more.

  Examples of acidic phosphate ester monomers include 2-acryloloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, and the like, but the present invention is not limited to such examples. These acidic phosphate ester monomers may be used alone or in combination of two or more.

  Examples of the monomer having a group having active hydrogen include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, and hydroxybutyl methacrylate. Examples include hydroxyl group-containing (meth) acrylic acid esters; α-hydroxymethyl acrylate esters such as methyl α-hydroxymethyl acrylate and ethyl α-hydroxymethyl acrylate, but the present invention is limited to such examples. It is not a thing. These monomers having a group having active hydrogen may be used alone or in combination of two or more.

  Examples of (meth) acrylic acid esters include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, and n-acrylate. (Meth) acrylic acid alkyl esters such as butyl, n-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate; isobornyl acrylate, isobornyl methacrylate, Cycloalkyl (meth) acrylates such as cyclohexyl acrylate and cyclohexyl methacrylate; cyclohexylmethyl acrylate, cyclohexylmethyl methacrylate, cyclohexylethyl acrylate, (Meth) acrylic acid cycloalkylalkyl such as cyclohexylethyl tacrylate, cyclohexylpropyl acrylate, cyclohexylpropyl methacrylate, 4-methylcyclohexylmethyl acrylate, 4-methylcyclohexylmethyl methacrylate, and the like, It is not limited only to such illustration. These (meth) acrylic acid esters may be used alone or in combination of two or more.

  Examples of the monomer having an epoxy group include epoxy group-containing (meth) acrylic acid esters such as glycidyl acrylate and glycidyl methacrylate, but the present invention is not limited to such examples. . These monomers having an epoxy group may be used alone or in combination of two or more.

  Examples of the monomer having a nitrogen atom include (meth) acrylamide such as acrylamide and methacrylamide, N, N′-dimethylaminoethyl acrylate, N, N′-dimethylaminoethyl methacrylate, and N, N acrylic acid. -N-vinyl compounds such as diethylaminoethyl, N, N-diethylaminoethyl methacrylate, nitrogen-containing (meth) acrylic acid such as acrylic imide and methacrylic imide, N-vinyl pyrrolidone, etc. However, the present invention is not limited to such examples. These monomers having a nitrogen atom may be used alone or in combination of two or more.

  Examples of the monomer having two or more polymerizable double bonds include ethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, and 1,4-butanediol di (meth) acrylate. , 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, etc., alkyl diol di (meth) acrylate having 2 to 10 carbon atoms, pentaerythritol monohydroxytri ( (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol (monohydroxy) penta (meth) acrylate, ethylene oxide modified 1,6-hex Diol di (meth) acrylate, propylene oxide modified neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane triethoxytri (meth) acrylate, bisphenol A di (meth) acrylate, ditrimethylolpropane tetra (Meth) acrylate, ethoxylated glycerin tri (meth) acrylate, triallyl isocyanurate, propylene oxide modified glycerol tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di Polyalkylene glycols such as (meth) acrylate and polypropylene glycol di (meth) acrylate Polyfunctional (meth) acrylic acid esters such as aldehyde di (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate; butadiene, isoprene, chloroprene, Although divinylbenzene, diallyl phthalate, etc. are mentioned, this invention is not limited only to this illustration. These monomers having two or more polymerizable double bonds may be used alone or in combination of two or more. Among these monomers having two or more polymerizable double bonds, a polyfunctional (meth) acrylic acid ester is preferable from the viewpoint of improving the weather resistance.

  Examples of the aromatic monomer include styrene compounds such as styrene and α-methylstyrene, but the present invention is not limited to such examples. These aromatic monomers may be used alone or in combination of two or more.

  Examples of the monomer having a halogen atom include vinyl chloride, but the present invention is not limited to such examples. Only one type of monomer having a halogen atom may be used, or two or more types may be used in combination.

  Examples of the vinyl ester monomer include vinyl acetate, but the present invention is not limited to such examples. Only one type of vinyl ester monomer may be used, or two or more types may be used in combination.

  Examples of vinyl ether monomers include butyl vinyl ether and cyclohexyl vinyl ether, but the present invention is not limited to such examples. These vinyl ether monomers may be used alone or in combination of two or more.

  Among the monomers other than diene structure-containing monomers, UV-absorbing properties such as benzotriazole monomers, benzophenone monomers, and triazine monomers from the viewpoint of improving weather resistance and blocking resistance Monomer having a group; Monomer having a UV-stable group; Glass transition when a homopolymer such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tert-butyl (meth) acrylate is used. A monomer having a property of imparting weather resistance such as a (meth) acrylic acid ester having a high temperature (hereinafter referred to as a weather resistant monomer) is preferable. A monomer having an ultraviolet absorbing group can be easily obtained commercially, for example, as Otsuka Chemical Co., Ltd., trade name: RUVA93, Osaka Organic Chemical Industry Co., Ltd., trade name: BP-1A. Can do. Monomers having a UV-stable group can be easily obtained commercially, for example, as ADK STAB series such as ADK STAB LA-82 and ADK STAB LA-87 manufactured by ADEKA Corporation.

  The content of the weatherable monomer in the monomer component is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 3% by mass or more, particularly preferably from the viewpoint of improving weatherability. Is 5% by mass or more, and from the viewpoint of improving the brittleness of the adhesive resin composition, it is preferably 90% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less, and still more preferably 50% by mass. % Or less.

  The monomer component has a hydroxyl group-containing (meth) acrylate ester such as 2-hydroxyethyl (meth) acrylate, caprolactone-modified hydroxy (meth) acrylate, α-hydroxymethyl acrylate ester, etc., from the viewpoint of improving adhesiveness. Hydroxyl group-containing monomers typified by: nitrogen atom-containing monomers typified by nitrogen atom-containing (meth) acrylic acid esters such as (meth) acrylic imide and morpholino (meth) acrylate; (meth) acrylic acid tetrahydro It is preferable to contain a cyclic ether group-containing (meth) acrylic acid ester such as furfuryl. As caprolactone-modified hydroxy (meth) acrylate, for example, commercially available as Daicel Chemical Industries, Ltd., trade name: Plaxel FM1, Plaxel FM1D, Plaxel FM2D, Plaxel FM3, Plaxel FA1DM, Plaxel FA2D, etc. Can do.

From the viewpoint of improving adhesiveness, the content of monomers that improve adhesion such as a hydroxyl group-containing monomer, a nitrogen atom-containing monomer, and a cyclic ether group-containing (meth) acrylate in the monomer component , Preferably 0.1% by mass or more, more preferably 0.3% by mass or more, further preferably 1% by mass or more, and from the viewpoint of enhancing hydrolysis resistance and insulation resistance, preferably 40% by mass or less, More preferably, it is 35 mass% or less.

  The monomer component preferably contains acrylic acid having a basic structure of bisarylfluorene from the viewpoint of improving hydrolysis resistance and insulation resistance. Acrylic acid having bisarylfluorene as a basic structure is commercially easily available as, for example, Osaka Gas Chemical Co., Ltd., trade names: Ogsol EA-0200, Ogsol EA-0200, Ogsol EA-0500, Ogsol EA-1000, etc. Can be obtained.

Further, cyclohexyl alkyl esters of (meth) acrylic acid, dicyclopentenyl (meth) acrylic acid, dicyclopentenyloxyethyl (meth) acrylic acid, dicyclopentanyl as disclosed in JP-A-2002-69130. (Meth) acrylic acid, tricyclo [5.2.1.0 ^2.6 ] dec-8-yl (meth) acrylic acid, terpene (meth) acrylic acid, and the like can also be used.

  When polymerizing the monomer component, a chain transfer agent may be used as necessary from the viewpoint of suppressing an increase in molecular weight distribution and gelation. Examples of the chain transfer agent include mercaptocarboxylic acids such as mercaptoacetic acid and 3-mercaptopropionic acid; methyl mercaptoacetate, methyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, and n-octyl 3-mercaptopropionate. , Methoxybutyl 3-mercaptopropionate, stearyl 3-mercaptopropionate, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercapto Mercaptocarboxylic esters such as propionate); alkyl such as ethyl mercaptan, tert-butyl mercaptan, n-dodecyl mercaptan, 1,2-dimercaptoethane Llucaptans; mercaptoalcohols such as 2-mercaptoethanol and 4-mercapto-1-butanol; aromatic mercaptans such as benzenethiol, m-toluenethiol, p-toluenethiol and 2-naphthalenethiol; tris [(3- Mercaptoisocyanurates such as mercaptopropionyloxy) -ethyl] isocyanurate; disulfides such as 2-hydroxyethyl disulfide and tetraethylthiuram disulfide; dithiocarbamates such as benzyldiethyldithiocarbamate; dimers such as α-methylstyrene dimer Alkyl halides such as carbon tetrabromide, and the like, but the present invention is not limited to such examples. These chain transfer agents may be used alone or in combination of two or more. Among these chain transfer agents, mercaptocarboxylic acids, mercaptocarboxylic acid esters, alkyl mercaptans are obtained because they are easily available, have excellent anti-crosslinking properties, and have a low degree of decrease in polymerization rate. Compounds having a mercapto group such as mercaptoalcohols, aromatic mercaptans and mercaptoisocyanurates are preferred.

  The amount of the chain transfer agent may be appropriately set according to the composition of the monomer component, the polymerization conditions such as the polymerization temperature, the molecular weight of the target polymer, etc., and is not particularly limited, but the weight average molecular weight is several thousand to When obtaining tens of thousands of polymers, the amount is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass per 100 parts by mass of the monomer component.

  Examples of the polymerization method of the monomer component include a bulk polymerization method, a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, and the like, but the present invention is not limited to such examples. Among the polymerization methods, since an environmentally friendly aqueous resin composition can be obtained directly, an emulsion polymerization method and a suspension polymerization method are preferable, and an emulsion polymerization method is more preferable. When the monomer component is polymerized by solution polymerization, an aqueous medium is preferably used as a solvent because an aqueous dispersion of the polymer can be easily obtained.

  In the present specification, the aqueous medium means water or a mixed solvent of water and a hydrophilic organic solvent having a water content of 50% by mass or more. Examples of the hydrophilic organic solvent include monohydric alcohols such as methanol, ethanol, isopropyl alcohol, n-propyl alcohol, and allyl alcohol, ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, and dipropyleneglycol. Polyhydric alcohols such as acetone, methyl ethyl ketone, ketones such as methyl propyl ketone, aliphatic organic acid alkyl esters such as methyl formate, ethyl formate, methyl acetate, methyl acetoacetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, Diethylene glycol diethyl ether, ethylene glycol monomethyl ether, ethylene glycol mono Chirueteru, although such polyhydric alkyl ethers of alcohols, such as dipropylene glycol monomethyl ether, the present invention is not limited those exemplified only. These hydrophilic organic solvents may be used alone or in combination of two or more. Of the aqueous media, water is preferred.

  When the monomer component is polymerized by emulsion polymerization, the embodiment for carrying out the emulsion polymerization is not particularly limited. Emulsion polymerization of the monomer component can be performed, for example, by appropriately adding a monomer component, an emulsifier and, if necessary, a polymerization initiator in an aqueous medium and polymerizing the monomer component. Moreover, in order to adjust the molecular weight of the obtained polymer, a polymerization chain transfer agent may be used as a monomer component, or the polymer may be cross-linked in the obtained emulsion particles.

  When the monomer component is polymerized by heating, electron beam irradiation or the like, a polymerization initiator is not particularly required, but a polymerization initiator is preferably used from the viewpoint of promoting the polymerization reaction.

  Examples of the polymerization initiator include water-soluble polymerization initiators and oil-soluble polymerization initiators such as ammonium persulfate, potassium persulfate, hydrogen peroxide, and butyl hydroperoxide. It is not limited. In order to promote emulsion polymerization, for example, sodium bisulfite, L-ascorbic acid or the like may be used as a reducing agent. These reducing agents may be used alone or in combination of two or more.

  When a polymerization initiator is used, the amount of the polymerization initiator per 100 parts by mass of the monomer component may be appropriately set according to the type of the polymerization initiator, but preferably 0.01 to 2 parts by mass, More preferably, it is 0.03-1 mass part, More preferably, it is 0.2-1 mass part.

  Examples of the emulsifier include an anionic emulsifier, a nonionic emulsifier, a cationic emulsifier, an amphoteric emulsifier, and a polymer emulsifier. These emulsifiers may be used alone or in combination of two or more.

  Examples of the anionic emulsifier include alkyl sulfate salts such as ammonium dodecyl sulfate and sodium dodecyl sulfate; alkyl sulfonate salts such as ammonium dodecyl sulfonate and sodium dodecyl sulfonate; alkyl aryl sulfonate salts such as ammonium dodecyl benzene sulfonate and sodium dodecyl naphthalene sulfonate; Examples include polyoxyethylene alkyl sulfate salts; polyoxyethylene alkyl aryl sulfate salts; dialkyl sulfosuccinates; aryl sulfonic acid-formaldehyde condensates; fatty acid salts such as ammonium laurate and sodium stearate. It is not limited to illustration only.

  Nonionic emulsifiers include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, condensate of polyethylene glycol and polypropylene glycol, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, fatty acid monoglyceride, ethylene oxide and aliphatic Although the condensation product with an amine etc. are mentioned, this invention is not limited only to this illustration.

  Examples of the cationic emulsifier include alkylammonium salts such as dodecylammonium chloride, but the present invention is not limited to such examples.

  Examples of amphoteric emulsifiers include betaine ester type emulsifiers, but the present invention is not limited to such examples.

  Examples of the polymer emulsifier include poly (meth) acrylates such as sodium polyacrylate; polyvinyl alcohol; polyvinylpyrrolidone; polyhydroxyalkyl (meth) acrylates such as polyhydroxyethyl (meth) acrylate; and polymers thereof. Although the copolymer etc. which use 1 or more types of the monomer to comprise as a copolymerization component are mentioned, this invention is not limited only to this illustration.

  Moreover, as an emulsifier, the emulsifier which has a polymeric group, ie, what is called a reactive emulsifier, from a viewpoint of improving the water resistance of a molded object is preferable, and a non-nonylphenyl type emulsifier is preferable from a viewpoint of environmental protection.

  As the reactive emulsifier, for example, propenyl-alkylsulfosuccinic acid ester salt, (meth) acrylic acid polyoxyethylene sulfonate salt, (meth) acrylic acid polyoxyethylene phosphonate salt [for example, manufactured by Sanyo Chemical Industries, Ltd., Trade name: Eleminool RS-30, etc.], polyoxyethylene alkylpropenyl phenyl ether sulfonate salt [for example, product name: Aqualon HS-10, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.], allyloxymethylalkyloxypolyoxy Sulfonate salt of ethylene, sulfonate salt of allyloxymethylnonylphenoxyethylhydroxypolyoxyethylene (for example, product name: Aqualon KH-10 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), allyloxymethylnonylphenoxyethylhydroxypolyoxye Sulfonate salt of Ren (for example, ADEKA Co., Ltd., trade name: ADEKA rear soap SE-10, etc.), allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfate salt [for example, ADEKA Corporation, trade name: ADEKA Rear soap SR-10, ADEKA rear soap SR-30, etc.], bis (polyoxyethylene polycyclic phenyl ether) methacrylated sulfonate salts (for example, Nippon Emulsifier Co., Ltd., trade name: Antox MS-60, etc.), Allyloxymethylalkoxyethylhydroxypolyoxyethylene [for example, manufactured by ADEKA Corporation, trade name: Adekaria soap ER-20, etc.], polyoxyethylene alkylpropenyl phenyl ether [for example, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., product Name: Aqualon RN-20, etc.) Examples include allyloxymethylnonylphenoxyethylhydroxypolyoxyethylene [for example, trade name: ADEKA rear soap NE-10 manufactured by ADEKA Corporation] and the like, but the present invention is not limited only to such illustration. .

  In the emulsion polymerization, if necessary, a chelating agent such as sodium ethylenediaminetetraacetate, a dispersing agent such as sodium polyacrylate, or an inorganic salt may be used. Examples of the method for adding a monomer component, a polymerization initiator, and the like include a batch addition method, a continuous addition method, a multi-stage addition method, and the like, but the present invention is not limited to such examples. . These addition methods may be used alone or in combination of two or more.

  What is necessary is just to set the reaction conditions in the case of emulsion polymerization suitably according to the composition of a monomer component, the kind of polymerization initiator, etc. The polymerization temperature is preferably 5 to 90 ° C, more preferably 20 to 85 ° C. The polymerization time is preferably about 3 to 8 hours, for example. Further, when the monomer component is polymerized, it is preferable to stir the reaction system.

  Since the weight average molecular weight of the polymer having a ring structure containing a hetero atom in the main chain obtained by polymerizing the monomer component as described above varies depending on the use of the aqueous resin composition of the present invention, From the viewpoint of improving the weather resistance, it is preferably 10,000 or more, more preferably 50,000 or more, and even more preferably 100,000 or more, since it cannot be determined, and is preferably adjusted as appropriate according to the application. . The upper limit of the weight average molecular weight of the polymer having a ring structure containing a hetero atom in the main chain is not particularly limited, but is preferably 1 million or less, more preferably 500,000 or less, from the viewpoint of improving adhesion. More preferably, it is 300,000 or less.

  In addition, in this specification, a weight average molecular weight means the weight average molecular weight (polystyrene conversion) measured using the gel permeation chromatography.

  After preparing the resin emulsion by emulsion polymerization of the monomer component, it is preferable from the viewpoint of stabilizing the resin emulsion that the obtained resin emulsion is neutralized with a neutralizing agent. Examples of the neutralizing agent include tertiary amines such as triethanolamine, dimethylethanolamine, diethylethanolamine and morpholine; aqueous ammonia; sodium hydroxide and the like, but the present invention is limited only to such examples. It is not a thing. These neutralizing agents may be used alone or in combination of two or more.

  The amount of the neutralizing agent is preferably 0.3 to 1.4 equivalents, more preferably 0.5 to 1.2 equivalents per equivalent of the acid groups of the emulsion particles. It is preferable to use it.

  When the monomer component is polymerized by solution polymerization, an aqueous medium is preferably used as a solvent. When the monomer component is solution polymerized using an organic solvent other than water, the resulting reaction mixture may be diluted with water, or the organic solvent may be replaced with water.

  The polymer content in the aqueous resin composition can be easily adjusted by adding an aqueous medium such as water, for example. Since the content of the polymer in the aqueous resin composition varies depending on the use of the aqueous resin composition and the like, it cannot be determined unconditionally. Therefore, it is preferable to appropriately determine the content in accordance with the use. Usually, the content of the polymer in the aqueous resin composition is preferably 1 to 70% by mass, more preferably 3 to 65% by mass, further preferably 10 to 65% by mass, still more preferably 15 to 60% by mass, Especially preferably, it is 15-50 mass%.

  The polymer contained in the aqueous resin composition of the present invention may be either crosslinked or non-crosslinked, but it is preferable to crosslink the polymer from the viewpoint of improving adhesiveness and blocking resistance. Crosslinking of the polymer is carried out after the coating film is formed by applying the aqueous resin composition of the present invention, which improves the adhesion between the formed coating film and the substrate and improves the durability of the coating film. From the viewpoint of improving the property. When the polymer is crosslinked, the polymer itself may be crosslinked, or the polymer may be crosslinked using a crosslinking agent.

  The aqueous resin composition of the present invention preferably contains a crosslinking agent from the viewpoint of improving the adhesion between the formed coating film and the substrate and improving the durability of the coating film.

  Examples of the crosslinking agent include a block polyisocyanate compound, an epoxy group-containing compound, a carbodiimide group-containing compound, an oxazoline group-containing compound, and an aminoplast resin. However, the present invention is not limited to such examples. . These crosslinking agents may be used alone or in combination of two or more.

  The block polyisocyanate compound has a property of crosslinking the aqueous resin composition by heating, a property of improving storage stability at room temperature, and a property of improving adhesiveness. Moreover, the block polyisocyanate compound is excellent in blocking resistance. The block polyisocyanate compound is usually one in which the isocyanate group of the polyisocyanate compound is blocked with a blocking agent. Examples of the blocking agent include ε-caprolactam, phenol, cresol, oxime, alcohol, and the like, but the present invention is not limited to such examples. Among the block polyisocyanate compounds, a non-yellowing polyisocyanate compound having no isocyanate group directly bonded to an aromatic ring is preferable from the viewpoint of preventing yellowing of the adhesive layer.

  The block polyisocyanate compound preferably has water dispersibility. Examples of the block polyisocyanate compound include products manufactured by Nippon Polyurethane Industry Co., Ltd., trade names: Aquanate 100, Aquanate 110, Aquanate 200, Aquanate 210; manufactured by Sumika Bayer Urethane Co., Ltd., trade name: Bihijoule TPLS -2032, SUB-isocyanate L801, bihijoule VPLS-2319, bihijoule 3100, VPLS-2336, VPLS-2150 / 1; manufactured by Mitsui Takeda Chemical Co., Ltd., trade names: Takenate WD-720, Takenate WD-725, Takenate WD- 220; manufactured by Dainichi Seika Kogyo Co., Ltd., trade name: Rezamin D-56, and the like, but the present invention is not limited to such examples.

  Examples of the epoxy group-containing compound include Mitsubishi Chemical Corporation, trade names: jER W2801, jER W2821R70, jER W3435R57, jER W8735R70; ADEKA Corporation, trade name: Adeka Resin EP-4100, etc. The present invention is not limited to such examples.

  Examples of the carbodiimide group-containing compound include Nisshinbo Chemical Co., Ltd., trade names: Carbodilite SV-02, Carbodilite E-01], etc., but the present invention is not limited to such examples.

  Examples of the oxazoline group-containing compound include Nippon Shokubai Co., Ltd., trade names: Epocross K-2000 series, Epocross WS-500, Epocross WS-700, etc., but the present invention is limited to such examples. It is not a thing.

  An aminoplast resin is an addition condensate of a compound having an amino group such as melamine or guanamine with formaldehyde, and is also called an amino resin.

  Examples of aminoplast resins include dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, hexamethylol melamine, fully alkyl methylated melamine, fully alkyl butylated melamine, fully alkyl isobutylated melamine, completely Melamine resins such as alkyl mixed etherified melamine, methylol group methylated melamine, imino group methylated melamine, methylol group mixed etherified melamine, imino group mixed etherified melamine; butylated benzoguanamine, methyl / ethyl mixed alkyl Benzoguanamine, methyl / butyl mixed alkylated benzoguanamine, guanamine resins such as butylated glycoluril, and the like, but the present invention is limited only to such examples. Not to.

  Among aminoplast resins, aqueous aminoplast resins are preferred. Aminoplast resins can be easily obtained commercially as, for example, trade names: Cymel 300, Cymel 303, Cymel 325, Cymel 701, Cymel 1123, Cymel 1170, My Coat 101, etc., manufactured by Mitsui Cytec Co., Ltd. .

  The amount of the cross-linking agent per 100 parts by mass of the polymer varies depending on the type of the cross-linking agent and cannot be determined unconditionally, but is usually preferable from the viewpoint of improving the adhesiveness and durability of the aqueous resin composition. Is 1 part by mass or more, more preferably 3 parts by mass or more. From the viewpoint of improving water resistance and insulation, it is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 30 parts by mass or less. is there. For example, when the polymer has a plurality of hydroxyl groups in one molecule, the amount of the crosslinking agent may be appropriately adjusted according to the number of hydroxyl groups that the polymer has. Moreover, there is no limitation in the addition method of a crosslinking agent, a dispersion method, etc., What is necessary is just to employ | adopt an appropriate method according to the kind of the said crosslinking agent.

  The aqueous resin composition can be used as a room temperature curable type, a heat curable type, an ultraviolet curable type, or an electron beam curable type. It is preferable to cure under the curing conditions suitable for the use of the aqueous resin composition, the kind of the crosslinking agent, and the like.

  In addition, you may make the aqueous resin composition contain the curing catalyst for accelerating the crosslinking reaction of a polymer and a crosslinking agent as needed. When using a block polyisocyanate compound as a crosslinking agent, it is preferable to use, for example, dibutyltin dilaurate, tertiary amine, etc. as a curing catalyst. Moreover, when using an aminoplast resin as a crosslinking agent, it is preferable to use what has acidity or basicity as a curing catalyst. Since the amount of the curing catalyst varies depending on the type and the like and cannot be determined unconditionally, it is preferable to appropriately adjust according to the type of the curing catalyst and the properties required for the aqueous resin composition.

  The aqueous resin composition may contain an additive, a thermoplastic resin, and the like. Examples of the additive include additives generally used in resin compositions that form films and coating films. Specific examples of additives include film forming aids; volatile organic solvents, tackifiers; leveling agents; inorganic fine particles such as colloidal silica and alumina sol; polymethylmethacrylate organic fine particles; antifoaming agents; Inhibitors; Silane coupling agents; Pigments such as titanium white, composite oxide pigments, carbon black, organic pigments, and pigment intermediates; Pigment dispersants; Antioxidants such as phosphorus antioxidants and phenolic antioxidants; Viscosity modifier; UV stabilizer; Metal deactivator; Peroxide decomposer; Flame retardant; Reinforcer; Plasticizer; Lubricant; Rust preventive agent; Fluorescent brightener; Organic UV absorber and inorganic Examples include ultraviolet absorbers; inorganic heat ray absorbers; organic flame retardants and inorganic flame retardants; organic antistatic agents and inorganic antistatic agents; and dehydrating agents such as methyl orthoformate. , Such an example The present invention is not limited to only. Since the amount of the additive varies depending on the type and the like and cannot be determined unconditionally, it is preferable to appropriately adjust depending on the type of the additive, the properties required for the aqueous resin composition, and the like.

  The tackifier may be contained in the aqueous resin composition of the present invention from the viewpoint of improving adhesiveness and durability. Examples of tackifiers include rosin tackifiers, rosin ester tackifiers, terpene tackifiers, terpene phenol tackifiers, saturated hydrocarbon resins, coumarone tackifiers. , Coumarone indene tackifier, styrene resin tackifier, xylene resin tackifier, phenol resin tackifier, petroleum resin tackifier, etc. However, the present invention is not limited to such examples. These tackifiers may be used alone or in combination of two or more.

  Examples of the rosin-based tackifier include those manufactured by Harima Kasei Co., Ltd. and trade name: Harrier Star DS-90, but the present invention is not limited to such examples.

  Examples of the rosin ester tackifier include Arakawa Chemical Industries, Ltd., trade names: Pine Crystal KE-100, Pine Crystal KE-311, and the like, but the present invention is limited to such examples. Is not to be done.

  Examples of the terpene tackifier include Yashara Chemical Co., Ltd., Clearon (registered trademark) M-115, Clearon (registered trademark) P-115, and the like, but the present invention is limited to such examples. Is not to be done.

  Examples of the terpene phenol tackifier include Arakawa Chemical Industries, Ltd., trade name: Tanomaru 803L, and the like, but the present invention is not limited to such examples.

  Examples of the saturated hydrocarbon resin include Arakawa Chemical Industries, Ltd., trade names: Alcon P-90, Alcon P-100, and the like, but the present invention is not limited to such examples. .

  Examples of the styrene resin-based tackifier include Mitsui Chemicals, Inc., product number: FTR-6000, but the present invention is not limited to such examples.

  The amount of the tackifier per 100 parts by mass of the polymer may be appropriately adjusted according to the desired adhesiveness, and is not particularly limited, but is preferably 3 parts by mass from the viewpoint of improving the adhesiveness to the adherend. As mentioned above, More preferably, it is 5 mass parts or more, From a viewpoint of suppressing the fall of adhesive force, Preferably it is 200 mass parts or less, More preferably, it is 150 mass parts or less.

  A thermoplastic resin may be contained in the aqueous resin composition of the present invention from the viewpoint of improving adhesiveness and durability. Examples of the thermoplastic resin include polyester-based resins, modified polyolefin-based resins, EVA, polyvinyl butyral (PVB), silicone resins, vinyl chloride resins, polyurethanes, amino group-containing resins, etc., but the present invention is illustrated as examples. It is not limited to only. These thermoplastic resins may be used alone or in combination of two or more. The thermoplastic resin may be used by dissolving in a monomer component, or may be used by mixing with an aqueous resin composition.

  Examples of polyester resins include Toyobo Co., Ltd., Byron (registered trademark) 103, Byron (registered trademark) 240, Byron (registered trademark) 500, GK110, GK640, and the like; Byronal (registered trademark) MD-1245, Vironal (registered trademark MD-1480 and the like; manufactured by Nippon Synthetic Chemical Industry Co., Ltd., Nichigo Polyester (registered trademark) TP-220, Nichigo Polyester (registered trademark) TP-235, Nichigo Polyester (registered trademark) TP-236 , Nichigo Polyester (registered trademark) TP-290, Nichigo Polyester (registered trademark) WR905, Nichigo Polyester (registered trademark) WR960 and the like, but the present invention is not limited to such examples.

  Examples of the modified olefin-based resin include, for example, Auroren (registered trademark) 100, Aurolen (registered trademark) 200, Aurolen (registered trademark) 350, Aurolen (registered trademark) S-, manufactured by Nippon Paper Chemicals Co., Ltd. 5189, etc .; Sanyo Kasei Kogyo Co., Ltd., trade names: Umex 1001, Umex 1010, Umex 2000, and the like can be mentioned, but the present invention is not limited to such examples.

  Examples of the EVA include, for example, Tosoh Corporation, Mersen (registered trademark) H-6051, Mersen (registered trademark) H-6410, etc .; Sumitomo Chemical Co., Ltd., Sumitate (registered trademark) KA-31, Smitate ( (Registered trademark) KA-42 and the like, but the present invention is not limited to such examples.

  Examples of the polyvinyl butyral (PVB) include Kuraray Co., Ltd., Mowital (registered trademark) series B30H, B45M, and B60H. However, the present invention is not limited to such examples.

  Examples of the silicone resin include Shin-Etsu Chemical Co., Ltd., product numbers: KE-103 and KE-1013, but the present invention is not limited to such examples.

  Examples of the vinyl chloride resin include Sekisui Chemical Co., Ltd., trade name: Sekisui PVCTS, but the present invention is not limited to such examples.

  Examples of the polyurethane include DIC Bayer Polymer Co., Ltd., trade name: Desmopan DP6580A, but the present invention is not limited to such examples.

  Examples of the amino group-containing resin include those manufactured by Nippon Shokubai Co., Ltd., trade names: Poliment NK-350, Poliment NK-380, etc., but the present invention is not limited to such examples.

  The amount of the thermoplastic resin per 100 parts by mass of the polymer may be appropriately adjusted according to the desired adhesive strength, durability, and the like, and is not particularly limited, but from the viewpoint of improving the adhesive strength and durability to the adherend. The amount is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and preferably 200 parts by mass or less, more preferably 150 parts by mass or less, from the viewpoint of suppressing a decrease in adhesive strength and durability.

  The nonvolatile content in the aqueous resin composition of the present invention is preferably 10% by mass or more, more preferably 20% by mass or more from the viewpoint of improving productivity, and preferably 65% by mass from the viewpoint of improving handleability. Hereinafter, it is 60 mass% or less more preferably.

In the present specification, the non-volatile content in the aqueous resin composition of the present invention is that 1 g of the aqueous resin composition is weighed and dried for 1 hour at a temperature of 110 ° C. with a hot air dryer, and the resulting residue is defined as non-volatile content. ,formula:
[Nonvolatile content in water-based resin composition (mass%)]
= ([Residue mass] ÷ [aqueous resin composition 1 g]) × 100
Means the value obtained based on

  The adhesive resin composition of the present invention contains the aqueous resin composition. The adhesive resin composition of this invention may be comprised only with the said aqueous resin composition, for example, other components, such as an additive and a solvent, may contain.

  The base material having the coating film of the present invention can be produced by applying the aqueous resin composition to the base material. The coating film of the base material having this coating film can also be used as a resin layer, an adhesive layer or the like. The formed coating film may be cross-linked if necessary. As a method of crosslinking the coating film, for example, a method of crosslinking the coating film by irradiating an electron beam or the like, a crosslinking agent is contained in the aqueous resin composition, and the crosslinking agent is included in the aqueous resin composition. Examples of such a method include a method for crosslinking a polymer, but the present invention is not limited to such a method.

  The substrate can be classified into an inorganic substrate and a resin substrate. These base materials may be used alone or in combination of two or more. Among these substrates, a resin-based substrate is preferable from the viewpoint of reducing weight and cost.

  Suitable inorganic base materials include, for example, glass base materials; ceramic base materials; inorganic base materials such as calcium silicate plates, asbestos slate plates, and cement slate plates; metal bases such as aluminum plates, copper plates, stainless steel plates, and plated steel plates. Materials: Wood based substrates such as plywood, MDF (medium density fiberboard), particle board, and the like can be mentioned, but the present invention is not limited to such examples.

  Suitable resin base materials include, for example, (meth) acrylic resins such as polymethyl methacrylate; polystyrene, polyvinyl toluene, polystyrene, styrene-methyl methacrylate copolymer, styrene-acrylonitrile copolymer, acrylonitrile-butadiene- Styrene resin such as styrene graft copolymer and poly (p-methylstyrene); polycarbonate; polyarylate; polyethersulfone; polyolefin resin such as polyethylene, polypropylene and ethylene-propylene; cyclic olefin resin such as norbornene resin; Halogen-containing resins such as vinyl chloride resin and chlorinated vinyl resin; polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycyclohexanedimethanol teref Polyester resins such as rate; polyamides such as nylon 6, nylon 66, nylon 610; cellulose resins such as cellulose triacetate, cellulose acetate propionate, and cellulose acetate butyrate; polyacetal resins; polyvinyl fluoride, polyvinylidene fluoride, Fluororesin such as polychlorotrifluoroethylene, polyethylenetetrafluoroethylene, polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer; polyphenylene oxide; polyphenylene sulfide; poly Ether ether ketone; polyether nitrile; polysulfone; polyether sulfone; polyoxybenzylene; Riamidoimido; Although substrate made of a resin such as a silicone resin, the present invention is not limited those exemplified only. Among the resins, (meth) acrylic resin, polyolefin resin, cyclic olefin resin, polyester resin, polyamide, cellulose resin, and fluororesin are preferable from the viewpoint of improving weather resistance and reducing cost. More preferred are system resins and fluororesins. Although the thickness of the resin base material is not particularly limited, it is usually preferably about 10 to 800 μm.

  The substrate having the coating film of the present invention can be produced by applying the aqueous resin composition to the substrate by a method such as gravure coating, roll coating, bar coating, reverse coating or the like. At this time, the substrate may be subjected to a surface treatment for improving adhesiveness such as corona treatment, flame treatment, and plasma treatment, if necessary. For example, when a base material made of a fluororesin is used as the base material, it is preferable to perform plasma treatment or the like on the base material. Although the thickness of the coating after drying varies depending on the use of the substrate having the coating, etc., it cannot generally be determined, but is usually preferably 0.03 to 200 μm, more preferably 0.1 to 20 μm. It is.

  The base material having the coating film of the present invention can be suitably used for an optical film or the like when, for example, a film-shaped resin base material is used as a building material or a base material.

  The adhesive resin composition of the present invention can also be used when a plurality of substrates are bonded together. In this case, the adhesive resin composition of the present invention has a thickness after drying of 0.1 to 20 μm by a method such as gravure coating, roll coating, bar coating, and reverse coating on a substrate. It can manufacture by forming the contact bonding layer which consists of an adhesive resin composition, after apply | coating an adhesive agent and bonding another base material on the base material by methods, such as dry lamination. At this time, the substrate may be subjected to a surface treatment for improving adhesiveness such as corona treatment, flame treatment, and plasma treatment, if necessary. For example, when a base material made of a fluororesin is used as the base material, it is preferable to perform plasma treatment or the like on the base material. As a base material, the thing similar to the base material used for the base material which has the said coating film can be illustrated.

  EXAMPLES Next, although this invention is demonstrated further in detail based on an Example, this invention is not limited only to this Example.

Preparation Example 1
In accordance with the description in JP-A-10-226669, 1,4-diazabicyclo [2.2.2] octane is used as a catalyst, and methyl α-hydroxymethyl acrylate and allyl alcohol are reacted to form α-allyl. Methyl oxymethyl acrylate (MeAMA) was prepared.

Preparation Example 2
Preparation of cyclohexyl α-allyloxymethyl acrylate (CHAMA) by transesterification of methyl α-allyloxymethyl acrylate and cyclohexanol using 1-chloro-3-methoxytetramethyldistanoxane as a catalyst did. The catalyst 1-chloro-3-methoxytetramethyldistanoxane was prepared according to the method described in Rokuro Okawara, Masanori Wada, Journal of Organometallic Chemistry, 1963, Vol. 1, pages 81-88.

Preparation Example 3
In Preparation Example 2, benzyl α-allyloxymethyl acrylate (BzAMA) was prepared by performing the same operation as in Preparation Example 2, except that benzyl alcohol was used instead of cyclohexanol.

Preparation Example 4
In Preparation Example 2, α-allyloxymethyl acrylate tetrahydrofurfuryl (THFAMA) was prepared by performing the same operation as in Preparation Example 2, except that tetrahydrofurfuryl alcohol was used instead of cyclohexanol.

Example 1
In a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer, and a reflux condenser, 133 g of deionized water was charged. To the dropping funnel, 16.0 g of 25% aqueous solution of emulsifier [Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon BC-20], 24.0 g of deionized water, 0.5 g of hydroxyethyl methacrylate, 2.0 g of acrylic acid, A first stage pre-emulsion consisting of 22.0 g of isobornyl methacrylate and 75.5 g of methyl α-hydroxymethyl acrylate was prepared, and 7.0 g corresponding to 5% of the pre-emulsion was added into the flask, and gently nitrogen was added. The temperature was raised to 75 ° C. with stirring while blowing gas. After the temperature increase, 1.0 g of 5% aqueous potassium persulfate solution was added to initiate polymerization. At this time, the temperature in the reaction system was raised to 80 ° C. over 20 minutes. This is the initial polymerization reaction.

  After completion of the initial polymerization reaction, while maintaining the temperature in the reaction system at 80 ° C., the remainder of the pre-emulsion for the first stage and 8.0 g of 2.5% potassium persulfate aqueous solution were uniformly added to the flask over 180 minutes. It was dripped in. After completion of the dropping, the dropping funnel was washed with 3.0 g of deionized water, and the washing solution was added to the flask and kept at 80 ° C. for 60 minutes. The reaction solution was cooled to room temperature and 1.25 g of 25% aqueous ammonia was added to the flask, and then the contents of the flask were filtered through a 100-mesh wire mesh to obtain a resin emulsion containing a polymer and an aqueous medium. The obtained resin emulsion was used as an aqueous resin composition (1).

Example 2
In Example 1, an aqueous resin composition (2) was obtained in the same manner as in Example 1 except that the composition of the monomer component was changed as shown in Table 1.

Example 3
In Example 1, the aqueous resin composition (3) was obtained like Example 1 except having changed the composition of the monomer component as shown in Table 1.

Example 4
In Example 1, the aqueous resin composition (4) was obtained like Example 1 except having changed the composition of the monomer component as shown in Table 1.

Example 5
In Example 1, the aqueous resin composition (5) was obtained like Example 1 except having changed the composition of the monomer component as shown in Table 1.

Example 6
In Example 1, the aqueous resin composition (6) was obtained like Example 1 except having changed the composition of the monomer component as shown in Table 1.

Reference example 1
A resin composition (1) was obtained in the same manner as in Example 1, except that the composition of the monomer component in Example 1 was changed as shown in Table 1.

Reference example 2
A resin composition (2) was obtained in the same manner as in Example 1, except that the composition of the monomer component in Example 1 was changed as shown in Table 1.

Reference example 3
A resin composition (3) was obtained in the same manner as in Example 1, except that the composition of the monomer component in Example 1 was changed as shown in Table 1.

In addition, the symbol of each component shown in Table 1 means the following.
MeAMA: α-methyl allyloxymethyl acrylate CHAMA: cyclohexyl α-allyloxymethyl acrylate BzAMA: benzyl α-allyloxymethyl acrylate THFAMA: α-allyloxymethyl acrylate tetrahydrofurfuryl 2EHA: 2-ethylhexyl acrylate HEMA : 2-hydroxyethyl methacrylate IBMA: isobornyl methacrylate MMA: methyl methacrylate AA: acrylic acid MAA: methacrylic acid

Examples 7-14 and Comparative Examples 1-5
For 100 parts by mass of the aqueous resin compositions obtained in Examples 1 to 6 and 100 parts by mass of the resin compositions obtained in Reference Examples 1 to 3, 5 parts by mass of the crosslinking agent shown in Table 2 and 2, 2 as a film forming aid. , 4-Trimethyl-1,3-pentanediol monoisobutyrate [manufactured by Chisso Corporation, product number: CS-12] was mixed with 10 parts by mass to obtain an adhesive resin composition.

  The adhesion and blocking resistance were examined by the following method using the adhesive resin composition obtained above. The results are also shown in Table 2.

〔Adhesiveness〕
The adhesive resin composition was applied onto a polyethylene terephthalate (hereinafter referred to as PET) film (hereinafter referred to as PET) having a thickness of 188 μm cut to a length of 60 mm and a width of 140 mm using a bar coater. Then, the film was dried for 1 minute in a dryer at 80 ° C., and cured for 7 days in a dryer at 40 ° C., thereby forming an adhesive layer having a thickness of 1 μm after drying, and a PET film having an adhesive layer was obtained.

An EVA (ethylene-vinyl acetate resin) sheet (made by Mitsui Chemicals Fabro Co., Ltd., trade name: RC02B) cut to a length of 60 mm and a width of 60 mm is stacked on a glass plate having a length of 60 mm and a width of 60 mm. In addition, the PET film having the adhesive layer obtained above was stacked so that the adhesive layer was in contact with the EVA sheet, and then pre-heated and pressure-bonded on a hot plate at 65 ° C. for 1 minute using a hand roller, A laminate was obtained. The obtained laminate was heated in a vacuum oven at 150 ° C. for 11 minutes while applying a pressure of 5 N / cm ² , and then the laminate was taken out of the oven and cooled to room temperature.

  The laminated PET film was cut into a 10 mm width to obtain six 10 mm wide test specimens. Of the six test specimens, the peel strength of four specimens excluding two at both ends was evaluated based on the following method. As a result, the minimum 180 ° peel strength was 76 N / cm, the maximum 180 ° peel strength was 89 N / cm, and the average 180 ° peel strength was 82 N / cm. Moreover, when the peeling situation was investigated based on the following method, interfacial peeling between the EVA sheet and the adhesive layer and interfacial peeling between the PET film and the adhesive layer were mixed in any of the four specimens. It was confirmed that

(1) Peel strength For the four test specimens, grip the glass / EVA sheet of the non-adhered part of the specimen with the upper grip of a tensile tester (manufactured by Shimadzu Corporation, Autograph) in an atmosphere at 23 ° C. Then, the PET film on the unbonded portion of the test specimen was held with the lower gripping tool, pulled at a crosshead speed of 100 mm / min, and the 180 ° peel strength was measured.

(2) Peeling condition After examining the peeling strength in (1), the peeling condition of the peeling surface was examined with an infrared spectrometer.

[Blocking resistance]
The adhesive resin composition was applied using a bar coater on a 188 μm thick PET film (trade name: Lumirror H10, manufactured by Toray Industries, Inc.) cut to a length of 50 mm and a width of 150 mm. And dried for 1 minute to form an adhesive layer having a thickness of 1 μm after drying. A PET film of the same size was overlaid on the adhesive layer, placed in a dryer at 40 ° C., held for 24 hours while applying a load of 4 kg, then removed from the dryer and cooled to room temperature. Thereafter, the superimposed PET film was peeled off, and the blocking resistance was evaluated based on the following evaluation criteria.

(Evaluation criteria)
○: The adhesive layer is not transferred to the peeled PET film.
X: The adhesive layer is transferred to the peeled PET film.

  In Table 2, in the item of “peeling situation”, “EVA-adhesive delamination” means interfacial delamination between the EVA sheet and the adhesive layer, and “PET-adhesive delamination” It means interfacial debonding with the adhesive layer.

  From the results shown in Table 2, it can be seen that the adhesive resin compositions obtained in each Example are excellent in adhesiveness and in blocking resistance.

Example 15
In a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer, and a reflux condenser, 133 g of deionized water was charged. One stage consisting of 16.0 g of 25% aqueous solution of emulsifier [Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon BC-20] in a dropping funnel, 24.0 g of deionized water, and 100 g of methyl α-allyloxymethylacrylate. A pre-emulsion of eyes was prepared, 7.0 g corresponding to 5% of the pre-emulsion was added to the flask, and the temperature was raised to 75 ° C. with stirring while gently blowing nitrogen gas. After the temperature increase, 1.0 g of 5% aqueous potassium persulfate solution was added to initiate polymerization. At this time, the temperature in the reaction system was raised to 80 ° C. over 20 minutes. This is the initial polymerization reaction.

  After completion of the initial polymerization reaction, while maintaining the temperature in the reaction system at 80 ° C., the remainder of the pre-emulsion for the first stage and 8.0 g of 2.5% potassium persulfate aqueous solution were uniformly added to the flask over 180 minutes. It was dripped in. After completion of the dropping, the dropping funnel was washed with 3.0 g of deionized water, and the washing solution was added to the flask and kept at 80 ° C. for 60 minutes. The reaction solution was cooled to room temperature and 1.25 g of 25% aqueous ammonia was added to the flask, and then the contents of the flask were filtered through a 100-mesh wire mesh to obtain a resin emulsion containing a polymer and an aqueous medium. The obtained resin emulsion was used as an aqueous resin composition.

  As the physical properties of the aqueous resin composition obtained above, the nonvolatile content, the polymerization rate, the glass transition temperature, the minimum film-forming temperature and the water resistance were examined based on the following methods. As a result, the non-volatile content of the aqueous resin composition obtained above was 36.4% by mass, the polymerization rate was 99.7%, the glass transition temperature was 60 ° C., and the minimum film-forming temperature was 50 ° C. Met. From the above results, it can be seen that the aqueous resin composition obtained in Example 15 can be formed even at a temperature lower than the glass transition temperature.

  Further, the water resistance and scratch resistance of the formed coating film were examined based on the following methods. As a result, since the whitening of the formed coating film was not recognized, it was confirmed that the coating film was excellent in water resistance despite being a coating film formed with the aqueous resin composition. It was. In addition, the steel wool test was conducted to examine the scratch resistance of the formed coating film, and the surface was not scratched. Therefore, although the coating film was not high in the glass transition temperature of the polymer. (Glass transition temperature: 60 ° C.), it can be seen that the film is excellent in scratch resistance.

[Non-volatile content]
1 g of the aqueous resin composition was weighed and dried with a hot air dryer at a temperature of 110 ° C. for 1 hour.
[Non-volatile content (% by mass)]
= [[Mass of residue] ÷ [Aqueous resin composition lg]] × 100
Based on the above, the nonvolatile content in the aqueous resin composition was determined.

(Polymerization rate)
First, the formula:
[Theoretical nonvolatile content (% by mass)]
= [[Theoretical product amount (g)] ÷ [Total charge (g)]] × 100
(In the formula, the theoretically generated resin amount is the mass of the polymer produced when all the monomer components react, the mass of the non-volatile content of the emulsifier, the mass and sum of the initiator, and the total charged amount is within the reaction system. Indicates the mass of the existing polymerization solution)
Based on the above, the theoretical non-volatile content in the aqueous resin composition was determined.

  The theoretically generated resin amount is the amount of polymer that is theoretically calculated from the charged amounts of the monomer, emulsifier and initiator used. Further, the total charge amount is an amount obtained by summing up the masses of all used raw materials.

Then the formula:
[Polymerization rate (%)]
= [[Nonvolatile content (mass%)] ÷ [Theoretical nonvolatile content (mass%)]] × 100
Based on the above, the polymerization rate was determined.

〔Glass-transition temperature〕
Using a differential scanning calorimeter [Bruker AXS Co., Ltd., product number: DSC3100S], the amount of the sample (aqueous resin composition) was adjusted to 10 to 20 mg, and nitrogen gas was flowed at a flow rate of 50 mL / min. The sample was introduced into a differential scanning calorimeter, the sample was heated from 0 ° C. to 130 ° C. at a heating rate of 10 ° C./min in a nitrogen gas atmosphere, and the differential scanning calorific value was measured.

  More specifically, first, a sample (aqueous resin composition) was placed on an aluminum pan, and the residue obtained by drying with a hot air dryer at a temperature of 110 ° C. for 1 hour was weighed. An aluminum pan on which this residue is placed and a reference aluminum pan (without a sample) are placed at a predetermined position of a differential scanning calorimeter, and the differential scanning is performed at a predetermined flow rate (50 mL / min) of nitrogen gas. After adjusting to be introduced into the calorimeter, the first temperature increase from 0 ° C. to 130 ° C. was started.

  After the temperature of the sample reached 130 ° C., the sample was once cooled, and the second temperature increase was performed again under the same conditions as the first temperature increase. Based on the baseline shift of the differential scanning calorimetry (DSC) curve obtained at this time, the glass transition temperature of the sample (polymer contained in the aqueous resin composition) was determined.

[Minimum film forming temperature (MFT)]
A water-based resin composition is applied on a glass plate placed on a thermal gradient tester with a 0.2 mm thick applicator, and the temperature of the formed coating film is increased with a thermal gradient tester. The temperature at which this occurred was defined as the minimum film-forming temperature (MFT).

〔water resistant〕
An aqueous resin composition was applied to a slate plate (manufactured by Nozawa Co., Ltd., trade name: Nozawa Flexible Sheet, JIS A5403 standard product) using a 6 mil applicator and dried at room temperature for 1 day. The film was visually observed after 7 days.

[Abrasion resistance]
A steel wool test was conducted to examine the scratch resistance of the coating film. More specifically, an aqueous resin composition is applied to a slate plate [manufactured by Nozawa Co., Ltd., trade name: Nozawa Flexible Sheet, JIS A5403 standard product] using a 6 mil applicator and dried at room temperature for 1 day. Thus, a coating film was formed. Using the Gakushin type abrasion resistance tester (manufactured by Suga Test Instruments Co., Ltd.) and applying a load of 100 g / cm ² to # 0000 steel wool (Japan Steel Wool Co., Ltd.), the steel wool is applied to the surface of the coating film. The surface was rubbed by 10 reciprocations, and the surface of the coating film was visually observed for scratches.

Reference example 4
A resin composition (4) was obtained in the same manner as in Example 15 except that the monomer component in Example 15 was changed to 70.0 g of methyl methacrylate, 28.0 g of butyl acrylate, and 2.0 g of acrylic acid. As the physical properties of the obtained resin composition (4), the nonvolatile content, polymerization rate, glass transition temperature, minimum film-forming temperature and water resistance were examined in the same manner as in Example 15. As a result, the nonvolatile content of the resin composition (4) was 36.4% by mass, the polymerization rate was 99.7%, and the glass transition temperature was 60 ° C. However, an attempt was made to measure the minimum film-forming temperature, but no film could be formed up to a temperature of 60 ° C. From the above results, it can be seen that the resin composition (4) obtained in Reference Example 4 cannot be formed at a temperature lower than the glass transition temperature. Further, when the scratch resistance was examined using the resin composition (4), it was confirmed that the surface of the coating film was scratched.

The aqueous resin composition and adhesive resin composition of the present invention are useful for adhesives, pressure-sensitive adhesives, paints, building material topcoats, building material backcoats, building material sealers, in-mold materials, optical films, and the like.

Claims (5)

  A monomer containing at least one diene structure-containing monomer selected from the group consisting of a 1,5-diene structure-containing monomer containing a heteroatom and a 1,6-diene structure-containing monomer containing a heteroatom An aqueous resin composition comprising: a polymer having a ring structure containing a heteroatom obtained by cyclopolymerizing a monomer component in a main chain; and an aqueous medium. The polymer is of formula (I):
(Wherein R ¹ is a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, R ² is a methylene group, R ³ is a direct bond or a methylene group, R ⁴ is a hydrogen atom, an alkyl having 1 to 4 carbon atoms) Group, phenyl group, carboxyl group, ester group or cyano group, R ⁵ is a direct bond or methylene group, X and Y are each independently a methylene group optionally having an alkyl group of 1 to 4 carbon atoms, imino A group, a carbonyl group, an oxygen atom or a sulfur atom, Z represents a direct bond, a methylene group which may have an alkyl group having 1 to 4 carbon atoms, an imino group, a carbonyl group, an oxygen atom or a sulfur atom; At least one group of Y and Z is an oxygen atom, a sulfur atom or an imino group which are not adjacent to each other)
The aqueous resin composition of Claim 1 which has a ring structure containing unit represented by these.   Furthermore, the aqueous resin composition of Claim 1 or 2 containing the at least 1 sort (s) of crosslinking agent chosen from an oxazoline group containing compound, a carbodiimide group containing compound, an aminoplast resin, an epoxy group containing compound, and a block polyisocyanate compound.   The adhesive resin composition containing the aqueous resin composition in any one of Claims 1-3.   A base material comprising a coating film obtained by applying the aqueous resin composition according to claim 1 to a base material.