JPH11116821A - Aqueous emulsion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aqueous emulsion, capable of providing a coated membrane excellent in water resistance, and excellent in a pot life by using a specific polymer as a dispersoid and a specific vinyl alcoholic polymer as a dispersing agent. SOLUTION: This aqueous emulsion is obtained by using (A) a polymer comprising an unsaturated monomer unit which is an ethylenically unsaturated monomer and/or a dienic monomer as a dispersoid and (B) a vinyl alcoholic polymer containing 0.01-30 mol.% unit having an amino group bound to a heterocycle in the molecule as a dispersing agent. The unit, preferably the unit of formula I [R<1> to R<5> are each H or a <=8C hydrocarbon; A is a bifunctional hydrocarbon; S is a sulfur atom; X is a monovalent group having an amino group bound to a heterocycle, preferably a group of formula II (Z is S, O, NH or CH2 ).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an aqueous emulsion. More specifically, the present invention relates to an aqueous emulsion having excellent water-resistant adhesive strength and suitable for woodworking adhesives, plywood adhesives, paints, textile processing agents, and paper processing agents.

[0002]

2. Description of the Related Art Conventionally, aqueous polymer emulsions have been widely used in many applications such as adhesives for wood, paper, plastics, etc., paints, fiber processing agents, and paper processing agents.
However, in recent years, with increasing demand for durability of adhesive products and the like, improvement of the water resistance of the aqueous emulsion has been strongly desired. Under such circumstances, many attempts have been made to introduce a crosslinkable group into the aqueous polymer emulsion,
The durability of the adhesive is also improving dramatically. For example, recently, a method of introducing an acetoacetyl group into an aqueous polymer emulsion has been studied, and a remarkable improvement in water resistance has been reported, but the pot life is poor because the acetoacetyl group itself is extremely reactive. In particular, there are severe restrictions when a third component is added to form a composition. Also, from before, carboxyl groups were introduced into the aqueous emulsion,
Many methods for adding a polyfunctional crosslinking agent that reacts with a carboxyl group to the aqueous emulsion have been studied. However, also in this case, it is difficult to balance water resistance and pot life.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide an aqueous emulsion having excellent water resistance of a film and a good pot life under such circumstances.

[0004]

The present inventors have made intensive studies to develop an aqueous emulsion having the above-mentioned properties, and as a result, have found that one kind selected from ethylenically unsaturated monomers and diene-based monomers is obtained. Alternatively, a polymer composed of two or more kinds of unsaturated monomer units is used as a dispersant, and a vinyl alcohol polymer containing 0.01 to 30 mol% of a unit containing an amino group bonded to a heterocyclic ring is used as a dispersant. The present invention has found an aqueous emulsion.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. As a representative example of such an aqueous emulsion,
(A) In an aqueous medium, in the presence of a vinyl alcohol-based polymer containing an amino group bonded to a heterocycle, one or more selected from ethylenically unsaturated monomers and diene-based monomers. An aqueous emulsion obtained by emulsion polymerization of an unsaturated monomer (hereinafter abbreviated as aqueous emulsion a); and (b) one or two selected from an ethylenically unsaturated monomer and a diene monomer. Aqueous emulsion obtained by adding a vinyl alcohol-based polymer having an amino group bonded to a heterocyclic ring to an aqueous emulsion containing a polymer composed of at least one kind of unsaturated monomer units as a dispersoid (hereinafter referred to as an aqueous emulsion) b).

The vinyl alcohol polymer containing an amino group bonded to a heterocycle (hereinafter abbreviated as amino group-containing PVA) used in the present invention will be specifically described. The amino group-containing PVA is not particularly limited as long as it is a vinyl alcohol polymer containing an amino group bonded to a heterocycle. This amino group-containing PVA can be obtained by various methods. Specific examples are shown below. (1) An ethylenically unsaturated monomer having a primary amino group or a secondary amino group bonded to a heterocyclic ring, or a functional group capable of forming a primary amino group or a secondary amino group bonded to a heterocyclic ring by hydrolysis or the like A method comprising copolymerizing an ethylenically unsaturated monomer having the formula (I) and vinyl acetate, followed by saponification. (2) A mercaptan having a primary amino group or a secondary amino group bonded to a heterocyclic ring in a side chain epoxy group of a polymer comprising a monomer having an epoxy group such as allyl glucidyl ether and vinyl acetate, and NaOH or the like. And then saponifying after an addition reaction using as a catalyst. (3) A method in which a compound having a functional group capable of reacting with a hydroxyl group of polyvinyl alcohol in a molecule and having a primary or secondary amino group bonded to a heterocyclic ring is reacted with a vinyl alcohol-based polymer. (4) A method of polymerizing an ethylenically unsaturated monomer having a primary amino group or a secondary amino group bonded to a heterocyclic ring in the presence of a vinyl alcohol polymer having a mercapto group. In this method, a polyvinyl alcohol-based block polymer is obtained.

[0007] The amino group-containing PVA used in the present invention is:
A unit containing an amino group bonded to a heterocyclic ring in an amount of 0.01 to
It is a vinyl alcohol polymer containing 30 mol%.
A more preferable range of the content of the unit is 0.5 to 25.
Mol%. When the content of the unit is less than 0.01 mol%, the effect of introduction is not sufficiently exhibited, and when it exceeds 30 mol%, the storage stability of the amino group-containing PVA solution decreases (for example, gelation). The distribution of the units in the amino group-containing PVA is not particularly limited. As the unit containing an amino group bonded to the heterocyclic ring, a unit represented by the following formula 3 is preferable.

[0008]

Embedded image

Here, R ¹ , R ² , R ³ , R ⁴ and R
⁵ represents a hydrogen atom or a hydrocarbon group having 8 or less carbon atoms, A represents a divalent hydrocarbon group, S represents a sulfur atom, and X represents a monovalent monovalent containing an amino group bonded to a heterocyclic ring. Represents a group.

R ¹ , R ² , R ³ ,
R ⁴ and R ⁵ are a hydrogen atom or a hydrocarbon group which may have a substituent having 8 or less carbon atoms. It is preferable that R ¹ is a hydrogen atom, R ² is a hydrogen atom or a methyl group, and R ³ , R ⁴ and R ⁵ are a hydrogen atom or a hydrocarbon having 8 or less carbon atoms, preferably 6 or less carbon atoms. Note that R ³ and R ⁴ (or R ⁵ ) may form a ring together.

A in the unit represented by Formula 3 is a nitrogen atom,
It is a divalent hydrocarbon group which may contain an oxygen atom or a sulfur atom. For _{example, - (CH 2 CH 2)} n - (n =
1-10, preferably _{n = 1~8), - CH 2} OCH 2 -,
_{-OCH 2 -, - CONH-φ} -OCH 2 -, - CONH
CH ₂ —, —CONHCH ₂ OCH ₂ —, —CONHCH ₂
OCH ₂ CH ₂ —, —CONHCH ₂ OCH ₂ CH ₂ CH
_2- , -CONHCH ₂ OCH ₂ CH ₂ CH ₂ CH _2- , -C
ONHCH ₂ —φ (CH ₃ ) ₂ —CH ₂ — and the like.
Here, φ means a phenylene group.

X in the unit represented by Formula 3 contains an amino group (including a primary amino group, a secondary amino group, and a tertiary amino group and salts thereof and a quaternary ammonium salt) bonded to a heterocyclic ring. Is a monovalent group. As the monovalent group containing an amino group bonded to a heterocyclic ring, a group represented by the following formula 4 is preferable.

[0013]

Embedded image

Here, Z represents S, O, NH or CH ₂ . Specific examples of the heterocyclic ring include, for example, mono-hetero five-membered ring compounds such as furan, pyrrole and thiophene; di-hetero five-membered ring compounds such as oxazole, imidazole, thiazole, isoxazole, pyrazole and isothiazole; triazole, oxadiazole and thiadiazole And hetero- and tetra-hetero five-membered ring compounds such as tetrazole and tetrazole; hetero-six-membered ring compounds such as pyran, pyridine, oxazine and pyridazine; and condensates thereof with benzene rings and the like. The amino group bonded to the heterocyclic ring in the present invention does not form a heterocyclic ring but is bonded to the heterocyclic ring from outside the heterocyclic ring.

The amino group-containing PVA of the present invention contains a vinyl alcohol unit or a vinyl alcohol unit and a vinyl ester unit, excluding a unit containing an amino group bonded to a heterocyclic ring. Examples of the vinyl ester unit include vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl trifluoroacetate, and vinyl 2-ethylhexanoate.

Further, within a range not to impair the gist of the present invention,
A monomer unit other than these may be contained. For example, olefins such as ethylene, propylene, 1-butene, and isobutene; unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, (phthalic anhydride), maleic anhydride, and itaconic acid, and salts thereof Or mono- or dialkyl esters having 1 to 18 carbon atoms; acrylamide, N-alkylacrylamide having 1 to 18 carbon atoms, N, N-dimethylacrylamide,
Acrylamides such as 2-acrylamidopropanesulfonic acid or a salt thereof, acrylamidopropyldimethylamine or an acid salt thereof or a quaternary salt thereof; methacrylamide, N-alkylmethacrylamide having 1 to 18 carbon atoms, N, N-dimethylmethacrylamide , 2-
Methacrylamidopropanesulfonic acid or a salt thereof,
Methacrylamides such as methacrylamidopropyldimethylamine or an acid salt or a quaternary salt thereof; N
N-vinylamides such as vinylpyrrolidone, N-vinylformamide and N-vinylacetamide; vinyl cyanides such as acrylonitrile and methacrylonitrile; alkyl vinyl ethers having 1 to 18 carbon atoms, hydroxyalkyl vinyl ethers and alkoxy alkyl vinyl ethers Vinyl ethers such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride and vinyl bromide; vinyl silanes such as trimethoxy vinyl silane; allyl acetate, allyl chloride, allyl alcohol, dimethyl allyl alcohol Is mentioned.

The degree of polymerization of the amino group-containing PVA is not particularly limited, but is preferably 100 or more, more preferably 200 to 8000. The saponification degree of the amino group-containing PVA is not particularly limited, but is preferably 50 mol% or more, and 80 to 9 mol%.
9.9 mol% is more preferred.

The amino group-containing PVA of the present invention can be obtained by a method comprising reacting a copolymer of a vinyl ester monomer and a vinyl monomer having an epoxy group with a thiol having an amino group bonded to a heterocycle, followed by hydrolysis. Obtainable.

Examples of the vinyl monomer having an epoxy group include allyl glycidyl ether, methallyl glycidyl ether, 1,2-epoxy-5-hexene, 1,2-epoxy-7-octene, and 1,2-epoxy-9-decene. , 8-hydroxy-6,7-epoxy-1-octene, 8-acetoxy-6,7-epoxy-1-octene, N- (2,3-epoxy) propylacrylamide, N- (2,3-epoxy) Propyl methacrylamide, 4-acrylamidophenyl glycidyl ether,
3-acrylamidophenyl glycidyl ether, 4-
Methacrylamide phenyl glycidyl ether, 3-methacrylamide phenyl glycidyl ether, N-glycidoxymethyl acrylamide, N-glycidoxymethyl methacrylamide, N-glycidoxyethyl acrylamide, N-glycidoxyethyl methacrylamide, N
-Glycidoxypropylacrylamide, N-glycidoxypropylmethacrylamide, N-glycidoxybutylacrylamide, N-glycidoxybutylmethacrylamide, 4-acrylamidomethyl-2,5-dimethyl-phenylglycidyl ether, 4- Methacrylamidomethyl-2,5-dimethyl-phenylglycidyl ether, acrylamidopropyldimethyl (2,3-epoxy) propylammonium chloride, methacrylamidopropyldimethyl (2,3-epoxy) propylammonium chloride, glycidyl methacrylate and the like. .

Examples of the thiol having an amino group bonded to a heterocyclic ring include 2-amino-5-mercapto-1,3,4
-Thiadiazole, 2-amino-5-mercapto-1,
3,4-oxydiazole, 2-amino-5-mercapto-1,3,4-triazole, 2-amino-5-mercapto-1,3,4-methylenediazole, 2-mercapto-5-amino- 1,3,4-thiadiazole, 5-
Amino-3-mercapto-1,2,4-triazole,
3-Amino-5-mercapto-1,2,4-triazole, 3-mercapto-4-amino-1,2,4-triazole and 5-mercapto-4-amino-1,2,4-triazole. . Further, esters such as these acetates and benzoates can also be used.

The reaction between the thiol group or the thioester group and the epoxy group is carried out without a solvent or in a solvent that dissolves or swells the compound having the thiol group or the thioester group and the compound having the epoxy group. Examples of such a solvent include alcohols such as methanol, ethanol, n-propyl alcohol and n-butyl alcohol; aromatics such as benzene, toluene and xylene; ethers such as tetrahydrofuran, dioxane and diethyl ether; and n-hexane. And the like. These may be used alone or as a mixture. The reaction conditions vary depending on the structure of the epoxy group and the structure of the thiol or thioester. When a solvent is used, the polymer concentration is 5 to 90%, and the concentration of the thiol group or thioester group / the concentration of the epoxy group is 1.0 to 5%. .
0 (molar ratio), the reaction temperature is 0 to 250 ° C, and the reaction time is 0.
01 to 20 hours. Here, in the reaction with thiol, basic compounds such as tertiary amines (eg, triethylamine, pyridine, etc.), phosphines (eg, tributylphosphine, triphenylphosphine, etc.), sodium hydroxide, tetraethylammonium hydroxide, sodium methylate, etc. It is effective as a reaction catalyst. In the reaction with a thioester, a quaternary ammonium salt such as tributylammonium chloride and tributylammonium bromide is effective as a reaction catalyst. In order to prevent thiol oxidation, the reaction system may be degassed or replaced with nitrogen, or an antioxidant may be added.

The hydrolysis subsequent to the reaction between the thiol group or thioester group and the epoxy group can be effected by a saponification reaction using a basic catalyst or an acid catalyst which is usually used in saponification of polyvinyl ester. That is, using a basic catalyst such as sodium hydroxide, potassium hydroxide or sodium methylate or an acidic catalyst such as p-toluenesulfonic acid, the reaction is carried out using an alcohol or glycol such as methanol, ethanol, propanol, butanol or ethylene glycol as a solvent. Is performed. In this case, a solvent such as tetrahydrofuran, dioxane, dimethyl sulfoxide, diethylene glycol dimethyl ether, toluene, acetone, or water is appropriately mixed and used in order to improve the solubility of the vinyl ester polymer and the catalyst. The conditions of the saponification reaction are appropriately adjusted depending on the structure of the vinyl ester polymer to be used and the desired degree of saponification of the amino group-containing PVA, and usually, the catalyst concentration / vinyl ester unit concentration (molar ratio) is 0.001 to 0.001. 1.2, reaction temperature 20-180
C. and a reaction time in the range of 0.1 to 20 hours.

Next, the aqueous emulsion a will be specifically described. Aqueous emulsion a contains amino group-containing PV
An aqueous emulsion obtained by emulsion polymerization of one or more unsaturated monomers selected from ethylenically unsaturated monomers and diene monomers in the presence of A. Examples of unsaturated monomers capable of emulsion polymerization in the presence of amino group-containing PVA include vinyl ester unsaturated monomers such as vinyl acetate, (meth) acrylic acid, and (meth) acrylic acid.
Acrylics such as methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylonitrile, (meth) acrylamide, 2-hydroxyethyl (meth) acrylate Unsaturated monomer, vinyl chloride, vinylidene chloride,
Examples include halogen-containing unsaturated monomers such as vinyl bromide, styrene monomers, olefin monomers such as ethylene and propylene, and diene monomers such as butadiene, isoprene and chloroprene. The aqueous emulsion a of the present invention can be obtained by emulsion polymerization of one or more of these unsaturated monomers in the presence of an amino group-containing PVA.

In the aqueous emulsion a, the ratio of the (co) polymer comprising the above-mentioned unsaturated monomer unit as the dispersoid and the amino group-containing PVA as the dispersant can be adjusted according to each situation. it can. From the viewpoint of storage stability and mechanical stability of the aqueous emulsion, the amount of the amino group-containing PVA per 100 parts by weight of the dispersoid is 0.5 to 300.
Part by weight is preferable, and 1 to 200 parts by weight is more preferable.
If the amount of the amino group-containing PVA is less than 0.5 parts by weight, it may not be possible to obtain a practical high solid content emulsion excellent in mechanical stability, which is a characteristic of the polyvinyl alcohol protective colloid system. . On the other hand, if the amount of the amino group-containing PVA is too large, problems such as a decrease in the storage stability of the emulsion may occur.

The aqueous emulsion a of the present invention may be used in an amount within a range not to impair the purpose, in the form of various PVA, water-soluble polymers such as water-soluble cellulose derivatives, anionic, cationic, nonionic or amphoteric low molecular surfactants. An agent may be contained. From the viewpoints of dispersion stability, handleability, etc., the total concentration of all the polymers in the aqueous emulsion a is about 20 to 7
It is preferably 0% by weight, more preferably 30 to 60% by weight.

The method for producing the aqueous emulsion a is not particularly limited. Preferably, the aqueous emulsion a is subjected to emulsion polymerization using one or more of the above unsaturated monomers in the presence of an amino group-containing PVA. Manufactured. The proportion of the unsaturated monomer and the amino group-containing PVA used in the emulsion polymerization is such that the proportion of the dispersoid (a polymer obtained by polymerization of the unsaturated monomer) and the amino group-containing PVA is in the above-mentioned preferred range. It is desirable to set as follows. Emulsion polymerization is carried out in the same manner as in a normal emulsion polymerization reaction, in the presence of an amino group-containing PVA in an aqueous medium, in the presence of one or two unsaturated monomers.
It is carried out by polymerizing the seed or more using a radical polymerization initiator. As a polymerization initiator at that time,
Hydrogen peroxide water, benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, azobisisobutyronitrile, persulfate (potassium, sodium or ammonium salt), t-butyl peracetate Tert-butyl benzoate, water-soluble azo initiators (V-50, etc.). Further, a reducing agent such as sodium sulfite, triethanolamine, Rongalit, L-ascorbic acid, tartaric acid and the like can be used in combination with these polymerization initiators.

The polymerization method for producing the aqueous emulsion a is not particularly limited. For example, a method in which the amino group-containing PVA, the above-mentioned unsaturated monomer and water are charged together and polymerized; In water containing PVA, a part of the unsaturated monomer was charged to start polymerization,
Then, a method of sequentially adding the remaining unsaturated monomer to the polymerization system to carry out polymerization; amino group-containing PVA, unsaturated monomer and water are mixed in advance, and a part thereof is charged to start polymerization, A method of sequentially adding the remainder to the polymerization system and polymerizing; adding two or more unsaturated monomers having different monomer compositions in water containing amino group-containing PVA in two or more stages and sequentially adding them to the polymerization system. And multi-stage copolymerization.

The aqueous emulsion a of the present invention is stable even when left for a long period of time, does not cause sedimentation, aggregation, or coagulation of the components contained in the emulsion, and has some external mechanical action (for example, stirring). , Rocking, etc.), the stable dispersion state is not destroyed, and good adhesive performance can be maintained for a long period of time.

Next, the aqueous emulsion b will be specifically described. The aqueous emulsion b is prepared by adding an amino group-containing PVA to an aqueous emulsion containing a polymer of one or more unsaturated monomer units selected from ethylenically unsaturated monomers and diene monomers as a dispersoid. To obtain an aqueous emulsion. This aqueous emulsion b contains an aqueous dispersion containing a polymer composed of one or more unsaturated monomer units selected from ethylenically unsaturated monomers and diene monomers prepared in advance. It can be obtained by directly mixing the amino group-containing PVA directly with the emulsion or by mixing an aqueous solution of the amino group-containing PVA. As an aqueous emulsion having a polymer composed of one or more unsaturated monomer units selected from ethylenically unsaturated monomers and diene monomers as a dispersoid, an aqueous emulsion used for the preparation of aqueous emulsion a Unsaturated monomers similar to those described above, for example, vinyl ester unsaturated monomers such as vinyl acetate, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate (Meth) acrylic acid alkyl esters such as 2-ethylhexyl (meth) acrylate, acrylic unsaturated monomers such as (meth) acrylonitrile, (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, vinyl chloride , Vinylidene chloride, halogen-containing unsaturated monomers such as vinyl bromide, styrene monomers, olefins such as ethylene and propylene Monomer, butadiene, isoprene, one or more diene monomers chloroprene, various PVA, water-soluble polymers such as water-soluble cellulose derivatives, anionic,
Emulsion polymerization using a cationic, nonionic or amphoteric low molecular surfactant in the presence of the same radical polymerization initiator as described above may be used.

The aqueous emulsion of the present invention may be prepared by mechanically post-emulsifying a polymer obtained by various polymerization methods in an aqueous medium using various emulsification dispersion stabilizers, or may be obtained by various polymerization methods. Self-emulsified polymer having water-soluble functional groups (carboxyl group, amino group, sulfonic acid group, etc.) in the molecule to be obtained, for example, polyurethane emulsion, polyolefin emulsion, epoxy emulsion, polyester emulsion, etc. May be mixed in a range that does not impair the performance. The aqueous emulsion containing a polymer composed of one or more unsaturated monomer units selected from the group consisting of ethylenically unsaturated monomers and diene monomers used in the present invention as a dispersoid is prepared by the method described above. May be used alone, but if necessary, two or more kinds may be used in combination.

In the aqueous emulsion b, the ratio of the (co) polymer comprising the above-mentioned unsaturated monomer unit, which is a dispersoid, to the amino group-containing PVA, which is a dispersant, can be adjusted according to each situation. it can. From the viewpoint of storage stability and mechanical stability of the aqueous emulsion, the amount of the amino group-containing PVA per 100 parts by weight of the dispersoid is 0.5 to 300.
Part by weight is preferable, and 1 to 200 parts by weight is more preferable.
If the amount of the amino group-containing PVA is less than 0.5 parts by weight, it may not be possible to obtain a practical high solid content emulsion excellent in mechanical stability, which is a characteristic of the polyvinyl alcohol protective colloid system. . On the other hand, if the amount of the amino group-containing PVA is too large, problems such as a decrease in the storage stability of the emulsion may occur.

The aqueous emulsion b of the present invention can be used in an amount within a range not to impair the purpose, in the form of various water-soluble polymers such as PVA and water-soluble cellulose derivatives, anionic, cationic, nonionic or amphoteric low molecular surfactants. An agent may be contained. From the viewpoints of dispersion stability, handleability, etc., the total concentration of all the polymers in the aqueous emulsion b is about 20 to 7
It is preferably 0% by weight, more preferably 30 to 60% by weight.

In the aqueous emulsion b, the ratio of the (co) polymer comprising the above-mentioned unsaturated monomer unit as a dispersoid and the amino group-containing PVA as a dispersant can be adjusted according to each situation. it can. From the viewpoint of storage stability and mechanical stability of the aqueous emulsion, the amount of the amino group-containing PVA per 100 parts by weight of the dispersoid is 0.5 to 300.
Part by weight is preferable, and 1 to 200 parts by weight is more preferable.
If the amount of the amino group-containing PVA is less than 0.5 parts by weight, it may not be possible to obtain a practical high solid content emulsion excellent in mechanical stability, which is a characteristic of the polyvinyl alcohol protective colloid system. . On the other hand, if the amount of the amino group-containing PVA is too large, problems such as a decrease in the storage stability of the emulsion may occur.

The production method of the aqueous emulsion b is not particularly limited, but generally comprises one or two or more unsaturated monomer units selected from ethylenically unsaturated monomers and diene monomers. It is produced by mixing an aqueous emulsion containing a polymer as a dispersoid with an aqueous solution of an amino group-containing PVA under stirring. The method for preparing the amino group-containing PVA aqueous solution is not particularly limited, but it can be usually prepared by dissolving the amino group-containing PVA in water at an appropriate temperature, preferably at a temperature of 50 to 100 ° C. Amino group-containing P in aqueous solution of amino group-containing PVA
The concentration of VA can be adjusted according to the type and concentration of other components contained in the aqueous emulsion b, but an aqueous solution having a concentration of 5 to 20% by weight is preferable from the viewpoint of storage stability, handleability, and the like.

Further, the aqueous emulsion b of the present invention includes those obtained by further adding an amino group-containing PVA or an aqueous solution thereof to the aqueous emulsion a.

Next, the water-proofing agent (B) constituting the composition of the present invention will be described. Examples of polyhydric epoxy compounds include bisphenol A diglycidyl ether, bisphenol A diβ-methyl glycidyl ether, bisphenol F diglycidyl ether, tetrahydroxyphenylmethane tetraglycidyl ether, resorcinol diglycidyl ether, brominated bisphenol A diglycidyl ether, and chlorinated Bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, diglycidyl ether of bisphenol A alkylene oxide adduct, novolak glycidyl ether, polyalkylene glycol diglycidyl ether,
Glycidyl ether type such as glycerin triglycidyl ether, pentaerythritol diglycidyl ether, epoxy urethane resin; glycidyl ether / ester type such as P-oxybenzoic acid glycidyl ether / ester; diglycidyl phthalate, diglycidyl tetrahydrophthalate Glycidyl ester type such as diglycidyl ester of hexahydrophthalic acid, diglycidyl acrylate, diglycidyl ester of dimer; glycidylamine type such as glycidylaniline, tetraglycidyldiaminodiphenylmethane, triglycidyl isocyanurate, triglycidylaminophenol; epoxy Linear aliphatic epoxy resins such as hydrogenated polybutadiene and epoxidized soybean oil; 3,4 epoxy-6 methylcyclohexylmethyl Tyl-3,4 epoxy-6 methylcyclohexanecarboxylate, 3,4 epoxycyclohexylmethyl (3,4-epoxycyclohexane) carboxylate, bis (3,4-epoxy-6methylcyclohexylmethyl) adipate, vinylcyclohexene diepoxide, Dicyclopentadiene oxide,
Examples include alicyclic epoxy resins such as bis (2,3-epoxycyclopentyl) ether and limonenedioxide, and polyamide epichlorohydrin.

Examples of the aldehyde compound include monoaldehydes such as formaldehyde, acetaldehyde, propionaldehyde, crotonaldehyde and benzaldehyde, and dialdehydes such as glyoxal, malonaldehyde, glutaraldehyde, pimerin dialdehyde, suberin dialdehyde and dialdehyde starch. Is mentioned.

Examples of the polyvalent isocyanate compound include tolylene diisocyanate (TDI); hydrogenated TDI; trimethylolpropane-TDI adduct (for example, Desmour L, trade name, manufactured by Bayer AG); triphenylmethane triisocyanate; (MDI); hydrogenated MDI; polymerized MDI; hexamethylene diisocyanate; xylylene diisocyanate; 4,4-dicyclohexylmethane diisocyanate; isophorone diisocyanate. Further, an isocyanate dispersed in water using an emulsifier can also be used.

The amino resin is obtained by a condensation reaction between an amino compound and an aldehyde. Examples of the amino compound subjected to the condensation reaction include melamine, urea, thiourea, dicyandiamide, benzoguanamine, acetoguanamine and the like. These can be used alone or in combination of two or more. As the aldehyde, formaldehyde is used in the form of an aqueous solution or alcohol solution, and a compound capable of generating formaldehyde under condensation reaction conditions, for example, paraformaldehyde is also used.

The phenol resin is obtained by a condensation reaction between a phenol compound and an aldehyde. Examples of the phenol compound to be subjected to the condensation reaction include phenol, m-cresol, O-cresol, p-cresol, 3,5-xylenol, 2,5-xylenol, 2,4-xylenol, 3,4-xylenol, saligenin , 2,3,5
-Trimethylphenol and the like. These can be used alone or in combination of two or more. As the aldehyde, formaldehyde is used in the form of an aqueous solution or alcohol solution, and a compound capable of generating formaldehyde under condensation reaction conditions, for example, paraformaldehyde, hexamethylenetetramine and the like are also used.

As di (meth) acrylamide, N,
N'-methylenebisacrylamide, N, N'-ethylenebisacrylamide, N, N'-propylenebisacrylamide.

In the resin composition of the present invention, the weight ratio (A) / (B) of the amino group-containing PVA (A) and the waterproofing agent (B) is from 99.99 / 0.01 to 10/90, preferably from 99.99 / 0.01 to 10/90. 99.9 / 0.1 to 70/30. (A) / (B) is 99.99 / 0.0
When it exceeds 1, the water resistance effect is low, and when it is less than 10/90, the viscosity stability of the aqueous solution of the composition decreases.

The composition of the present invention may optionally contain
Various organic solvents such as toluene, perclene, dichlorobenzene, and trichlorobenzene, starch, modified starch, oxidized starch, sodium alginate, carboxymethylcellulose, methylcellulose, in order to prepare the drying property, setting property, viscosity, film forming property, etc. Hydroxymethyl cellulose, maleic anhydride / isobutene copolymer,
Maleic anhydride / styrene copolymer, maleic anhydride /
Water-soluble polymers such as methyl vinyl ether copolymer and thermosetting resins such as urea / formalin resin, urea / melamine / folimarin resin, phenol / folimarin resin,
In addition, clay, kaolin, talc, calcium carbonate,
Fillers such as wood flour, extenders such as flour, pigments such as titanium oxide, or other additives containing various additives such as antifoaming agents, dispersants, antifreezing agents, preservatives, and rust inhibitors may be used.

The composition of the present invention makes use of the characteristic of high water resistance, and is used for woodworking adhesive, paper processing adhesive, paint,
Used in various applications such as fiber treatment agents.

[0045]

EXAMPLES The present invention will now be described specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following Examples and Comparative Examples, “parts” and “%” mean on a weight basis unless otherwise specified. Also, the water resistance of the obtained emulsion film,
The water resistance and the viscosity stability were evaluated in the following manner.

(Evaluation of Emulsion) (1) Water Resistance of Film The obtained aqueous emulsion was prepared at 20 ° C. and 65% RH.
It was cast on PET and dried for 7 days to obtain a dry film of 500 μm. When this film is punched into a diameter of 2.5 cm and immersed in water at 20 ° C. for 24 hours as a sample,
The water absorption and elution rate of the film were determined. (2) Water resistant adhesive strength 150 g of the obtained aqueous emulsion was applied to hemlock material (straight grain).
/ M ² , and bonded together and pressed under a load of 7 kg / m ² for 16 hours. Then, after decompressing and curing for 5 days at 20 ° C. and 65% RH, it was immersed in hot water at 60 ° C. for 3 hours, and the compressive shear strength was measured in a wet state. (3) Viscosity stability 30 minutes when the emulsion is left at 5 ° C. or 50 ° C.
The change in viscosity after one day was observed.

Synthesis Example 1 [Synthesis of amino group-containing PVA] 405 parts of vinyl acetate monomer, 11 parts of allyl glycidyl ether and 30 parts of methanol were placed in a reactor equipped with a stirrer, a reflux condenser, a nitrogen inlet tube and a thermometer. Charged and degassed by bubbling nitrogen gas for 15 minutes. Separately, an initiator solution was prepared by dissolving 4.5 parts of 2,2-azobisisobutyronitrile in 15 parts of methanol, and nitrogen was replaced by bubbling with nitrogen gas. Start raising the temperature of the reactor until the internal temperature reaches 6
When the temperature reached 0 ° C., a separately prepared initiator solution was added to initiate polymerization. Polymerization was carried out at 60 ° C. for 4 hours, and the polymerization was stopped by cooling. At this time, the solid content concentration was 54.8%. Subsequently, unreacted vinyl acetate monomer was removed while occasionally adding methanol at 30 ° C. under reduced pressure, and a methanol solution of polyvinyl acetate copolymer (concentration: 44.5%)
I got This copolymer was a polyvinyl acetate copolymer containing 2.1 mol% of allyl glycidyl ether units (epoxy groups) and having a viscosity average molecular weight of 80 × 10 ³ .
Next, a methanol solution of the polyvinyl acetate copolymer having an epoxy group obtained above (concentration: 44.5) was placed in a reactor equipped with a stirrer, a reflux condenser, a nitrogen inlet, and a thermometer.
%), Weighing out 100 parts, bubbling nitrogen gas for 15 minutes, and dissolving 8.5 parts of 2-amino-5-mercapto-1,3,4-thiadiazole and 0.03 part of sodium hydroxide in 48 parts of methanol. I put things in. After reacting at 50 ° C. for 2 hours with stirring, the mixture was cooled to 40 ° C., and 40 parts of a 10% methanol solution of sodium hydroxide was added to perform saponification. After leaving at 40 ° C for 5 hours, pulverize,
The mixture was neutralized by adding 8 parts of acetic acid. After performing Soxhlet extraction with methanol for 48 hours, amino group-containing PVA was obtained by drying at 60 ° C. for 20 hours. The PVA (PV
In A-1), 2.1 mol% of amino groups were introduced, the vinyl alcohol content was 97.0 mol%, and the polymerization degree was 1,000.

Synthesis Example 2 [Synthesis of amino group-containing PVA] The 2-amino-5-mercapto-1, used in Synthesis Example 1,
An amino group-containing PVA was obtained in the same manner as in Synthesis Example 1 except that 5-amino-3-mercapto-1,2,4-triazole was used instead of 3,4-thiadiazole. The PV
A (PVA-2) had 2.1 mol% of amino groups introduced therein, had a vinyl alcohol content of 97.0 mol% and a degree of polymerization of 1,000.

Example 1 The amino group-containing PVA of Synthesis Example 1 (polymerization degree 1000, saponification degree 97.0%, amino group content 2.1 mol%, PVA
-1) 100 parts of water was added to 5 parts, and PVA was heated and dissolved at 95 ° C. The PVA aqueous solution was charged into a pressure-resistant autoclave, 100 parts of vinyl acetate was added, and after purging with nitrogen, ethylene was injected to 40 kg / cm ² . Then, the internal temperature was raised to 60 ° C., and copolymerization was carried out in the presence of a hydrogen peroxide / tartaric acid redox initiator system. The copolymerization was completed in 3 hours, and a stable vinyl acetate-ethylene copolymer emulsion having a solid concentration of 52.9% and a viscosity of 1110 mPa · s (E
m-1) was obtained. Using this, the water resistance, the water resistance adhesive strength, and the viscosity stability of the film were tested by the above-described methods. The results are shown in Tables 1 and 2.

Example 2 A 1-liter glass polymerization vessel equipped with a reflux condenser, a dropping funnel, a thermometer and a nitrogen inlet was charged with 100 parts of ion-exchanged water.
Part, amino group-containing PVA of Synthesis Example 1 (polymerization degree 1000,
A saponification degree of 97.0%, a primary amino group content of 2.1 mol%, and 5 parts of PVA-1) were charged and completely dissolved at 95 ° C. Next, the PVA aqueous solution was cooled and replaced with nitrogen.
While stirring at 0 rpm, 10 parts of vinyl acetate was charged,
After heating to 60 ° C., polymerization was initiated in the presence of a hydrogen peroxide / tartaric acid redox initiator system. From 15 minutes after the start of the polymerization, 90 parts of vinyl acetate was continuously added over 3 hours to complete the polymerization. A polyvinyl acetate emulsion (Em-2) having a solid content of 48.5% was obtained. 5 parts of dibutyl phthalate was added to and mixed with 100 parts by weight of this emulsion. Using this, a test similar to that of Example 1 was performed. The results are shown in Tables 1 and 2.

Comparative Example 1 The same test as in Example 1 was conducted using an ethylene-vinyl acetate copolymer emulsion (OM-4200 manufactured by Kuraray, solid content concentration 55%, Em-3). The results are shown in Tables 1 and 2.

Comparative Example 2 The procedure of Example 1 was repeated, except that in place of the amino group-containing PVA (PVA-1) in Synthesis Example 1, unmodified polyvinyl alcohol (polymerization degree 1000, saponification degree 98.5%, PVA-3) was used. Polyvinyl acetate emulsion (Em-4) as in 2
Was prepared, and the same test as in Example 1 was performed. The results are shown in Tables 1 and 2.

Example 3 Ethylene-vinyl acetate copolymer emulsion (OM-4200 manufactured by Kuraray, solid content concentration 55%, Em-3) 100
Parts, 15% aqueous solution of PVA-1 of Synthesis Example 1
An aqueous emulsion was prepared by adding parts. The same test as in Example 1 was performed using this aqueous emulsion.
The results are shown in Tables 1 and 2.

Example 4 Ethylene-vinyl acetate copolymer emulsion (OM-4200 manufactured by Kuraray, solid content concentration 55%, Em-3) 100
The aqueous emulsion was prepared by adding 1 part of a 15% aqueous solution of PVA-1 of Synthesis Example 1 to the parts. The same test as in Example 1 was performed using this aqueous emulsion. The results are shown in Tables 1 and 2.

Example 5 Ethylene-vinyl acetate copolymer emulsion (OM-4200 manufactured by Kuraray, solid content concentration 55%, Em-3) 100
Parts of a 15% aqueous solution of PVA-1 in Synthesis Example 1
An aqueous emulsion was prepared by adding 0 parts. The same test as in Example 1 was performed using this aqueous emulsion. The results are shown in Tables 1 and 2.

Example 6 Polyvinyl acetate emulsion (Em-4) 1 of Comparative Example 2
An aqueous emulsion was prepared by adding 10 parts of a 15% aqueous solution of PVA-1 of Synthesis Example 1 to 00 parts. The same test as in Example 1 was performed using this aqueous emulsion. The results are shown in Tables 1 and 2.

Example 7 A 1-liter glass polymerization vessel equipped with a reflux condenser, a dropping funnel, a thermometer and a nitrogen inlet was charged with 100 parts of ion-exchanged water.
, 3 parts of a nonionic surfactant (Nonipol 200, manufactured by Sanyo Chemical Co., Ltd.) and 0.5 part of an anionic surfactant (Sandet BL, manufactured by Sanyo Chemical Co., Ltd.) were charged and dissolved. Next, after nitrogen replacement, 1.3 parts of n-butyl acrylate and 1.3 parts of methyl methacrylate were charged while stirring at 140 rpm, and
Temperature, and then a 5% aqueous solution of ammonium persulfate 2.5%
Was added to initiate polymerization. After 15 minutes from the start of the polymerization, a mixture of 50 parts of n-butyl acrylate and 50 parts of methyl methacrylate was continuously added over 2 hours to complete the polymerization. Poly (n-butyl acrylate / methyl methacrylate) emulsion having a solid content of 46.5% (E
m-5) was obtained. An aqueous emulsion was prepared by adding 10 parts of a 15% aqueous solution of PVA-1 of Synthesis Example 1 to 100 parts by weight of this emulsion. The same test as in Example 1 was performed using this aqueous emulsion. The results are shown in Tables 1 and 2.

Comparative Example 3 Ethylene-vinyl acetate copolymer emulsion of Example 3 (OM-4200 manufactured by Kuraray, solid content concentration 55%, Em-
3) An aqueous emulsion was prepared by adding 10 parts of a 15% aqueous solution of unmodified polyvinyl alcohol (PVA-3) to 100 parts. The same test as in Example 1 was performed using this aqueous emulsion. The results are shown in Tables 1 and 2.

Example 8 In place of PVA-1 of Synthesis Example 1, the amino group-containing PVA of Synthesis Example 2 (polymerization degree 1050, saponification degree 97.0%, amino group content 2.1 mol%, PVA-2 ), Except
As in Example 1, the solid content concentration was 52.8% and the viscosity was 1
A stable vinyl acetate-ethylene copolymer emulsion (Em-6) of 090 mPa · s was obtained. Using this, the same test as in Example 1 was performed. The results are shown in Tables 1 and 2.

Example 9 Ethylene-vinyl acetate copolymer emulsion (OM-4200 manufactured by Kuraray, solid content concentration 55%, Em-3) 100
To 15 parts of a 15% aqueous solution of PVA-2 of Synthesis Example 2
An aqueous emulsion was prepared by adding parts. The same test as in Example 1 was performed using this aqueous emulsion.
The results are shown in Tables 1 and 2.

Example 10 An aqueous emulsion was prepared by adding 3 parts of ethylene glycol diglycidyl ether to 100 parts of the ethylene-vinyl acetate copolymer emulsion (Em-1) of Example 1. The same test as in Example 1 was performed using this aqueous emulsion. The results are shown in Tables 1 and 2.

Example 11 A test was conducted in the same manner as in Example 10 except that the ethylene glycol diglycidyl ether used in Example 10 was changed to glyoxal. The results are shown in Tables 1 and 2.

Example 12 A test was conducted in the same manner as in Example 10 except that the ethylene glycol diglycidyl ether used in Example 10 was changed to a water-dispersible isocyanate. Table 1 with the results
And Table 2.

Example 13 A test was conducted in the same manner as in Example 10 except that the ethylene glycol diglycidyl ether used in Example 10 was changed to an amino resin. The results are shown in Tables 1 and 2.

Example 14 A test was conducted in the same manner as in Example 10 except that the ethylene glycol diglycidyl ether used in Example 10 was changed to a phenol resin. The results are shown in Tables 1 and 2.

Example 15 Example 10 was repeated except that the ethylene glycol diglycidyl ether used in Example 10 was changed to diacrylamide.
The test was performed in the same manner as described above. The results are shown in Tables 1 and 2.

[0067]

[Table 1]

(Footnote to Table 1) Em-1: Ethylene-vinyl acetate copolymer emulsion (protective colloid containing amino group-containing PVA (PVA-1), solid content concentration: 53.0%) Em-2: Polyvinyl acetate emulsion (Amino group-containing PVA (PVA-1) protective colloid, solid content concentration 48.
Em-3: Ethylene-vinyl acetate copolymer emulsion (OM-4200 manufactured by Kuraray, solid content concentration 55%) Em-4: Polyvinyl acetate emulsion Em-5: Poly (n-butyl acrylate / methacrylic acid) Methyl) Emulsion Em-6: Ethylene-vinyl acetate copolymer emulsion (protective colloid containing amino group-containing PVA (PVA-2), solid content concentration 52.8%) PVA-1: 2.1 mol% containing amino group, saponification Degree 97.
0 mol%, polymerization degree 1000 PVA-2: 2.1 mol% containing amino group, saponification degree 97.
0 mol%, polymerization degree 1000 PVA-3: unmodified, saponification degree 98.5 mol%, polymerization degree 1000 Water-dispersible isocyanate: Coronate C-3053 (manufactured by Nippon Polyurethane Industry) Amino resin: Euroid S-22 (Mitsui Toatsu) Phenolic resin: Phenolite TD-617 (manufactured by Dainippon Ink and Chemicals) Diacrylamide: N, N'-methylenebisacrylamide

[0069]

[Table 2]

[0070]

The aqueous emulsion of the present invention has excellent stability in standing viscosity and excellent water-resistant adhesive strength, and is widely used as an adhesive for woodworking, an adhesive for plywood, a paper processing agent, a paint, a fiber processing agent and the like. It is preferably used.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 29/04 C08L 29/04 GC // C08F 8/34 C08F 8/34 (C08F 216/06 226: 06)

Claims (4)

[Claims] 1. A polymer comprising one or more unsaturated monomer units selected from an ethylenically unsaturated monomer and a diene monomer is used as a dispersoid, and is bonded to a heterocycle in the molecule. 0.01 to 30 mol% of the unit containing an amino group
An aqueous emulsion containing a vinyl alcohol polymer as a dispersant. 2. The aqueous emulsion according to claim 1, wherein the unit having an amino group bonded to the heterocyclic ring is a unit represented by the following chemical formula 1. Embedded image (Where R ¹ , R ² , R ³ , R ⁴ and R ⁵ represent a hydrogen atom or a hydrocarbon group having 8 or less carbon atoms, A represents a divalent hydrocarbon group, and S represents a sulfur atom. And X represents a monovalent group containing an amino group bonded to the heterocyclic ring.) 3. The aqueous emulsion according to claim 1, wherein the monovalent group containing an amino group bonded to the heterocycle is a group represented by the following chemical formula 2. Embedded image (Where Z represents S, O, NH or CH ₂ ) 4. The aqueous emulsion (A) according to claim 1, and at least one selected from the group consisting of polyepoxy compounds, aldehyde compounds, polyisocyanate compounds, amino resins, phenol resins and diacrylamide. A water-resistant composition comprising the above water-resistant agent (B).