JP2003082309A - Latex for aqueous vinylurethane adhesive - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a copolymer latex for an aqueous vinylurethane adhesive having an excellent pot life as well as high initial adhesive strength and repeated boiling strength. SOLUTION: In the copolymer latex for the aqueous vinylurethane adhesive comprising emulsion obtained by copolymerizing 20-60 wt.% of an aliphatic conjugated diene monomer, 0.1-5 wt.% of an ethylenically unsaturated dicarboxylic acid monomer, 0.1-15 wt.% of a hydroxy group-containing ethylenically unsaturated monomer, and 20-79.8 wt.% of the other monomer copolymerizable with the monomers, a toluene-insoluble content of the copolymer is >=85 wt.%.

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention
Suitable for use, and the pot life of the adhesive
Provides long, high initial bond strength, and repeated boiling strength
Aqueous polymer isocyanate (aqueous vinyl urethane
G) a copolymer latex for an adhesive; 2. Description of the Related Art Conventionally, urea-based resins, melamine
Min-based resin, phenol-based resin, and resorcinol-based
Formaldehyde heat-condensed thermosetting resins such as resins
Has been used. On the other hand, about 25 years ago
It contains almost no heat, and is high with relatively short pressing at room temperature.
Synthetic rubber latex with normal adhesive strength and water resistant adhesive strength
, Polyvinyl alcohol and isocyanate compounds
Water-based vinyl urethane adhesive used for laminated wood
(Japanese Unexamined Patent Publication No. 49-26343,
0-69137, JP-A-50-69138
Information). Recently, this aqueous vinyl urethane adhesive
Is a formaldehyde condensation type
It is used in large quantities in place of fat. [0003] Laminated rubber used in aqueous vinyl urethane adhesives
Tex includes synthetic rubber latex and acrylic acid
Stel copolymer latex, ethylene-vinyl acetate
Copolymer latex and the like are used. Synthetic rubber
Tex is a styrene-butadiene copolymer (SB copolymer).
Combined) latex, carboxyl group, hydroxyl group, amide
Group such as an amino group, an amino group or a sulfonic acid group
SB type copolymer with large particle size, added to B copolymer
Unified latex is disclosed in JP-A-59-59768,
It is disclosed in JP-A-49-26343 and the like. [0004] Aqueous vinyl urethane adhesives have various functional groups.
Contains isocyanate compounds that easily react with
Because the complex reaction in the adhesive system proceeds at room temperature,
Viscosity tends to increase rapidly after a short period of storage (pot
Is short), but on the other hand, the reaction of isocyanate groups is rapid.
The intense progress generally results in an undried
Adhesion strength in the state (initial adhesion strength) or after applying and drying the adhesive
Water resistance (boiled repeated strength) of processed wood
No. However, as the pot life of the adhesive becomes longer,
In addition, the initial bond strength and the boiling strength are considerably reduced.
On the other hand, recently, the production speed of wood processing has been improved.
And the first time the adhesive is used in the bonding process
It is becoming necessary to increase the initial adhesive strength. Copolymer
Latex is closely related to these properties,
Always difficult, but excellent in pot life
If is long) and at the same time high boiling repetition strength, and the first
Development of Copolymer Latex that Gives Initial Bond Strength
Is needed for The above-mentioned known copolymer latte
Excellent pot life, boiled simply by applying
Adhesive performance with both boiling repeat strength and initial adhesive strength
It is difficult to give to the agent. [0005] The present invention is directed to a potter.
Excellent if and high initial bond strength and boiling
Copolymer for aqueous vinyl urethane adhesive giving repetitive strength
To provide body latex. Means for Solving the Problems When the pot life is excellent,
Both have high initial adhesive strength and boiling repeated strength
Obtain copolymer latex for aqueous vinyl urethane adhesive
The effect of latex copolymers on these properties
Factors such as synthesis, copolymerization formulation, and particle size
As a result, it is simultaneously modified with two types of monomers having specific functional groups.
Copolymer latex of a specific composition
Surprisingly, gels with a specific high range
Excellent initial life and high boiling strength
It turned out that it has repetition strength, and reached the present invention.
That is, the present invention relates to aliphatic conjugated diene monomers 20 to
60% by weight, ethylenically unsaturated dicarboxylic acid monomer 0.1%
1 to 5% by weight, a hydroxyl group-containing ethylenically unsaturated monomer 0.1.
1 to 15% by weight, and other monomers copolymerizable therewith
20 to 79.8% by weight of emulsion copolymerized,
The toluene insoluble content of the copolymer is 85% by weight or more
Copolymer latte for aqueous vinyl urethane adhesive characterized by the following
Box, concerning. DETAILED DESCRIPTION OF THE INVENTION The present invention will be specifically described below.
I do. Copolymer of the present invention used for aqueous vinyl urethane adhesive
The coalesced latex is composed of an aliphatic conjugated diene monomer,
Unsaturated dicarboxylic acid monomer, hydroxyl group-containing ethylene
Unsaturated monomers and other monomers copolymerizable therewith.
It is obtained by emulsion polymerization. Conjugated diene monomer
Examples of the body include 1,3-butadiene, isoprene,
2,3-dimethyl-1,3-butadiene, 2-ethyl-
1,3-butadiene, 2-methyl-1,3-butadiene
1,3-pentadiene, chloroprene, 2-chloro
-1,3-butadiene, cyclobutadiene, etc.
Can be used alone or in combination of two or more.
Can be used. Among these, 1,3-butadiene is preferred.
Can be used appropriately. The usage ratio of the conjugated diene monomer is 2
It is 0 to 60% by weight, preferably 30 to 50% by weight.
If it is less than 20% by weight, the normal adhesive strength is particularly reduced, and
If the weight percent is exceeded, the pot life is particularly shortened,
The initial bond strength is also low, which is not preferable. [0008] As an ethylenically unsaturated dicarboxylic acid monomer
Examples include itaconic acid, fumaric acid, maleic acid, etc.
be able to. Unsaturation such as acrylic acid and methacrylic acid
The use of monocarboxylic acid is preferred because it shortens the pot life.
Not good. 0.1-5% by weight of unsaturated dicarboxylic acid
Need to be. If less than 0.1% by weight, the initial adhesive strength
Is low and exceeds 5% by weight, latex during polymerization
Weight increases due to increased viscosity or large amounts of polymerization residue
In addition to the difficulties, the pot life is shortened
Is not preferred. Hydroxyl-containing ethylenically unsaturated monomer
As hydroxyethyl acrylate, hydroxy
Methyl acrylate, hydroxyethyl methacrylate
G, hydroxypropyl acrylate, hydroxypro
Pill methacrylate, allyl alcohol, polyhydric alcohol
Monoallyl ether of
The amount used is 0.1 to 15% by weight. Less than 0.1% by weight
Low initial bond strength, exceeding 15% by weight
The pot life is significantly reduced, and the boiling strength
It is not preferable because it tends to decrease. [0009] Aliphatic conjugated dienes, ethylenically unsaturated dica
With rubonic acid or a hydroxyl group-containing ethylenically unsaturated monomer
Other copolymerizable monomers include aromatic vinyl monomer
Body, (meth) alkyl ester monomer, vinyl cyanide
Monomer, (meth) acrylamide monomer, etc.
Can be Examples of aromatic vinyl monomers include styrene.
Len, α-methylstyrene, vinyltoluene, p-methyl
Styrene, o-methylstyrene, m-methylstyrene
, Ethyl styrene, hydroxymethyl styrene, vinyl
Luxylene, bromostyrene, vinylbenzyl chloride
, Chlorostyrene, divinylbenzene, trivinylbenzene
And so on. (Meth) alkyl ester alone
Examples of the monomer include methyl (meth) acrylate,
Chill (meth) acrylate, propyl (meth) acryle
, N-butyl (meth) acrylate, t-butyl
(Meth) acrylate, isobutyl (meth) acrylate
G, n-amyl (meth) acrylate, isoamyl hex
Sil (meth) acrylate, octyl (meth) acryle
, Nonyl (meth) acrylate, decyl (meth) acrylate
Acrylate, dodecyl (meth) acrylate, octade
Sil (meth) acrylate, cyclohexyl (meth) a
Acrylate, phenyl (meth) acrylate, benzyl
(Meth) acrylate, 2-ethylhexyl (meth) a
Acrylate, glycidyl (meth) acrylate, ethyl
Glycol di (meth) acrylate, 1-3-butyl
Glycol di (meth) acrylate, 1,4-butyle
Glycol di (meth) acrylate, propylene glycol
Cole di (meth) acrylate, 1,5-pentadiau
Luji (meth) acrylate, neopentyl glycol di
(Meth) acrylate, 1,6-hexanediol di
(Meth) acrylate, diethylene glycol di (meth)
TA) acrylate, polyethylene glycol di (meth)
Acrylate, polypropylene glycol di (meth) a
Acrylate, pentaerythritol tri (meth) acryl
Rate, trimethylolpropane tri (meth) acryle
Or tetramethylolmethanetetra (meth) acryle
, Allyl (meth) acrylate, bis (4-acrylic)
Roxypolyethoxyphenyl) propane, phenoxye
Tyl (meth) acrylate, 2,2-bis [4-((meth
TA) acryloxyethoxy) phenyl] propane, 2,
2-bis [4-((meth) acryloxydiethoxy)
Phenyl] propane, 2,2-bis [4-((meth) a
Cryoxy / polyethoxy) phenyl] propane, iso
Bornyl (meth) acrylate
Use these alone or in combination of two or more
Can be Examples of the vinyl cyanide monomer include, for example,
Acrylonitrile, methacrylonitrile, α-chlorur
Acrylonitrile and the like.
Or a combination of two or more.
Examples of (meth) acrylamide monomers include, for example,
TA) acrylamide, N-methylol (meth) acryl
N- such as amide and N-methyl (meth) acrylamide
Monoalkyl (meth) acrylamide, N, N-dimethyl
N, N-dialkyl such as (meth) acrylamide
(Meth) acrylamide, glycidyl methacrylamide
, N-alkoxy (meth) acrylamide, 2-ac
Rilamide-2-methylpropanesulfonic acid and the like
Can be used alone or in combination of two or more.
Can be used. Other monomers include, for example, aminoethyl
(Meth) acrylate and dimethylaminoethyl (meth)
Amino groups such as acrylates and 2-vinylpyridine
Containing ethylenic monomer, vinyl acetate
Nyl esters, vinyl chloride and vinylidene chloride
Vinylogen, styrene sulfonate and 2- (meth)
Acryloyloxyethylsulfonic acid and (meth) a
Sulfonic acid group-containing monomers such as lylsulfonate, phosphoric acid
Ethylene (meth) acrylate or propylene phosphate (meth
(T) acrylate and 2- (meth) acryloyloxy
Phosphoric acid group-containing monomers such as ciethyl acid phosphate
These can be used alone or in combination of two or more.
The above can be used in combination. [0012] The copolymer latex of the present invention is an aqueous medium.
Emulsifier, radical polymerization of monomers, chain transfer agents, etc. in the body
With initiator and, if necessary, other additive components
It is obtained by a conventionally known emulsion polymerization method for polymerization. Communicating
Examples of the chain transfer agent include α-methylstyrene dimer
Dimers of nuclear-substituted α-methylstyrene such as n-butyl
Mercaptan, n-octyl mercaptan, n-lauri
Rumercaptan, n-dodecyl mercaptan, and t-
Mercaptans such as dodecyl mercaptan, tetrame
Tilthiuram disulfide and tetraethylthiuram
Disulfides such as disulfide, 2-ethylhexyl
Luthioglycolate, terpinolene, cyclopente
, Cyclohexene, etc., alone or
Can be used in combination of two or more. As the emulsifier, for example, aliphatic soaps,
Acid soap, alkyl sulfonate, dialkylaryl
Sulfonate, alkyl sulfosuccinate, polyoxy
Ethylene alkyl sulfate and polyoxyethylene alcohol
Anionic emulsifiers such as
Siethylene alkyl ether, polyoxyethylene al
Killed aryl ethers and polyoxyethyleneoxy
Nonionic emulsifiers such as propylene block copolymer
Known materials alone or in combination of two or more
Can be used. In addition to these, hydrophilic groups and lipophilic groups
Ethylene double bond in chemical formula of surfactant
A reactive emulsifier into which a mixture is introduced can also be suitably used.
Amphoteric emulsifier such as tine type, and polyvinyl alcohol
, Modified polyvinyl alcohol (with a mercapto group at the end)
Etc.), carboxymethylcellulose, methyl
Water-soluble components such as cellulose and polyvinylpyrrolidone
Use of protective colloid emulsifiers etc. as necessary
Can be. The radical polymerization initiator may be heat or a reducing substance.
Radical polymerization in the presence of a substance to initiate addition polymerization of monomers
And an inorganic initiator, and an organic initiator.
Either can be used. Such as, for example,
Water-soluble or oil-soluble peroxodisulfate, peroxide
Products, azobis compounds, etc., specifically, peroxodisulfur
Potassium, sodium peroxodisulfate, peroxo
Ammonium disulfate, hydrogen peroxide, t-butylhydrope
Oxide, benzoyl peroxide, 2,2-azobisbutyl
Ronitrile, cumene hydroperoxide
And POLYMER HANDBOOK
(3rd. Edition); Brandrup and
And E. H. By Immergut, John Willy
& Sons (1989)
Can be. Also, sodium acid sulfite, Asco
Rubic acid and its salts, erythorbic acid and its salts, Rongari
Using a reducing agent such as a combination with a polymerization initiator,
A so-called redox polymerization method can also be employed. This
The amount of polymerization initiator used is based on the weight of all monomers and is usually
0.1-5.0% by weight, preferably 0.2-3.0% by weight
%use. Polymerizing the copolymer latex of the present invention
During and after polymerization, various regulators may be added as necessary.
Can be added. For example, as a pH adjuster, hydroxyl
Potassium hydroxide, sodium hydroxide, ammonium hydroxide,
Sodium hydrogen carbonate, sodium carbonate, dihydrogen phosphate
Thorium or the like can be added. Also, ethylenedi
Various chelating agents such as sodium amine tetraacetate
It can be added as a coordinator. Copolymer of the present invention
When the latex is obtained by emulsion polymerization, the polymerization temperature is usually 5 to 5.
The temperature is 120 ° C., but is not particularly limited. Departure
Light copolymer latex can be used not only in one-stage polymerization but also in multi-stage polymerization.
Can be manufactured. Addition of monomer mixture to polymerization system
Is added all at once, intermittently or intermittently
Methods, methods combining these methods (eg,
After adding a part of the polymer mixture,
Any method such as continuous or intermittent addition)
No. In the polymerization, a seed polymerization method is also employed.
be able to. Seed latex composition is particularly limited
Is not the same, even if the composition is the same as that of the copolymer latex.
Latex for seeds can be manufactured in the same reaction vessel
Using a different reaction vessel
The particle size, particle size distribution, and the amount used
It is not limited to. Conversion of monomers in emulsion polymerization
Is not particularly limited, but is usually 60% or more, preferably 8% or more.
0% or more. The copolymer of the present invention has a copolymer composition
Is extremely specific, and in addition,
Must have at least 85% by weight of toluene insoluble content
is necessary. When the toluene insoluble content is less than 85% by weight
The water-based vinyl urethane adhesive has a shorter pot life
Is not preferred. The toluene insoluble content of the copolymer was used
Control depending on the monomer composition, polymerization recipe, polymerization conditions, etc.
It can be rolled, but depending on the amount of chain transfer agent
Control and increase the amount of chain transfer agent.
As a result, the toluene insoluble content decreases. Average particle size of the copolymer latex of the present invention
Is not particularly limited, but is preferably about 100 to 600 nm.
No. In order for pot life to be prolonged, especially 200 to 5
A range of 00 nm is preferred. Particles over 600 nm
Are not preferable because they will remarkably settle. latté
The solid content and pH of the box are not particularly limited.
Solids in the range of 40-65% by weight, 4.0-12.
The pH may be in the range of 0. However, pH of latex
Too high can damage the wood,
The range of 4.0 to 9.0 is preferred. The aqueous vinyl urethane adhesive is used in the present invention.
Polymer latex, vinyl alcohol-based polymer, and
A base compound is created by blending fillers, etc.
Adding an isocyanate compound as a crosslinking agent
Thus obtained. Vinyl alcohol-based polymers are partially
Saponified polyvinyl alcohol, fully saponified polyvinyl alcohol
Coal, polyvinyl alcohol derivatives, vinyl acetate
Which vinyl ester monomers and ethylenically unsaturated monomers
Copolymerized and saponified (sulfonic acid-modified,
Carboxy modification, silanol group modification, acetoacetylation
Such as modified polyvinyl alcohol) and thiolacetic acid
In the presence of a thiol compound, a vinyl ester monomer
Copolymerized Tylene unsaturated monomer and saponified it
It is possible to use modified polyvinyl alcohol such as
it can. Degree of polymerization of these vinyl alcohol polymers,
Although the saponification degree is not particularly limited, it is 300 to
Having a degree of polymerization of 3,000 and a degree of saponification of 75 mol% or more
Is preferred. The proportion of the vinyl alcohol polymer used is as follows:
100 parts by weight (solid content) of the copolymer latex of the present invention
On the other hand, the amount is preferably 5 to 200 parts by weight. Less than 5 parts by weight
Has a remarkable decrease in the adhesive strength and exceeds 200 parts by weight.
The viscosity immediately after making the adhesive increases,
In addition to being difficult to handle, pot life is also non-
It is not preferable because it is always shorter. Isocyanate compound
Are compounds having two or more isocyanate groups in the molecule
Or a polymer, such as tolylene diisocyanate
And its hydride, triphenylmethane triiso
Cyanate, trimethylolpropane-tolylenediiso
Cyanate adduct, diphenylmethane diisocyanate
[MDI (methylene di (4-phenyl isocyanate)
G), crude MDI)) and its hydrides,
Xamethylene diisocyanate, xylene diisocyanate
, Isophorone diisocyanate, 4,4'-disc
Examples include rohexyl methane diisocyanate.
It is possible to use those containing high boiling point solvents etc.
Wear. In addition, the above iso
Excess mixture of cyanate compound, polyol
And pre-polymerized OH with excess polyisocyanate
Base-terminated prepolymer, pre-polymerized with excess polyol
Of polyisocyanate to OH-terminated prepolymer
Compound in excess, containing nonionic surfactant
Polyisocyanates can also be used. The use ratio of the isocyanate compound is
For 100 parts by weight (solid content) of light copolymer latex
In the range of 10 to 500 parts by weight. 10 parts by weight not yet
In the case of full, the boiling adhesive strength and initial adhesive strength are very low.
If the amount exceeds 500 parts by weight,
It is not preferable because the life becomes very short. As a filler
Calcium carbonate, clay, kaolin, talc, hydroxyl
Inorganic and organic materials such as aluminum chloride, palm husk powder, and wood powder
Fillers can be mentioned. The filler is the copolymer latex 1 of the present invention.
A range of 10 to 500 parts by weight based on 00 parts by weight (solid content).
It is preferable to use the box. If less than 10 parts by weight,
The production cost of the adhesive becomes high, and it becomes economically disadvantageous.
If it exceeds 00 parts by weight, the normal adhesive strength is remarkably reduced.
Therefore, it is not preferable. Using the copolymer latex of the present invention
Water-based vinyl urethane adhesives include vinyl alcohol
In addition to polymers, isocyanate compounds and fillers, wheat
Flour, starches (starch such as wheat, potato, rice, tapioca,
And esterified starch, etherified starch, cationic starch
Which starch derivatives, oxidized starch, dextrin
Etc.), bulking agents such as defatted soybean powder, blood powder, calcium chloride
Deliquescent compounds such as and magnesium chloride, boric acid, boric acid
Acid salts, aluminum sulfate, alum, chromium borate, etc.
Reaction accelerators, ethylene glycol and propylene glycol
Deicing agents such as polyethylene oxide propylene
Oxide copolymers and polyethylene oxides
Kill phenol ether and polyethylene oxide
・ Nonionic surfactants such as alkyl ethers
Nonionic surfactants, glucose, trehalose, etc.
Sugars, polysaccharides, carboxymethylcellulose, methyl
Cells such as cellulose and hydroxymethylcellulose
Loose derivatives and maleic anhydride-isobutene copolymer
Coalescence, maleic anhydride-styrene copolymer, maleic anhydride
Acid-methyl vinyl ether copolymer, alginic acid
, Water-soluble polymer water retention agents such as sodium polyacrylate,
Urea-formalin resin, urea-melamine resin, phenol
Thermosetting resins such as ru-formalin resin, rosin and
Gin ester type, terpene phenol resin and terpene weight
If necessary, tackifiers such as coalescence, various preservatives, etc.
Can be added. Aqueous solution using the copolymer latex of the present invention
Vinyl urethane adhesive can be used for laminated wood, plywood, LVL (single veneer)
For bonding wood such as laminated materials), particle board, furniture
Suitable for use, but wood and paper, textiles, minerals
It can also be used for bonding to plates, films, etc. Glue thick
Although the degree and application amount need to be adjusted appropriately depending on the application,
Usually 35-70% by weight (solid content), 50-500
g / m ^Two Is the application amount. Copolymer latex of the present invention
Aqueous vinyl urethane adhesive using
Paint on the adherend with a coater, spray, curtain coater, etc.
Cloth, deposition, pressing, drying (hot press etc.)
Thus, an adhesive product can be obtained. Compression and drying temperature
Can be arbitrarily selected from room temperature to high temperature (about 200 ° C)
However, it usually adheres well at room temperature even if pressed within 60 minutes. Next
Now, the present invention will be described in more detail with reference to Examples and Comparative Examples.
The present invention is not limited to these. In addition,
“%” And “parts” are based on weight. Latex particle size and toluene-insoluble content
Measurement, adjustment of aqueous vinyl urethane adhesive, and
Tri-life, initial bond strength, normal bond strength, repeated boiling
The measurement of the adhesive strength was performed according to the following method. (1) Particle size Light is applied to the fine particles moving in Brownian motion and returns from the particles.
Changes in the frequency (frequency of light) of incoming light (backscattered light)
Measured by the method of determining the particle size of fine particles from the amount measuring device
Is a micro truck UPA150 (Nikkiso Co., Ltd.)
Using. (2) Toluene insoluble content (%) About latex sample on Teflon (registered trademark) sheet
1 g is dried at 130 ° C. for 30 minutes. Dry sample
Approximately 0.5g is precisely weighed and placed in a container containing 30ml of toluene.
Add and shake for 3 hours with a shaker. Torue after shaking
The dispersion was filtered through a 325 mesh stainless steel mesh,
The filtration residue is dried at 130 ° C. for 1 hour and measured. Torr
Ene insoluble content is calculated as the dry amount of filtration residue relative to the dry sample amount.
It was determined from the ratio. (3) Adjustment of Adhesive Polyvinyl alcohol adjusted to 15% concentration
40 parts of Kuraray's Poval 217) aqueous solution, dispersant (F
0.1 part of sodium oxametaphosphate, 6 parts of water, calcium carbonate
Um (NS100, manufactured by Nitto Toka Co., Ltd.) and 21 parts
33 parts copolymer latex (solid content 50%) mixed
The mixture was stirred to form a base compound. Then this
Diphenylmethane as a cross-linking agent in the base compound
-4, 4'-diisocyanate compound 15 parts
Then, the mixture was stirred to form an aqueous vinyl urethane adhesive. (4) Pot life Preparation of aqueous vinyl urethane adhesive prepared in (3) above
The viscosity immediately after and the viscosity after standing at 25 ° C. for 60 minutes are BH type.
Measure with a viscometer and leave it for 60 minutes after the viscosity
It was determined that the higher the viscosity ratio, the shorter the pot life. (5) Initial adhesive strength Cover having a thickness of 11 mm, a length of 25 mm and a width of 30 mm
A water-based plastic (25 mm x 25 mm)
Apply the urethane adhesive and place the same birch
The pulls were overlaid and clamped. Initial bond strength at 15 ° C for 30 minutes
Immediately after tightening, press according to JIS K 6852.
The shear strength was measured. Coating amount: 250 g / m ^Two Pressing conditions: pressure 0.15MPa, time 30 minutes, temperature 15
° C (6) Normal state adhesive strength A sample pressed in the same manner as in the initial adhesive strength measurement test was used for 20
After curing for 7 days at ℃, pressure according to JIS K 6852
The shear strength was measured. (7) Bonded sun prepared for measurement of normal bonding strength of repeated boiling bonding strength (6)
Regarding pull, repeated boiling test of JISK 6852
It measured based on. EXAMPLE 1 A stirrer and a jacket for temperature control were provided.
70 parts of ion-exchanged water in a pressure-resistant reaction vessel, average particle size of about 15
2.0 parts of an aqueous dispersion (solid content) of a seed having 0 nm,
0.1 parts of sodium lauryl sulfate, 1.5 parts of itaconic acid
, The internal temperature was raised to 85 ℃, 55.5 parts of styrene,
Butadiene 37 parts, hydroxyethyl methacrylate 6
Parts, 0.2 parts of t-dodecyl mercaptan
The mixture was poured over 7 hours. Add the monomer mixture
Almost at the same time, 20 parts of water, sodium lauryl sulfate
0.1 part, sodium hydroxide 0.25 part, peroxo
An aqueous solution consisting of 1.0 part of potassium disulfate over 8 hours
Was added. After the addition is completed, raise the temperature of the reaction system to 85 ° C for about 2 hours.
Then, the polymerization was completed. 98% polymerization conversion of monomer
Met. Then, sodium hydroxide is added to the reaction system.
Adjust the pH to about 6.0 and leave with steam stripping.
Remove the distillate monomer, concentrate by heating under reduced pressure, and cool.
Filter with a filter cloth, and adjust the solid concentration to 50%.
A copolymer latex of Example 1 was obtained. This copolymer latte
When the average particle size of the
nm. The copolymer had a toluene-insoluble content of 9%.
1%. This copolymer latex is treated with polyvinyl alcohol.
Rucol, calcium carbonate, dispersant (hexametaphosphate
Soda) and the base formulation
Compound and then the isocyanate compound
Aqueous vinyl urethane based on the above formulation
An adhesive was obtained. About the obtained aqueous vinyl urethane adhesive
To measure the initial viscosity and the viscosity after standing for 60 minutes.
Evaluation of if, initial bond strength, normal bond strength
And the boiling repetition strength was measured. Table 1 shows these results.
Shown in Examples 2 to 9 Monomers corresponding to Examples 2 to 9 in Table 1
As in Example 1 using the blending composition and the amount of chain transfer agent
The polymerization was performed under the polymerization conditions and polymerization conditions of
A polymer latex was obtained. These copolymers obtained
Measure the toluene-insoluble content and particle size of TEX.
Was. Table 1 shows the measurement results. In addition, these copolymer latte
The same raw material formulation and formulation as in Example 1 using
Vinyl urethane corresponding to each copolymer latex
Adhesives, evaluation of pot life, and initial bond strength
Then, the normal adhesive strength and the repeated boiling strength were measured. this
Table 1 also shows these results. Comparative Examples 1 to 7 Examples of the present invention shown in Comparative Examples 1 to 7 in Table 1.
Monomer composition outside the box, and the copolymer latex insoluble in toluene
In the same polymerization recipe and polymerization conditions as in Example 1.
Obtained by polymerization. These comparative latexes were also
Each copolymer was mixed under the same raw material blending recipe and blending conditions as in Example 1.
Obtain an aqueous vinyl urethane adhesive compatible with Tex
Evaluation of life, initial bond strength, normal bond strength,
The boiling repetition strength was measured. These results are also shown in Table 1.
You. [Table 1] The results of the above Examples and Comparative Examples (Table 1)
Of a specific monomer composition and a specific high gel content
Water produced using the copolymer latex of the present invention having
Vinyl urethane adhesive has excellent pot life
In addition, it has a high initial bond strength and boiling strength
You can see that According to the present invention, the specific monomer composition and the specific range
Using latex copolymer latex with high toluene-insoluble content
Water-based vinyl urethane adhesive has excellent pot life and
Combines high initial bond strength and repeated boiling strength
It has unprecedented performance.

   ────────────────────────────────────────────────── ─── Continuation of front page    F term (reference) 4J040 EF101 EF251 EF301 GA01                       GA03 GA05 GA08 GA11 GA20                       GA22 GA25 KA18 LA06 LA08                       MA08 PA30                 4J100 AB02P AD03R AG15R AJ08S                       AJ09S AL03P AL04P AL09R                       AM02P AM15P AM17P AR16Q                       AS02Q AS03Q AS04Q AS07Q                       FA20 JA03

Claims (1)

Claims: 1. An aliphatic conjugated diene monomer is 20 to 60% by weight, and an ethylenically unsaturated dicarboxylic acid monomer is 0.1 to 5%.
% By weight, 0.1 to 1 hydroxyl group-containing ethylenically unsaturated monomer
5% by weight, and 20 to 20% of other monomers copolymerizable therewith.
A copolymer latex for an aqueous vinyl urethane adhesive, wherein 79.8% by weight of the copolymer is emulsion-copolymerized, and the toluene-insoluble content of the copolymer is 85% by weight or more.