JP2017014382A - Aqueous emulsion composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous emulsion composition excellent in water adhesive resistance and boiling adhesive resistance, having practical pot life and capable of exhibiting sufficient boiling resistance without applying just after mixing.SOLUTION: There is provided an aqueous emulsion composition consisting of an ethylenically unsaturated monomer (B), an aqueous emulsion obtained by copolymerizing a monomer (C) represented by the following formula (I) and (II) and a polyvalence aldehyde compound (E) in presence of a polyvinyl alcohol resin (A). (I), where meanings of symbols are omitted. (II), where meanings of symbols are omitted.SELECTED DRAWING: None

Description

  The present invention relates to an aqueous emulsion composition having excellent water-resistant adhesion and boiling-resistant adhesion and having a practical pot life.

  Conventional adhesives used for woodworking, paperwork, fiber processing, etc., where high adhesive strength, water resistance, etc. are required, thermosetting resins such as melamine resin and urea resin, or N-methylol A vinyl acetate resin emulsion obtained by copolymerizing a crosslinkable monomer such as acrylamide has been used. However, all of these resins emit formaldehyde. Although formaldehyde was known to be harmful, the use of materials that emit formaldehyde above a certain level was prohibited or restricted by the amendment of the Building Standards Act. There is a tendency to avoid the use of an agent and a member manufactured using the agent.

  As a means corresponding to this, acetoacetylated polyvinyl alcohol obtained by introducing acetoacetyl groups into polyvinyl alcohol (hereinafter abbreviated as PVA) is used as a protective colloid, and an acetoacetyl group-containing monomer and vinyl acetate are emulsion-copolymerized. Further, a method for realizing water resistance, adhesion strength enhancement, etc. by cross-linking of acetoacetyl groups has been studied (Patent Document 1). On the other hand, there is a problem that the self-crosslinking reaction between acetoacetyl groups proceeds during storage of the adhesive, resulting in thickening and solidification. Although improvement studies with additives and the like have been conducted, no effective method has been found yet.

  Moreover, although the method of using polyvalent isocyanate compounds, such as diphenylmethane diisocyanate, is also examined as a crosslinking agent, it had the problem illustrated below. (1) Isocyanate compound has a significant increase in viscosity after blending, so pot life is short. (2) Since it is deactivated by water, boiling resistance is not exhibited unless it is immediately after mixing. (3) Reacts with water. (4) The applicator (spreader roll in many cases for woodworking) is not cleanable. Although the use of blocked polyisocyanate has been proposed as an improvement method (Patent Document 2), the application range is limited because the heating of the adhesive layer is necessary for performance development. In addition, when a diphenyl diisocyanate (hereinafter abbreviated as MDI) type curing agent that is widely used is used because it is fast curing and inexpensive, the adhesive layer turns brown. Therefore, it is difficult to adapt to a light-colored laminated material that has been bleached because it impairs the appearance, and improvements are required.

JP 2000-282004 A JP 2007-246728 A

  An object of the present invention is to provide an aqueous emulsion composition that is excellent in water- and water-resistant adhesion, has a practical pot life, and can exhibit sufficient boiling resistance without being applied immediately after mixing. is there.

  Therefore, as a result of intensive studies, the present inventors have represented an ethylenically unsaturated monomer (B) and the following formula (I) or (II) in the presence of the polyvinyl alcohol resin (A). It was found that an aqueous emulsion composition comprising an aqueous emulsion (D) obtained by copolymerizing a monomer (C) and a polyhydric aldehyde compound (E) can solve the above problems. The invention has been completed.

（式中、Ｒ¹は水素原子、炭素数１〜８の直鎖状のアルキル基又は−ＣＨ₂−ＣＯＯＭであり、ここでＭは水素原子、メチル基、アルカリ金属又はアンモニウム基であり、Ｒ²及びＲ³は同一又は異なって、炭素数１〜８のアルキル基又は炭素数２〜８のアルキルカルボニル基であり、Ｒ⁴は水素原子又は−ＣＯＯＭであり、ここでＭは水素原子、メチル基、アルカリ金属又はアンモニウム基であり、Ｘは−（ＣＨ₂）_n−、−ＣＯ−ＮＨ−（ＣＨ₂）_n−、−ＮＨ−ＣＯ−（ＣＨ₂）_n−、−ＣＯ−（ＣＨ₂）_n−、−ＣＯ−Ｏ−（ＣＨ₂）_n−、−Ｏ−ＣＯ−（ＣＨ₂）_n−、−ＮＲ⁵−ＣＯ−（ＣＨ₂）_n−、又は−ＣＯ−ＮＲ⁵−（ＣＨ₂）_n−であり、ここでＲ⁵は水素原子又は炭素数１〜４のアルキル基であり、ｎは０〜８の整数である。）

（式中、Ｒ¹ _、Ｒ⁴及びＸは、上記と同一意味を有し、Ｒ⁶は−（ＣＨ₂−ＣＨ₂）_m−であり、ｍは１〜３の整数である。）

(In the formula, R ¹ is a hydrogen atom, a linear alkyl group having 1 to 8 carbon atoms or —CH ₂ —COOM, where M is a hydrogen atom, a methyl group, an alkali metal or an ammonium group; ² and R ³ are the same or different and are an alkyl group having 1 to 8 carbon atoms or an alkylcarbonyl group having 2 to 8 carbon atoms, R ⁴ is a hydrogen atom or —COOM, where M is a hydrogen atom, methyl X is — (CH ₂ ) _n —, —CO—NH— (CH ₂ ) _n —, —NH—CO— (CH ₂ ) _n —, —CO— (CH ₂ ) _N —, —CO—O— (CH ₂ ) _n —, —O—CO— (CH ₂ ) _n —, —NR ⁵ —CO— (CH ₂ ) _n —, or —CO—NR ⁵ — (CH ₂ ) _n- , wherein R ⁵ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n is an integer of 0 to 8. is there.)

(Wherein R ¹ _, R ⁴ and X have the same meaning as above, R ⁶ is — (CH ₂ —CH ₂ ) _m —, and m is an integer of 1 to 3).

  INDUSTRIAL APPLICABILITY The present invention can provide an aqueous emulsion composition that is excellent in water- and water-resistant adhesion and has a sufficiently long pot life. Moreover, this invention can provide the aqueous | water-based emulsion composition which is excellent in the coloring resistance of the film | membrane obtained, and can express sufficient boiling resistance performance, without apply | coating immediately after mixing. Furthermore, this invention can provide the aqueous emulsion composition which is excellent also in safety from the point which does not diffuse formaldehyde.

Hereinafter, the present invention will be described in detail.
The aqueous emulsion composition of the present invention comprises an ethylenically unsaturated monomer (B) and a monomer (C) represented by the following formula (I) or (II) in the presence of the polyvinyl alcohol resin (A). And an aqueous emulsion (D) obtained by copolymerization with a polyvalent aldehyde compound (E). In this specification, (meth) acryl is a general term for acrylic and methacrylic, and the same applies to similar expressions.

（式中、Ｒ¹は水素原子、炭素数１〜８の直鎖状のアルキル基又は−ＣＨ₂−ＣＯＯＭであり、ここでＭは水素原子、メチル基、アルカリ金属又はアンモニウム基であり、Ｒ²及びＲ³は同一又は異なって、炭素数１〜８のアルキル基又は炭素数２〜８のアルキルカルボニル基であり、Ｒ⁴は水素原子又は−ＣＯＯＭであり、ここでＭは水素原子、メチル基、アルカリ金属又はアンモニウム基であり、Ｘは−（ＣＨ₂）_n−、−ＣＯ−ＮＨ−（ＣＨ₂）_n−、−ＮＨ−ＣＯ−（ＣＨ₂）_n−、−ＣＯ−（ＣＨ₂）_n−、−ＣＯ−Ｏ−（ＣＨ₂）_n−、−Ｏ−ＣＯ−（ＣＨ₂）_n−、−ＮＲ⁵−ＣＯ−（ＣＨ₂）_n−、又は−ＣＯ−ＮＲ⁵−（ＣＨ₂）_n−であり、ここでＲ⁵は水素原子又は炭素数１〜４のアルキル基であり、ｎは０〜８の整数である。）

（式中、Ｒ¹ _、Ｒ⁴及びＸは、上記と同一意味を有し、Ｒ⁶は−（ＣＨ₂−ＣＨ₂）_m−であり、ｍは１〜３の整数である。）

(In the formula, R ¹ is a hydrogen atom, a linear alkyl group having 1 to 8 carbon atoms or —CH ₂ —COOM, where M is a hydrogen atom, a methyl group, an alkali metal or an ammonium group; ² and R ³ are the same or different and are an alkyl group having 1 to 8 carbon atoms or an alkylcarbonyl group having 2 to 8 carbon atoms, R ⁴ is a hydrogen atom or —COOM, where M is a hydrogen atom, methyl X is — (CH ₂ ) _n —, —CO—NH— (CH ₂ ) _n —, —NH—CO— (CH ₂ ) _n —, —CO— (CH ₂ ) _N —, —CO—O— (CH ₂ ) _n —, —O—CO— (CH ₂ ) _n —, —NR ⁵ —CO— (CH ₂ ) _n —, or —CO—NR ⁵ — (CH ₂ ) _n- , wherein R ⁵ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n is an integer of 0 to 8. is there.)

(Wherein R ¹ _, R ⁴ and X have the same meaning as above, R ⁶ is — (CH ₂ —CH ₂ ) _m —, and m is an integer of 1 to 3).

  The aqueous emulsion of the present invention can be obtained by copolymerizing the ethylenically unsaturated monomer (B) and the monomer (C) using the polyvinyl alcohol resin (A) as a protective colloid.

The symbols of the formulas (I) and (II) will be described below. For the same symbol (eg, R ¹ ) used in two or more different formulas (eg, Formula (I) and Formula (II)) of the present invention, the content of the symbol is as long as it does not exceed a prescribed range. In the formula, they may be the same or different.

Examples of the linear alkyl group having 1 to 8 carbon atoms in R ¹ include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, and an n-heptyl group. , N-octyl group, and a methyl group is preferable. Examples of the alkali metal represented by M in R ¹ and R ⁴ include lithium, sodium, potassium, rubidium, cesium, and the like. Lithium, sodium, or potassium is preferable, and sodium or potassium is more preferable.

Examples of the alkyl group having 1 to 8 carbon atoms in R ² and R ³ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group N-pentyl group, isopentyl group, sec-pentyl group, neopentyl group, tert-pentyl group, 1-ethylpropyl group, n-hexyl group, isohexyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl Group, 3,3-dimethylbutyl group, 2-ethylbutyl group, n-heptyl group, n-octyl group, and the like. Among these, a group having 1 to 6 carbon atoms is preferable. Examples of the alkylcarbonyl group in R ² and R ³ include an acetyl group, a propanoyl group, a butanoyl group, a pentanoyl group, a hexanoyl group, a heptanoyl group, an octanoyl group, and the like. An acetyl group, a propanoyl group, a butanoyl group, a pentanoyl group Or a hexanoyl group is preferable.

X represents — (CH ₂ ) _n —, —CO—NH— (CH ₂ ) _n —, —NH—CO— (CH ₂ ) _n —, —CO— (CH ₂ ) _n —, —CO—O— ( CH ₂ ) _n —, —O—CO— (CH ₂ ) _n —, —NR ⁵ —CO— (CH ₂ ) _n —, or —CO—NR ⁵ — (CH ₂ ) _n —, and — (CH ₂ ) _n- is preferred.

  N in X is preferably 0, 1, 2, 3, 4, 5 or 6.

Examples of the alkyl group having 1 to 4 carbon atoms in R ⁵ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. .

M of R ⁶ is preferably 1, 2, and more preferably 1.

As the linear alkyl group having 1 to 6 carbon atoms in R ^7, R ⁸ and R ^9, among the straight-chain alkyl group having 1 to 8 carbon atoms exemplified in R ^1, 1 to 6 carbon atoms Things.

The monomer (C) represented by the formula (I) or (II) is not particularly limited, and examples thereof include the following:
Acetalized products of (meth) acrolein such as (meth) acrolein dimethyl acetal, (meth) acrolein diethyl acetal, 2-vinyl-1,3-dioxolane, 2-isopropenyl-1,3-dioxolane, 3-methyl-3- Acetalized products of 3-methyl-3-butenal such as butenal dimethyl acetal, 3-methyl-3-butenal diethyl acetal, 2- (2-methyl-2-propenyl) -1,3-dioxolane, 3- Acetalized products of 3-butenal such as butenal dimethyl acetal, 3-butenal diethyl acetal, 2- (2-propenyl) -1,3-dioxolane, 4-pentenal dimethyl acetal, 4-pentenal diethyl acetal, 4-Pen such as 2- (3-butenyl) -1,3-dioxolane Acetalized product of nal, 5-hexenal dimethyl acetal, 5-hexenal diethyl acetal, acetalized product of 5-hexenal such as 2- (5-pentenyl) -1,3-dioxolane, 6-heptenal dimethyl acetal, 6-hept Acetalized products of 6-heptenal such as tenal diethyl acetal, 2- (6-hexenyl) -1,3-dioxolane, 7-octenal dimethyl acetal, 7-octenal diethyl acetal, 2- (1-heptenyl) -1 An acetalized product of an aliphatic aldehyde having an ethylenically unsaturated double bond, such as an acetalized product of 7-octenal such as 1,3-dioxolane, 2- (6-heptenyl) -1,3-dioxolane;

  N- (2,2-dimethoxyethyl) (meth) acrylamide, N- (2,2-diethoxyethyl) (meth) acrylamide, N- (2,2-diisopropoxyethyl) (meth) acrylamide, N- (2,2-dibutoxyethyl) (meth) acrylamide, N- (2,2-di-t-butoxyethyl) (meth) acrylamide, N- (3,3-dimethoxypropyl) (meth) acrylamide, N- (3,3-diethoxypropyl) (meth) acrylamide, N- (3,3-diisopropoxypropyl) (meth) acrylamide, N- (3,3-dibutoxypropyl) (meth) acrylamide, N- ( 3,3-di-t-butoxypropyl) (meth) acrylamide, N- (4,4-dimethoxybutyl) (meth) acrylamide, N- (4,4-di Toxibutyl) (meth) acrylamide, N- (4,4-diisopropoxybutyl) (meth) acrylamide, N- (4,4-dibutoxybutyl) (meth) acrylamide, N- (4,4-di-t -Butoxybutyl) (meth) acrylamide, N-methyl-N- (2,2-dimethoxyethyl) (meth) acrylamide, N-methyl-N- (2,2-diethoxyethyl) (meth) acrylamide, N- Methyl-N- (2,2-diisopropoxyethyl) (meth) acrylamide, N-methyl-N- (2,2-dibutoxyethyl) (meth) acrylamide, N-methyl-N- (2,2- Dialkoxyalkyl (meth) acrylamide compounds such as di-t-butoxyethyl) (meth) acrylamide; 4-{(2,2-dimethoxyethyl) amino -4-oxo-2-butenoic acid, 4-{(2,2-diethoxyethyl) amino} -4-oxo-2-butenoic acid, 4-{(2,2-diisopropoxyethyl) amino}- Butenoic acids having a dialkoxy group such as 4-oxo-2-butenoic acid and 4-{(2,2-dibutoxyethyl) amino} -4-oxo-2-butenoic acid; 5,5-dimethoxy-3- Oxo-1-pentene, 5,5-diethoxy-3-oxo-1-pentene, 5,5-diisopropoxy-3-oxo-1-pentene, 5,5-dibutoxy-3-oxo-1-pentene, etc. Pentenes having the following dialkoxy groups; 4-{(2,2-dimethoxyethyl) amino} -4-oxo-3-methylene-butanoic acid, 4-{(2,2-diethoxyethyl) amino} -4 -Oxo-3-methylene-butanoic acid, 4-{(2,2-diisopropoxyethyl) amino} -4-oxo-3-methylene-butanoic acid, 4-{(2,2-dibutoxyethyl) amino} -4-oxo-3-methylene- Butanoic acids having a dialkoxy group such as butanoic acid; 3- [N- (2,2-dimethoxyethyl) carbamoyl] propenoic acid, 3- [N- (2,2-diethoxyethyl) carbamoyl] propenoic acid, 3 -[N- (2,2-diisopropoxyethyl) carbamoyl] propenoic acid, 3-[(N-2,2-dibutoxyethyl) carbamoyl] propenoic acid, 3- [N- (2,2-di- t-butoxyethyl) carbamoyl] propenoic acid and the like propenoic acid compounds having two alkoxy groups in one molecule; methyl 3- [N- (2,2-dimethoxyethyl) carbamoyl] propenoate, 3- Methyl N- (2,2-diethoxyethyl) carbamoyl] propenoate, methyl 3- [N- (2,2-diisopropoxyethyl) carbamoyl] propenoate, 3- [N- (2,2-dibutoxy) Ethyl) carbamoyl] propenoate methyl, 3- [N- (2,2-di-t-butoxyethyl) carbamoyl] propenoate methyl and the like propenoic acid ester compounds having two alkoxy groups in one molecule; 2 , 2-dimethoxyethyl (meth) acrylate, 2,2-diethoxyethyl (meth) acrylate, 2,2-diisopropoxyethyla (meth) acrylate, 2,2-dibutoxyethyl (meth) acrylate, etc. Acetalized products of alkoxyalkyl (meth) acrylates; or alkyl (meth) acrylamide compounds, Lumpur product, acetalized aliphatic aldehyde having an unsaturated double bond such as an acetal compound of acetalized or butane acids pentenes. As carbon number of the said alkoxy group, 1-6 are preferable and 1-4 are more preferable. As carbon number of the alkyl group of the said alkyl (meth) acrylamide type compound or alkyl (meth) acrylate, 1-6 are preferable, 1-4 are more preferable, and 1-2 are more preferable.

  In the aqueous emulsion of the present invention, one or more of the unsaturated monomers (C) described above can be used.

  The monomer unit represented by the formula (I) or (II) is preferably 0.01 to 10% by mass with respect to the total amount of the ethylenically unsaturated monomer unit, and 0.05 to 5 More preferably, it is mass%. When the monomer unit represented by the formula (I) or (II) is 0.01% by mass or less, water-resistant adhesiveness and boiling resistance are insufficient, and when it is 10% by mass or more, polymerization is difficult. It becomes.

  In the present invention, the ethylenically unsaturated monomer (B) used for copolymerization with the monomer (C) is not particularly limited as long as the effects of the present invention are not impaired. For example, vinyl ester monomers , (Meth) acrylic acid ester monomers, α, β-unsaturated mono- or dicarboxylic acid monomers, diene monomers, olefin monomers, (meth) acrylamide monomers, nitrile monomers Monomers, aromatic vinyl monomers, heterocyclic vinyl monomers, vinyl ether monomers, allyl monomers, polyfunctional acrylate monomers, and the like. These may be used alone or in combination of two or more. Among these, at least one unsaturated monomer selected from the group consisting of vinyl ester monomers and diene monomers is preferable, and vinyl ester monomers are more preferable.

  The vinyl ester monomer is not particularly limited. For example, vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl versatate, vinyl cinnamate, vinyl crotonate, decane. Vinyl acetate, vinyl hexanoate, vinyl octoate, vinyl isononanoate, vinyl trimethyl acetate, vinyl 4-tert-butylbenzene, vinyl 2-ethylhexanoate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl palmitate , Vinyl stearate, vinyl oleate, vinyl benzoate and the like, and vinyl acetate is particularly preferable from an industrial viewpoint. Although it does not specifically limit as a (meth) acrylic-ester type monomer, For example, (meth) acrylic acid methyl, (meth) acrylic acid ethyl, (meth) acrylic acid n-propyl, (meth) acrylic acid i- Propyl, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, (meth) acrylic acid Examples include octadecyl, 2-hydroxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2- (dimethylamino) ethyl (meth) acrylate, and the like. The α, β-unsaturated mono- or dicarboxylic acid-based monomer is not particularly limited, and examples thereof include (meth) acrylic acid, crotonic acid, isocrotonic acid, citraconic acid, itaconic acid, maleic acid, maleic anhydride, and fumaric acid. An acid etc. are mentioned. The diene monomer is not particularly limited, and examples thereof include conjugated dienes such as butadiene, isoprene and chloroprene.

  Although it does not specifically limit as an olefin type monomer, For example, monoolefin compounds, such as ethylene, propylene, 1-butene, and isobutene; Halogens, such as vinyl chloride, vinyl bromide, vinylidene chloride, vinyl fluoride, and vinylidene fluoride And olefinic compounds. Although it does not specifically limit as a (meth) acrylamide type monomer, For example, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, diacetone, for example (Meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N-methylol (meth) acrylamide and the like can be mentioned. The nitrile monomer is not particularly limited, and examples thereof include (meth) acrylonitrile. Although it does not specifically limit as an aromatic vinyl-type monomer, For example, styrene, (alpha) -methylstyrene, p-methylstyrene, chlorostyrene, (alpha) -butoxystyrene, vinyl naphthalene, vinyl biphenyl, 1-ethyl-2-vinyl Examples include benzene. Although it does not specifically limit as a heterocyclic vinyl type monomer, For example, vinylpyrrolidone etc. are mentioned. The vinyl ether monomer is not particularly limited, and examples thereof include methyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, dodecyl vinyl ether, stearyl vinyl ether and the like. Can be mentioned. The allylic monomer is not particularly limited, and examples thereof include allyl acetate, allyl chloride, allyl sulfonate, diallyl phthalate, triallyl cyanurate, and triallyl isocyanurate. Although it does not specifically limit as a polyfunctional acrylate-type monomer, For example, a pentaerythritol triacrylate, a pentaerythritol tetraacrylate, a pentaerythritol hexaacrylate, a trimethylol propane triacrylate etc. are mentioned. Furthermore, as the ethylenically unsaturated monomer, vinyl compounds such as vinyl phosphonic acid, vinyl sulfonic acid and salts thereof can be used. These may be used alone or in combination of two or more.

  The saponification degree of PVA (A) used as a protective colloid in the present invention is usually 70 to 99.9 mol%, preferably 75 to 99.5 mol%. When the degree of saponification is less than 70 mol%, the effect as a protective colloid is poor and a stable aqueous emulsion cannot be obtained. On the other hand, when the degree of saponification exceeds 99.9 mol%, the temperature dependency of the viscosity of the resulting aqueous emulsion increases, and the object of the present invention cannot be achieved. In addition, as long as the PVA has a saponification degree in the above range, those having different saponification degrees may be used in combination. The saponification degree is a value obtained by the method described in JIS K 6726 (1994). As long as the PVA has a saponification degree within the above range, it may be unmodified PVA or modified PVA. The modified PVA is not particularly limited. For example, anion-modified PVA such as sulfonic acid group-modified PVA and carboxylic acid group-modified PVA; cation-modified PVA such as quaternary amine group-modified PVA; amide-modified PVA; acetoacetyl group-modified PVA; diacetone acrylamide modified PVA; ethylene modified PVA and the like. These may be used alone or in combination of two or more. Among these, at least one PVA selected from the group consisting of non-modified PVA, ethylene-modified PVA, and anion-modified PVA such as carboxylic acid group-modified PVA is preferable. The content of the modifying group is not particularly limited, but may be 0.5 to 10 mol%. Moreover, although it does not specifically limit, As modified PVA used as a protective colloid, modified PVA which has an aldehyde group in a side chain may be excluded.

The viscosity average polymerization degree of the PVA (A) (hereinafter sometimes simply referred to as polymerization degree) may be in a range generally used for emulsion polymerization, and is preferably from 300 to 4000. When the degree of polymerization is 300 or more, sufficient stability at the time of emulsion polymerization is obtained, and when the degree of polymerization is 4000 or less, the solution viscosity at the time of emulsion polymerization does not become too high, and stirring and heat removal are easy. This is preferable because it can be performed. The degree of polymerization is a value determined by the method described in JIS K 6726 (1994). Specifically, when the saponification degree is less than 99.5 mol%, the intrinsic viscosity [η] (liter / liter) measured in water at 30 ° C. is used for the saponified PVA until the saponification degree is 99.5 mol% or more. The viscosity average degree of polymerization (P) was determined by the equation using g).
P = ([η] × 10 ⁴ /8.29) ^{(1 / 0.62)}

  The usage-amount of PVA (A) is 2-20 mass% normally with respect to the whole quantity of an ethylenically unsaturated monomer (for example, vinyl acetate), Preferably it is 3-10 mass%. If it is less than 2% by mass, sufficient stability at the time of emulsion polymerization may not be obtained. If it exceeds 20% by mass, the water resistance and boiling water resistance of the film using the resulting aqueous emulsion composition may be reduced, or the viscosity may be reduced. The temperature dependence of may increase.

  The aqueous emulsion (D) of the present invention is produced by a production method having a step of copolymerizing the ethylenically unsaturated monomer (B) and the monomer (C) in the presence of the PVA resin (A). can do. The aqueous emulsion (D) of the present invention can be produced, for example, by commonly performed emulsion polymerization. It is preferable that the usage-amount of a monomer (C) is 0.01-10 mass% with respect to an ethylenically unsaturated monomer (B), and it is more preferable that it is 0.05-5 mass%. . Although the temperature at the time of superposition | polymerization changes with the polymerization catalyst to be used, it is 20-100 degreeC normally, Preferably it is 40-90 degreeC, More preferably, it is 50-90 degreeC. The reaction time is not particularly limited and may be appropriately adjusted according to the blending amount of each component, the reaction temperature, and the like.

  The aqueous emulsion composition of the present invention may contain an alkali metal compound. The alkali metal compound is not particularly limited as long as it contains an alkali metal (sodium, potassium, rubidium, cesium), and may be an alkali metal ion itself or a compound containing an alkali metal.

  The content of alkali metal compound (in terms of alkali metal) can be appropriately selected according to the type of alkali metal compound used, but the content of alkali metal compound (in terms of alkali metal) is the emulsion (solid basis). 100-15000 ppm is preferable with respect to the total weight, 120-12000 ppm is more preferable, and 150-8000 ppm is the most preferable. When the content of the alkali metal compound is lower than 100 ppm, the emulsion polymerization stability of the aqueous emulsion may be lowered, and when it exceeds 15000 ppm, the film made of the aqueous emulsion may be colored, which is not preferable. Note that the content of the alkali metal compound may be a value measured by an ICP emission analyzer.

  Specific examples of the compound containing an alkali metal include weakly basic alkali metal salts (for example, alkali metal carbonates, alkali metal acetates, alkali metal bicarbonates, alkali metal phosphates, alkali metal sulfates, alkalis). Metal halide salts, alkali metal nitrates), strongly basic alkali metal compounds (for example, alkali metal hydroxides, alkali metal alkoxides) and the like. These alkali metal compounds may be used alone or in combination of two or more.

  Examples of weakly basic alkali metal salts include alkali metal carbonates (for example, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate), alkali metal bicarbonates (for example, sodium bicarbonate, potassium bicarbonate, etc.), alkalis Metal phosphates (sodium phosphate, potassium phosphate, etc.), alkali metal carboxylates (sodium acetate, potassium acetate, cesium acetate, etc.), alkali metal sulfates (sodium sulfate, potassium sulfate, cesium sulfate, etc.), alkali metals Examples thereof include halide salts (cesium chloride, cesium iodide, potassium chloride, sodium chloride, etc.) and alkali metal nitrates (sodium nitrate, potassium nitrate, cesium nitrate, etc.). Of these, alkali metal carboxylates, alkali metal carbonates, and alkali metal bicarbonates that can act as salts of weakly acidic strong bases during dissociation are preferably used from the viewpoint that the emulsion is basic, and alkali metal carboxylic acids. A salt is more preferred.

  By using these weakly basic alkali metal compounds to effect pH buffering in the aqueous emulsion polymerization system of the present invention, emulsion polymerization can be stably advanced.

  In the emulsion polymerization, a surfactant, a polymerization initiator, a reducing agent, a buffering agent, a polymerization degree adjusting agent, and the like may be appropriately used as long as the effects of the present invention are not impaired.

  As the surfactant, any of a nonionic surfactant, an anionic surfactant and a cationic surfactant may be used. The nonionic surfactant is not particularly limited. For example, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyalkylene alkyl ether, polyoxyethylene derivative, sorbitan fatty acid ester, Examples include polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester and the like. The anionic surfactant is not particularly limited, and examples thereof include alkyl sulfates, alkylaryl sulfates, alkyl sulfonates, hydroxyalkanol sulfates, sulfosuccinates, alkyl and alkylaryl polyethoxyalkanol sulfates and phosphates, and the like. Is mentioned. Although it does not specifically limit as a cationic surfactant, For example, an alkylamine salt, a quaternary ammonium salt, polyoxyethylene alkylamine etc. are mentioned. It is preferable that the usage-amount of surfactant is 2 mass% or less with respect to the whole quantity of an ethylenically unsaturated monomer (for example, vinyl acetate). When the usage-amount of surfactant exceeds 2 mass%, since water resistance, warm water resistance, and boiling water resistance may fall, it is unpreferable.

  As the polymerization initiator, a catalyst that forms a radical usually used in emulsion polymerization can be used. Specific examples include hydrogen peroxide, potassium persulfate, ammonium persulfate, tertiary butyl hydroperoxide, azobis- (2-amidinopropane) hydride, lauroyl peroxide, 2,2′-azobisisobutyronitrile, Examples thereof include ketone hydroperoxide. These polymerization initiators can be used as a redox catalyst either alone or in an appropriate combination with a reducing agent.

  Reducing agents include amines, ferrous salts (eg, ferrous sulfate, ferrous ammonium sulfate, ferrous pyrophosphate, etc.), sodium thiosulfate, sodium sulfite, sodium hyposulfite, sodium formaldehyde sulfoxylate, tartaric acid And salts thereof, ascorbic acid and salts thereof, erythorbic acid and salts thereof, and the like. The usage-amount of a catalyst and the reducing agent added as needed is 0.001-10 mass% normally with respect to the whole quantity of an ethylenically unsaturated monomer (for example, vinyl acetate). As a method for adding the catalyst and the reducing agent, the whole amount may be added at the beginning of the polymerization, or a part of the catalyst and the reducing agent may be added as the polymerization proceeds.

  Examples of the buffer include acids such as acetic acid, hydrochloric acid and sulfuric acid; bases such as ammonia, amine cargo soda, cargo potassium and calcium hydroxide; or alkali carbonates, phosphates and acetates. Examples of the polymerization degree regulator include mercaptans and alcohols.

  The solid content concentration contained in the aqueous emulsion (D) may be appropriately set according to the use, but is preferably 30 to 60% by mass as the solid content.

  The aqueous emulsion composition of the present invention can be used for paint applications, fiber processing, and the like, as well as adhesive applications such as woodworking and paper processing. The aqueous emulsion obtained by the above method may be used as it is, and if necessary, an antifoaming agent, a pH adjusting agent, a solvent, a pigment, a dye, a preservative, a thickener, a crosslinking agent, a plasticizer, etc. may be added. May be used. In addition, an acid catalyst can be added to cause cross-linking by an acetal bond exchange reaction with the coexisting PVA and improve water resistance. In principle, the acid catalyst is not particularly limited. For example, mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and nitric acid; heteropolyacids such as phosphotungstic acid; paratoluenesulfonic acid, uric acid, barbituric acid, maleic acid, Organic acids such as citraconic acid; isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, diisopropyl bis (Dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2 Diallyloxymethyl-1-butyl) bis (ditridecyl phosphite) titanate, isopropyl tridodecyl benzene sulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene Titanate, diisopropylbis (dioctylpyrophosphate) titanate, tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, tetramethyl titanate, titanium acetylacetonate, titanium tetraacetylacetonate, polytitanium acetyl Acetonate, Titanium octylene glycolate, Titanium lactate an Organic titanium compounds such as nium salt, titanium lactate (titanium lactate), titanium triethanolamate, polyhydroxytitanium stearate; zirconium halides such as zirconium oxychloride, hydroxy zirconium chloride, zirconium tetrachloride, zirconium bromide; zirconium sulfate Zirconium salts of mineral acids such as zirconium nitrate; Zirconium salts of organic acids such as zirconyl acetate and zirconyl formate; Zirconium complex salts such as zirconium carbonate ammonium, zirconium zirconium sulfate, ammonium zirconium acetate, sodium zirconium oxalate, zirconium ammonium citrate, etc. Zirconium compounds; aluminum chloride and hydrates thereof; aluminum nitrate and hydrates thereof; aluminum compounds such as aluminum sulfate; Sulfonic acid type strongly acidic ion exchange resins such as Nmberlist (registered trademark), Amberlite (registered trademark) and Dowex (registered trademark); Sulfonic acid type fluorinated alkylene resins such as sulfonated tetrafluoroethylene resin; Mordenite, zeolite In addition, various conventionally known acids such as inorganic solid acids such as activated clay and acid clay can be used, and these acids may be used alone or in combination of two or more. Among these, sulfuric acid, a titanium lactate compound, an aluminum compound, and a solid acid are particularly preferable.

  The polyvalent aldehyde compound (E) used in the present invention is not particularly limited as long as it has two or more aldehyde groups. For example, it contains two or more aldehyde groups, and all aldehyde groups are masked with protective groups (protection). And polyvalent aldehyde derivative (E-2) in which at least one aldehyde group is masked. These can use a commercial item. These may be used alone or in combination of two or more. For example, the polyvalent aldehyde (E-1) and the polyvalent aldehyde derivative (E-2) may be used in combination, or only two or more types of the polyvalent aldehyde derivative (E-2) may be used in combination. In the present invention, the masked polyvalent aldehyde derivative means a polyvalent aldehyde masked so as to liberate an aldehyde group again in an acidic medium.

  Examples of the masked polyvalent aldehyde derivative (E-2) include adducts of S-, O- and / or N-nucleophiles and polyvalent aldehydes. Although it does not specifically limit as S-nucleophile, For example, bisulfites, such as sodium hydrogensulfite or potassium hydrogensulfite, etc. are mentioned. The O-nucleophile is not particularly limited, but may be a number of linear or branched aliphatic monoalcohols having 1 to 6 carbon atoms, such as ethylene glycol, 1,2-propylene glycol, and 1,3-propylene glycol. And monohydric alcohols. Examples of O-nucleophilic adducts include open chain acetals, cyclic acetals, enol ethers, enol esters, acrylates and mixed acrylate ethers of polyvalent aldehydes. These include aldehyde group-containing compounds which are exclusively enol type for structural reasons, such as oxypyruvate aldehyde (reduction). The reaction products of these enols, which may be further masked with residual aldehyde groups that are not present in the enol form, are likewise suitable derivatives. N-nucleophiles are not particularly limited, and examples thereof include aliphatic monoamines, amides, ureas, and cyclic ureas. The N-nucleophilic adduct is a cleavage reaction product between a polyvalent aldehyde and a nitrogen compound. Examples of these include polyhydric aldehyde oximes, oxime esters, oxime ethers, imines (Schiff base) enamines, aminals, hydrazones, semicarbazones, α, α-diurethanes, enamine urethanes, etc. Is mentioned.

  Moreover, as a polyhydric aldehyde compound (E), the natural logarithm (LogKow) of n-octanol / water partition coefficient is 0.5 or more in the point which lengthens a pot life, maintaining high boiling resistance performance. Those are preferred. The n-octanol / water partition coefficient can be measured by the method described in JIS Z 7260-107 (2000).

  Examples of the polyvalent aldehyde (E-1) include glyoxal, glutaraldehyde, nonanedialdehyde, terephthalaldehyde, cyclohexanedialdehyde, tricyclodecanedialdehyde, norbornanedialdehyde, suberaldehyde, and dialdehyde starch.

  Examples of the polyvalent aldehyde derivative (E-2) masked with at least one aldehyde group include glyoxal bis sodium bisulfite, glutardialdehyde bis sodium bisulfite, malondialdehyde bisdimethyl acetal, glutaraldehyde di Aldehyde bisdimethylacetal, succindialdehyde monodimethylacetal and bisdimethylacetal, succinaldehyde bisdiethylacetal, oximinosuccinaldehyde bisdimethylacetal, maleidialdehyde bisdimethylacetal and bisdiethylacetal, 2,3-hydroxy-1, 4-dioxane 2,5-dimethoxytetrahydrofuran, 2,5-diethoxytetrahydrofuran, and 2,6-dimethoxytetrahydro 2H-pyran and 2,6-diethoxytetrahydro-2H-pyran, 1,1,2,2-tetramethoxyethane, 1,1,2,2-tetraethoxyethane, 1,1,3,3-tetramethoxy Propane, 1,1,3,3-tetraethoxypropane, 1,1,6,6-tetramethoxyhexane, bis-1,3- (2,2-dimethoxy-1-hydroxyethyl) urea (trade name “Hi Link DU "(manufactured by Clariant), bis-1,3- (2,2-dimethoxy-1-hydroxyethyl) -2-imidazolidinone (trade name" Hilink DMU ", Clariant), 1,1 ', 1' '-(1,3,5-triazine-2,4,6-triyltriimino) tris [2,2-dimethoxyethanol] (trade name “Hilink DMM”, manufactured by Clariant), 3 4-dihydroxyethylene urea, glutaric acid dialdehyde-dioxime, phthalic acid dialdehyde-mono- and dioxime, phthalic acid dialdehyde-oxime semicarbazone, isophthalic acid aldoxime, terephthalic acid aldehyde-dihydrazone, and malonic acid dialdehyde, succinic acid Chloromalondi, a polyvalent aldehyde derivative in which part or all of the aldehyde group of the compound exemplified in the above-mentioned polyvalent aldehyde (E-1), such as anil of glutaric acid dialdehyde and glutaric acid dialdehyde, is masked A polyvalent aldehyde in which part or all of the aldehyde group of a compound not exemplified in the above-mentioned polyvalent aldehyde (E-1) such as aldehyde bisdiethylacetal, 2-bromosuccindialdehydebisdimethylacetal, etc. is masked Derivatives for all aldehydes Examples thereof include polyvalent aldehyde derivatives masked with dodo groups.

  Although the usage-amount of a polyhydric aldehyde compound (E) is not specifically limited, 0.05-20 weight part is preferable with respect to 100 weight part of aqueous | water-based emulsion (D), 0.1-15 weight part is more preferable, 0.5-10 weight part is further more preferable.

  In order to improve water resistance, the aqueous emulsion composition of the present invention may contain a hydrazine compound. The hydrazine compound is not particularly limited, and includes hydrazine, hydrazine hydrard, hydrazine, hydrazine hydrard, hydrazine hydrochloric acid, sulfuric acid, nitric acid, sulfurous acid, phosphoric acid, thiocyanic acid, carbonic acid and other inorganic salts and formic acid, oxalic acid, etc. Organic salts, monosubstituted hydrazines such as methyl, ethyl, propyl, butyl, and allyl, and symmetric disubstituted ones such as 1,1-dimethyl, 1,1-diethyl, 4-n-butyl-metal, etc. Furthermore, as dihydrazine, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, maleic acid dihydrazide, diglycolic acid dihydrazide, Tartaric acid dihydrazide Malic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide dimer acid, any of various conventionally known can be used, these compounds may be used alone or alone or in combination. Among these, adipic acid dihydrazide is particularly preferable. The aqueous emulsion composition of the present invention may contain a polyvalent isocyanate compound and an amine compound.

  When the aqueous emulsion composition of the present invention is used as an adhesive, the aqueous emulsion composition is preferably a sachet type containing an aqueous emulsion (D) and a polyvalent aldehyde compound (E) separately.

  The present invention includes embodiments in which the above-described configurations are variously combined within the technical scope of the present invention as long as the effects of the present invention are exhibited.

  EXAMPLES Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples at all, and many variations are within the technical idea of the present invention. This is possible by those with ordinary knowledge. In the examples and comparative examples, “%” and “parts” represent “% by mass” and “parts by mass”, respectively, unless otherwise specified.

  Emulsion polymerization stability of aqueous emulsion, adhesiveness under various conditions of aqueous emulsion composition (normal state, water resistance, boiling resistance), pot life, resistance to boiling adhesiveness after mixing, colorability during heat treatment are as follows Evaluation was performed by the method shown.

(1) Evaluation of emulsion polymerization stability 500 g of the aqueous emulsion obtained in Examples and Comparative Examples was filtered through a 60-mesh wire mesh, and the filtration residue was weighed and evaluated as follows.
○: Filtration residue is 1.0% or less Δ: Filtration residue is greater than 1.0% ×: Polymerization becomes unstable and cannot be filtered due to coarse particles

(2) Test using water and boiling-resistant adhesive beech material The obtained aqueous emulsion composition was applied to 150 g / m ² of European beech material (Lepidoptera) and bonded to a load of 7 kg / m ^2. The time was pressed. After decompression and curing for 7 days at 20 ° C. and 65% RH, British Standard BS EN204 D3 standard (Serial number of conditioning sequence 1, 2, 3) and D4 standard (Serial number of conditioning sequence 4, The tensile shear bond strength (N / mm ² ) was measured according to 5). Each test condition of Serial number of conditioning sequence is shown.
1: Measured as it is after standing at 20 ° C. and 65% RH for 7 days.
2: Immerse in 20 ° C. water for 4 days and measure while wet.
3: After dipping in 20 ° C. water for 4 days, air-dried at 20 ° C. and 65% RH for 7 days and measured.
4: Soaked in boiling water for 6 hours, immersed in 20 ° C. water for 2 hours, and measured while wet.
5: Immersion in boiling water for 6 hours, immersion in 20 ° C. water for 2 hours, air dry at 20 ° C. and 65% RH for 7 days, and measurement.

(3) Pot Life Viscosity (η0) of the aqueous emulsion compositions obtained in Examples and Comparative Examples was measured with a B-type viscometer (40 ° C., 20 rpm). Thereafter, the aqueous emulsion composition was allowed to stand at 40 ° C. for 1 month. After standing, the viscosity (η30) was measured again with a B-type viscometer (40 ° C., 20 rpm). The thickening factor was defined as η30 / η0 and evaluated as follows.
○: Thickening factor is smaller than 2 Δ: Thickening factor is 2.0 or more and 5.0 or less ×: Thickening factor is larger than 5.0

(4) Degradation of boiling resistance after mixing The aqueous emulsion (D) and the polyhydric aldehyde compound (E) were mixed to form an aqueous emulsion composition, and the adhesive strength of the wood applied immediately after application and 2 hours after mixing. Using the ratio of the adhesive strength of the finished wood, the evaluation was as follows. The evaluation of the adhesive strength was carried out under the test conditions of Serial number if conditioning sequence 4 after performing pressing and curing according to the method described in (2) Water resistance and boiling water resistant adhesive strength.
○: (Adhesion strength after 2 hours after mixing / Adhesion strength immediately after mixing) is 1 or more ×: (Adhesion strength after 2 hours after mixing / Adhesion strength immediately after mixing) is 1 or less

(5) Evaluation of coloration resistance of film The aqueous emulsion compositions obtained in Examples and Comparative Examples were cast on a PET film at 20 ° C. and 65% RH, dried for 7 days, and peeled off from the PET film. A 500 μm dry film was obtained. This film was fixed to a stainless steel metal frame (20 cm × 20 cm and 1 cm wide metal frame) with a clip, and when the film was heat-treated at 120 ° C. for 3 hours in a gear oven, the coloration of the film was visually observed as follows. The street was evaluated.
○: Not colored △: Slightly colored ×: Colored brown

Example 1
(Synthesis of Em-1)
In a 1 liter glass polymerization vessel equipped with a reflux condenser, a dropping funnel, a thermometer, and a nitrogen inlet, 300 g of ion exchange water, “PVA-117” (manufactured by Kuraray Co., Ltd., saponification degree 98.5 mol%, average polymerization) 1700) 20.7 g was charged and stirred at 95 ° C. for 2 hours to completely dissolve. Further, 0.2 g of sodium acetate (NaOAc) was added and mixed and dissolved. Next, this PVA aqueous solution was cooled, purged with nitrogen, heated to 60 ° C. while stirring at 200 rpm, and then 4.4 g of 10% aqueous solution of tartaric acid and 3 g of 5% aqueous hydrogen peroxide (total amount of initial charge) After adding 0.15) by mole ratio to the body, 28 g of vinyl acetate and 0.55 g of acrolein dimethyl acetal were charged to initiate polymerization. After 30 minutes from the start of polymerization, the completion of the initial polymerization was confirmed (the remaining amount of vinyl acetate was less than 1%). After adding 0.9 g of a 10% aqueous solution of tartaric acid and 3 g of 5% hydrogen peroxide water, 244 g of vinyl acetate and 4.98 g of acrolein dimethyl acetal were continuously added over 2 hours, and the polymerization temperature was maintained at 80 ° C. Polymerization was completed, and a polyvinyl acetate emulsion having a solid content concentration of 48.4% (2% by mass of acrolein dimethyl acetal based on the total amount of vinyl acetate) was obtained. 5 parts by mass of phenoxyethanol as a plasticizer was added to and mixed with 100 parts by mass (solid content) of the emulsion. When the polymerization stability of the obtained emulsion (Em-1) was evaluated, the filtration residue was 1.0% or less. Table 1 shows the evaluation results of Em-1 material and polymerization stability.

(Em-1 evaluation)
Using 100 parts by mass of the aqueous emulsion Em-1, an aqueous emulsion composition obtained by adding 0.6 parts by mass of nonanedialdehyde as the polyvalent aldehyde compound (E) and 0.2 parts by mass of phosphoric acid to the catalyst, According to the above method, the evaluation of adhesiveness under various conditions, the evaluation of pot life, the evaluation of the degree of resistance to boiling adhesiveness after mixing, and the evaluation of the coloring resistance of the film were performed. The obtained results are shown in Table 2.

(Example 2)
An aqueous emulsion (Em-2) was obtained in the same manner as in Example 1 except that 5% by mass of acrolein diethyl acetal was used instead of acrolein dimethyl acetal. Table 1 shows the evaluation results of Em-2 material and polymerization stability. Using 100 parts by weight of the aqueous emulsion Em-2, an aqueous emulsion composition in which 0.6 parts by weight of nonanedialdehyde as a polyvalent aldehyde compound (E) and 0.2 parts by weight of phosphoric acid are added to the catalyst, According to the above method, the evaluation of adhesiveness under various conditions, the evaluation of pot life, the evaluation of the degree of resistance to boiling adhesiveness after mixing, and the evaluation of the coloring resistance of the film were performed. The obtained results are shown in Table 2.

(Example 3)
An aqueous emulsion (Em-3) was obtained in the same manner as in Example 1 except that 8% by mass of N-2,2-dimethoxyethyl methacrylamide was used instead of acrolein dimethyl acetal. Table 1 shows the evaluation results of the material of Em-3 and the polymerization stability. Using 100 parts by weight of the aqueous emulsion Em-3, an aqueous emulsion composition in which 0.6 parts by weight of nonanedialdehyde as a polyvalent aldehyde compound (E) and 0.2 parts by weight of phosphoric acid are added to the catalyst, According to the above method, the evaluation of adhesiveness under various conditions, the evaluation of pot life, the evaluation of the degree of resistance to boiling adhesiveness after mixing, and the evaluation of the coloring resistance of the film were performed. The obtained results are shown in Table 2.

Example 4
An aqueous emulsion (Em-4) was obtained in the same manner as in Example 1 except that 1% by mass of 2- (2-methyl-2-propenyl) -1,3-dioxolane was used instead of acrolein dimethyl acetal. Table 1 shows the evaluation results of Em-4 material and polymerization stability. Using 100 parts by mass of the aqueous emulsion Em-4, an aqueous emulsion composition obtained by adding 0.6 parts by mass of nonanedialdehyde as the polyvalent aldehyde compound (E) and 0.2 parts by mass of phosphoric acid to the catalyst, According to the above method, the evaluation of adhesiveness under various conditions, the evaluation of pot life, the evaluation of the degree of resistance to boiling adhesiveness after mixing, and the evaluation of the coloring resistance of the film were performed. The obtained results are shown in Table 2.

(Example 5)
An aqueous emulsion (Em-5) was obtained in the same manner as in Example 1 except that 0.05% by mass of 2- (6-heptenyl) -1,3-dioxolane was used instead of acrolein dimethyl acetal. Table 1 shows the evaluation results of Em-5 material and polymerization stability. Using 100 parts by weight of the aqueous emulsion Em-5, 0.6 part by weight of nonanedialdehyde as a polyvalent aldehyde compound (E) and 0.2 parts by weight of phosphoric acid as a catalyst were used. According to the above method, the evaluation of adhesiveness under various conditions, the evaluation of pot life, the evaluation of the degree of resistance to boiling adhesiveness after mixing, and the evaluation of the coloring resistance of the film were performed. The obtained results are shown in Table 2.

(Example 6)
(Synthesis of Em-6)
Ethylene-modified PVA1 (degree of polymerization) prepared according to the method described in Examples of Patent No. 477175 in a 1-liter glass polymerization vessel equipped with a reflux condenser, a dropping funnel, a thermometer, and a nitrogen inlet. (1700, degree of saponification 95 mol%, ethylene modification amount 5 mol%) 19.5 g was charged and stirred at 95 ° C. for 2 hours to completely dissolve. Further, 0.2 g of sodium acetate (NaOAc) was added and mixed and dissolved. Next, this PVA aqueous solution was cooled, purged with nitrogen, heated to 60 ° C. while stirring at 200 rpm, and then 4.4 g of 10% aqueous solution of tartaric acid and 3 g of 5% aqueous hydrogen peroxide (total amount of initial charge) After adding 0.15) by mole ratio to the body, 30 g of vinyl acetate and 0.02 g of 2- (6-heptenyl) -1,3-dioxolane were charged to initiate polymerization. After 30 minutes from the start of polymerization, the completion of the initial polymerization was confirmed (the remaining amount of vinyl acetate was less than 1%). After shot addition of 0.9 g of 10% aqueous solution of tartaric acid and 3 g of 5% aqueous hydrogen peroxide, 272 g of vinyl acetate and 0.14 g of 2- (6-heptenyl) -1,3-dioxolane were continuously added over 2 hours. The polymerization temperature is maintained at 80 ° C. to complete the polymerization, and a polyvinyl acetate emulsion having a solid content concentration of 49.1% (2- (6-heptenyl) -1,3-dioxolane of 0.1% relative to the total amount of vinyl acetate) is obtained. 05% by mass) was obtained. 5 parts by mass of phenoxyethanol as a plasticizer was added to and mixed with 100 parts by mass (solid content) of the emulsion. When the polymerization stability of the obtained emulsion (Em-6) was evaluated, the filtration residue was 1.0% or less. Table 1 shows the evaluation results of Em-6 material and polymerization stability.

(Em-6 evaluation)
Using 100 parts by mass of the aqueous emulsion Em-6, an aqueous emulsion composition in which 0.6 parts by mass of nonanedialdehyde as a polyvalent aldehyde compound (E) and 0.2 parts by mass of phosphoric acid were added to the catalyst, According to the above method, the evaluation of adhesiveness under various conditions, the evaluation of pot life, the evaluation of the degree of resistance to boiling adhesiveness after mixing, and the evaluation of the coloring resistance of the film were performed. The obtained results are shown in Table 2.

(Example 7)
(Synthesis of Em-7)
In a 1 liter glass polymerization vessel equipped with a reflux condenser, a dropping funnel, a thermometer, and a nitrogen inlet, 300 g of ion-exchanged water, ethylene-modified PVA2 (degree of polymerization) prepared according to the method described in the example of Japanese Patent No. 477175 1700, degree of saponification 93 mol%, ethylene modification amount 2 mol%) 20.7 g was charged and stirred at 95 ° C. for 2 hours to completely dissolve. Further, 0.2 g of sodium acetate (NaOAc) was added and mixed and dissolved. Next, this PVA aqueous solution was cooled, purged with nitrogen, heated to 60 ° C. while stirring at 200 rpm, and then 4.4 g of 10% aqueous solution of tartaric acid and 3 g of 5% aqueous hydrogen peroxide (total amount of initial charge) After adding 0.15) by mole ratio to the body, 28 g of vinyl acetate and 0.03 g of 2- (6-heptenyl) -1,3-dioxolane were charged to initiate polymerization. After 30 minutes from the start of polymerization, the completion of the initial polymerization was confirmed (the remaining amount of vinyl acetate was less than 1%). After shot addition of 0.9 g of 10% aqueous solution of tartaric acid and 3 g of 5% aqueous hydrogen peroxide, 249 g of vinyl acetate and 0.25 g of 2- (6-heptenyl) -1,3-dioxolane were continuously added over 2 hours. The polymerization temperature was maintained at 80 ° C. to complete the polymerization, and a polyvinyl acetate emulsion having a solid content concentration of 47.2% (2- (6-heptenyl) -1,3-dioxolane of 0.1% relative to the total amount of vinyl acetate) was obtained. 1% by weight) was obtained. 5 parts by mass of phenoxyethanol as a plasticizer was added to and mixed with 100 parts by mass (solid content) of the emulsion. When the polymerization stability of the obtained emulsion (Em-7) was evaluated, the filtration residue was 1.0% or less. The material of Em-7 and the evaluation results of the polymerization stability are shown in Table 1.

(Em-7 evaluation)
Using 100 parts by mass of the aqueous emulsion Em-7, an aqueous emulsion composition obtained by adding 0.6 parts by mass of nonanedialdehyde as a polyvalent aldehyde compound (E) and 0.2 parts by mass of phosphoric acid to a catalyst, According to the above method, the evaluation of adhesiveness under various conditions, the evaluation of pot life, the evaluation of the degree of resistance to boiling adhesiveness after mixing, and the evaluation of the coloring resistance of the film were performed. The obtained results are shown in Table 2.

(Example 8)
An aqueous emulsion (Em-8) was obtained in the same manner as in Example 1 except that 11% by mass of arylidene diacetate was used instead of acrolein dimethyl acetal. Table 1 shows the evaluation results of Em-8 material and polymerization stability. Using an aqueous emulsion composition in which 0.6 parts by weight of nonanedialdehyde and 0.2 parts by weight of phosphoric acid are added to the catalyst as the polyvalent aldehyde compound (E), the adhesive properties under various conditions are Evaluation, evaluation of pot life, evaluation of boiling resistance deterioration after mixing, and evaluation of coloring resistance of the film were performed. The obtained results are shown in Table 2.

Example 9
(Synthesis of Em-9)
In a 1.5 liter stainless steel autoclave equipped with an irrigation type stirrer, 360 g of ion exchange water, polyvinyl alcohol “PVA-205” (manufactured by Kuraray Co., Ltd., saponification degree 88 mol%, average polymerization degree 500) 24.3 g And 2.9 g of “PVA-217” (manufactured by Kuraray Co., Ltd., saponification degree: 88 mol%, average polymerization degree: 1700) was stirred at 95 ° C. for 2 hours and completely dissolved. Further, 0.04 g of sodium acetate (NaOAc) was added. Next, 350 g of vinyl acetate and 7.29 g of acrolein dimethyl acetal were charged, and the air in the autoclave was sufficiently replaced with ethylene. Subsequently, 19.5 g of a 10% ascorbic acid aqueous solution was charged, and under stirring, the polymerization temperature was increased to 60 ° C., and the ethylene pressure was increased to 5.0 MPa. 100 g of 1% hydrogen peroxide solution was uniformly added over 8 hours, and 117 g of vinyl acetate and 2.44 g of acrolein dimethyl acetal were uniformly added over 6 hours. The ethylene pressure was maintained at 5.0 MPa until the end of the addition of vinyl acetate and acrolein dimethyl acetal. It cooled after completion | finish of catalyst addition, the antifoamer and the pH adjuster were added, and the aqueous emulsion (Em-9) was obtained. When the polymerization stability of the obtained emulsion (Em-9) was evaluated, the filtration residue was 1.0% or less. The material of Em-9 and the evaluation results of the polymerization stability are shown in Table 1.

(Em-9 evaluation)
Using 100 parts by weight of the aqueous emulsion Em-9, an aqueous emulsion composition in which 0.6 parts by weight of nonanedialdehyde as a polyvalent aldehyde compound (E) and 0.2 parts by weight of phosphoric acid are added to the catalyst, According to the above method, the evaluation of adhesiveness under various conditions, the evaluation of pot life, the evaluation of the degree of resistance to boiling adhesiveness after mixing, and the evaluation of the coloring resistance of the film were performed. The obtained results are shown in Table 2.

  Among the above emulsions, (Em-2), (Em-3), (Em-8), and (Em-9), an ICP emission analyzer (manufactured by Nippon Jarrell Ash, model number: IRIS-AP) As a result of measuring the sodium content at 1, the content of sodium atoms contained in each emulsion was 300 ppm relative to the total amount of the emulsion.

(Example 10)
In accordance with the above method, 100 parts by weight of the aqueous emulsion Em-6 was used, using an aqueous emulsion composition in which 8 parts by weight of glyoxal as the polyvalent aldehyde compound (E) and 0.2 parts by weight of phosphoric acid were added to the catalyst. Evaluation of adhesiveness under various conditions, evaluation of pot life, evaluation of boiling resistance deterioration after mixing, and evaluation of coloring resistance of the film were performed. The obtained results are shown in Table 2.

(Example 11)
Using the aqueous emulsion composition in which 3 parts by mass of glutaraldehyde as the polyvalent aldehyde compound (E) and 0.2 parts by mass of phosphoric acid are added to the catalyst are added to 100 parts by mass of the aqueous emulsion Em-6. According to the above, the evaluation of adhesiveness under various conditions, the evaluation of pot life, the evaluation of the degree of deterioration of boiling resistance after mixing, and the evaluation of the coloring resistance of the film were performed. The obtained results are shown in Table 2.

(Example 12)
Using the aqueous emulsion composition in which 10 parts by mass of terephthalic acid dialdehyde as a polyvalent aldehyde compound (E) and 0.2 parts by mass of phosphoric acid as a catalyst are added to 100 parts by mass of the aqueous emulsion Em-6, According to the method, the evaluation of adhesiveness under various conditions, the evaluation of pot life, the evaluation of the resistance to boiling adhesiveness after mixing, and the evaluation of the coloring resistance of the film were performed. The obtained results are shown in Table 2.

(Comparative Example 1)
Using an aqueous emulsion composition obtained by adding 0.2 parts by mass of phosphoric acid as a catalyst to the polyvalent aldehyde compound (E) to the aqueous emulsion Em-1, according to the above method, evaluation of adhesiveness under various conditions, pot Evaluation of life, evaluation of the degree of deterioration in boiling resistance after mixing, and evaluation of the color resistance of the film were performed. The obtained results are shown in Table 2.

(Comparative Example 2)
An aqueous emulsion (Em-10) was obtained in the same manner as in Example 1 except that acrolein dimethyl acetal was not used. Table 1 shows the evaluation results of Em-10 material and polymerization stability. According to the above-mentioned method, various conditions were used using the aqueous emulsion composition in which 3 parts by mass of nonanedialdehyde as a polyvalent aldehyde compound (E) and 0.2 parts by mass of phosphoric acid were added to the catalyst. The evaluation of the adhesiveness below, the evaluation of pot life, the evaluation of the degree of deterioration in boiling adhesiveness after mixing, and the evaluation of the coloring resistance of the film were performed. The obtained results are shown in Table 2.

(Comparative Example 3)
In accordance with the contents described in Example 2 of JP-B-7-13223, an emulsion composition (36% vinyl acetate emulsion (Aika Avon A-340K) 100 parts by mass, heavy calcium carbonate (Shiraishi calcium, Whiten WA) ) 20 parts by mass, 20 parts by mass of methylenebis (4-phenylisocyanate) (manufactured by Nippon Polyurethane, Polymeric MDI), and using the resulting emulsion composition, the adhesive properties under various conditions were Evaluation, evaluation of pot life, evaluation of boiling resistance deterioration after mixing, and evaluation of coloring resistance of the film were performed. The obtained results are shown in Table 2.

  The aqueous emulsion composition of the present invention can be used for adhesives for woodworking and paper processing, paints, fiber processing and the like.

Claims (7)

Obtained by copolymerizing an ethylenically unsaturated monomer (B) and a monomer (C) represented by the following formula (I) or (II) in the presence of the polyvinyl alcohol resin (A). An aqueous emulsion composition comprising an aqueous emulsion (D) and a polyvalent aldehyde compound (E).

(In the formula, R ¹ is a hydrogen atom, a linear alkyl group having 1 to 8 carbon atoms or —CH ₂ —COOM, where M is a hydrogen atom, a methyl group, an alkali metal or an ammonium group; ² and R ³ are the same or different and are an alkyl group having 1 to 8 carbon atoms or an alkylcarbonyl group having 2 to 8 carbon atoms, R ⁴ is a hydrogen atom or —COOM, where M is a hydrogen atom, methyl X is — (CH ₂ ) _n —, —CO—NH— (CH ₂ ) _n —, —NH—CO— (CH ₂ ) _n —, —CO— (CH ₂ ) _N —, —CO—O— (CH ₂ ) _n —, —O—CO— (CH ₂ ) _n —, —NR ⁵ —CO— (CH ₂ ) _n —, or —CO—NR ⁵ — (CH ₂ ) _n- , wherein R ⁵ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n is an integer of 0 to 8. is there.)

(Wherein R ¹ _, R ⁴ and X have the same meaning as above, R ⁶ is — (CH ₂ —CH ₂ ) _m —, and m is an integer of 1 to 3).   The aqueous emulsion composition according to claim 1, wherein the monomer (C) is a monomer represented by the formula (II). The aqueous emulsion composition according to claim 2, wherein in formula (II), X is — (CH ₂ ) _n —.   The aqueous solution according to any one of claims 1 to 3, wherein the ethylenically unsaturated monomer (B) is at least one selected from the group consisting of vinyl ester monomers and diene monomers. Emulsion composition.   The aqueous emulsion composition according to any one of claims 1 to 4, wherein the amount of the monomer (C) used is 0.01 to 10% by mass relative to the ethylenically unsaturated monomer (B). object.   The aqueous emulsion composition according to any one of claims 1 to 5, comprising 0.05 to 20 parts by weight of the polyvalent aldehyde compound (E) with respect to 100 parts by weight of the aqueous emulsion (D).   The aqueous emulsion composition according to any one of claims 1 to 6, wherein a natural logarithm (Log Kow) of an octanol / water partition coefficient of the polyvalent aldehyde compound (E) is 0.5 or more.