JPH03227304A - Production of copolymer latex and composition using same latex - Google Patents

Abstract

PURPOSE:To obtain the title latex extremely slightly causing a fine coagulated substance, having excellent mechanical stability, blister resistance, bond strength, etc., by subjecting a specific monomer to emulsion polymerization in the presence of a specific unsaturated heterocyclic compound as a polymerization chain transfer agent. CONSTITUTION:A monomer containing (A) 10-70wt.% conjugated diene based monomer (preferably butadiene), (B) 20-89.5wt.% ethylenic unsaturated monomer (preferably styrene) and (C) 0.5-10wt.% ethylenic unsaturated carboxylic acid monomer (e.g. acrylic acid) is subjected to emulsion polymerization in the presence of a compound (preferably 4H-chromene), an unsaturated heterocyclic compound containing C-C double bond in the hetero ring and a hetero ring constituting saturated carbon atom adjoining to the C-C double bond in which the saturated carbon atom contains hydrogen atom to give the objective latex.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is characterized in that the generation of fine coagulum during polymerization is extremely small;
It has excellent mechanical stability, and when used in various applications that utilize adhesive functions, it has excellent adhesive strength and blister resistance.
Furthermore, the present invention relates to a method for producing a copolymer latex that further improves properties specific to various uses, and to paper coating compositions, carpet backing agent compositions, and adhesive compositions that utilize the copolymer latex.

[Prior art] Copolymer latex obtained by emulsion polymerization of monomers containing conjugated diene compounds, (meth)acrylic acid alkyl esters, etc. as essential components has a rubber-like appearance and has an adhesive function. It is widely used in various applications that take advantage of its functions. Such uses include, for example, paper coating compositions, carpet backing compositions, various adhesive compositions, and paints.

Examples include cement modifiers and asphalt modifiers.

In all of these applications, there is a strong demand for improved productivity and higher quality, and for this reason, the conditions for producing and using copolymer latex are becoming stricter. In order to meet these harsh conditions, copolymer latex must be made to minimize the amount of fine coagulation that can cause quality deterioration, to have excellent mechanical stability throughout each process of production and use, and to Most of the various applications in which combined latex is used require a drying process, so it is required that no blistering occurs during high temperature drying (blister resistance) and that it has excellent adhesive strength.

However, conventional copolymer latexes cannot be said to be sufficient in mechanical stability, blister resistance, and adhesive strength of these fine coagulates.

[Problems to be Solved by the Invention] Conventional copolymer latexes are insufficient in the mechanical stability of fine coagulates, blister resistance, and adhesive strength, and the adhesive function of copolymer latexes is insufficient. In the applications in which they are used, there are problems such as the performance specific to the application being not sufficiently improved, and the present invention is intended to solve these problems.

[Means for Solving the Problems] The present inventors have discovered that a copolymer latex obtained by emulsion polymerization of a specific monomer in the presence of a specific unsaturated heterocyclic compound has extremely few fine coagulums. The present inventors have discovered that the mechanical stability, blister resistance, and adhesive strength are further improved, and that when used in various applications, the performance specific to the application is improved, and the present invention has been achieved.

That is, the first invention of the present invention includes (a) conjugated diene monomer 10 to 70% by weight (b)
Ethylenically unsaturated monomer 20-89.5% by weight (c) Ethylenically unsaturated carboxylic acid monomer 0.5-10
% by weight of an unsaturated heterocyclic compound having a carbon-carbon double bond in the heterocycle, the unsaturated heterocyclic compound having a carbon-carbon double bond adjacent to the heterocycle. The present invention relates to a method for producing a copolymer latex, characterized in that emulsion polymerization is carried out in the presence of a compound having at least one saturated carbon atom, and the saturated carbon atom having at least one hydrogen atom.

The second invention of the present invention is characterized in that 100 parts by weight of the pigment and claim (1)
) and 3 to 30 parts by weight (solid content) of a copolymer latex.

The third invention of the present invention is characterized in that 100 parts by weight of the pigment and claim (1)
) Copolymer latex of 3 to 30 parts by weight (solid content).

The fourth invention of the present invention provides at least 3 calcium carbonate.
100 parts by weight of pigment containing 0% by weight and 0.01 part by weight of water-soluble polymer
~10 parts by weight and 5-2 of the copolymer latex shown below
0 parts by weight (solid content), and the solid content concentration is 6
The present invention relates to a paper coating composition characterized in that the content is 0% by weight or more.

Copolymer latex; (a) Conjugated diene monomer 15 to 55% by weight (b)
Ethylenically unsaturated monomer 30-83.5% by weight (c) Ethylenically unsaturated carboxylic acid monomer 0.5-10
Weight% (d) Vinyl cyanide monomer A monomer containing 1 to 30% by weight is added to an unsaturated heterocyclic compound having a carbon-carbon double bond in the heterocycle, wherein the unsaturated heterocyclic compound is , emulsion polymerization in the presence of a compound having at least one saturated carbon atom constituting a heterocycle adjacent to a carbon-carbon double bond, and the saturated carbon atom having at least one hydrogen atom. The resulting copolymer latex.

A fifth invention of the present invention relates to a paper coating composition characterized by containing 100 parts by weight of a pigment and 3 to 30 parts by weight (solid content) of the following copolymer latex.

Copolymer latex; (a) Conjugated diene monomer 10 to 70% by weight (b)
Ethylenically unsaturated monomer 0 to 40% by weight (c) Ethylenically unsaturated carboxylic acid monomer 0.5 to 10%
Weight% (e) Aromatic vinyl monomer 10-65% by weight (f)
A monomer containing 0.1 to 10% by weight of an amide vinyl monomer and/or a hydroxyalkyl-containing (meth)acrylate monomer is used as an unsaturated heterocyclic compound having a carbon-carbon double bond in the heterocycle. and the unsaturated heterocyclic compound has at least one saturated carbon atom adjacent to a carbon-carbon double bond and forming a heterocycle, and the saturated carbon atom has at least one hydrogen atom. copolymer latex obtained by emulsion polymerization in the presence of a compound containing

The sixth aspect of the present invention is (g) a conjugated diene, an acrylic acid alkyl ester having an alkyl group having 2 to 10 carbon atoms, and a conjugated diene having 6 to 1 carbon atoms.
2 to 70% by weight of at least one monomer selected from methacrylic acid alkyl esters having an alkyl group (b) 22 to 98% by weight of an ethylenically unsaturated monomer (c) ethylenically unsaturated carboxylic acid A monomer containing 0 to 8% by weight of a monomer is an unsaturated heterocyclic compound having a carbon-carbon double bond in the heterocycle, wherein the unsaturated heterocyclic compound has a carbon-carbon double bond in the heterocycle. A copolymer that undergoes emulsion polymerization in the presence of a compound having at least one saturated carbon atom constituting a heterocycle adjacent to and in which the saturated carbon atom has at least one hydrogen atom. This invention relates to a method for producing latex.

The seventh invention of the present invention is characterized in that 100 parts by weight (solid content) of the copolymer latex of claim (6) and 30 to 800 parts of the inorganic filler are combined.
Parts by weight of a carpet backing agent composition.

The eighth invention of the present invention is characterized in that the copolymer latex of claim (6) is combined with 10 to 90% by weight (solid content) and 10 to 90% by weight of the thermoplastic polymer.
90% by weight.

The ninth invention of the present invention is characterized in that the copolymer latex of claim (6) 10 to 90% by weight (solid content) and the thermosetting resin 10 to 90% by weight
90% by weight of the adhesive composition.

The present invention will be explained in detail below.

(Monomer components of copolymer latex) (1) First invention 1-(a) Conjugated diene monomer Specific examples of the conjugated diene monomer include butadiene, isoprene, 2-chloro-1 , 3-butadiene, 2-methyl-1,3-butadiene, and the like. These can be used alone or in combination of two or more.

Among these, butadiene is particularly preferred.

The conjugated diene monomer is used to impart appropriate elasticity and film hardness to the obtained copolymer, and the amount used is 10 to 70% by weight, preferably 10 to 70% by weight based on the total monomer. 2
It is selected from the range of 0 to 65% by weight. This usage amount is 10
If it is less than 70% by weight, sufficient adhesive strength cannot be obtained, whereas if it exceeds 70% by weight, water resistance and adhesive strength will decrease, which is not preferable.

1-(b) Ethylenically unsaturated monomer This ethylenically unsaturated monomer is a monomer 1-(
c), and specific examples thereof include aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, and p-methylstyrene, methyl acrylate, ethyl acrylate, butyl acrylate, and acrylic acid. Acrylic acid or methacrylic acid alkyl ester compounds such as 2-hydroxyethyl, 2-hydroxyethyl methacrylate, glycidyl methacrylate, acrylic/L,
Acrylamide or methacrylamide compounds of ethylenically unsaturated carboxylic acids such as 7-amide, methacrylamide, N,N-dimethylacrylamide, N-methylolacrylamide, carboxylic acid vinyl esters such as vinyl acetate, 2-cyanoethyl acrylate, acrylonitrile, methacrylamide, etc. Vinyl cyanide compounds such as lonitrile, α-chloroacrylonitrile, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)
Examples include basic monomers such as acrylate, 2-vinylpyridine, and 4-vinylpyridine. These can be used alone or in combination of two or more. Among these, styrene is particularly preferably used as the aromatic vinyl compound, methyl methacrylate as the alkyl ester compound, and acrylonitrile as the vinyl cyanide compound.

The ethylenically unsaturated monomer is used to impart appropriate hardness, elasticity, and water resistance to the resulting copolymer.
The amount used is 20 to 89.5% by weight based on the total monomer.
, preferably from 20 to 79.5% by weight. If the amount used is less than 20% by weight, the water resistance will be poor, while if it exceeds 89.5% by weight, the copolymer will become too hard.
This is not preferable because the adhesive strength decreases.

1-(c) Ethylenically unsaturated carboxylic acid monomer Specific examples of the ethylenically unsaturated carboxylic acid monomer include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, maleic acid, and fumaric acid.

Examples include dicarboxylic acids such as itaconic acid, and half esters such as methyl maleate, methyl itaconate, and β-methacryloxyethyl acid hexahydrophthalate.

Anhydrides of dicarboxylic acids can also be used.

These can be used alone or in combination of two or more.

The amount of the ethylenically unsaturated carboxylic acid monomer used is 0.5 to 10% by weight, preferably 1 to 7% by weight based on the total monomers.
selected from the range. If the amount used is less than 0.05% by weight, the adhesive strength and mechanical stability of the copolymer latex will decrease, while if it exceeds 10% by weight, the viscosity of the copolymer latex will increase, making handling difficult. This is undesirable because it becomes difficult and the operability decreases.

(2) Fourth invention 2-(a) Conjugated diene monomer This conjugated diene monomer includes the above-mentioned 1-(a)
Compounds similar to can be mentioned. The amount of the conjugated diene monomer used is 15 to 55% by weight, preferably 20 to 55% by weight based on the total monomers. Usage amount is 15% by weight
If it is less than 55% by weight, sufficient adhesive strength will not be obtained, while if it exceeds 55% by weight, water resistance and adhesive strength will decrease.

2-(b) Ethylenically unsaturated monomer This ethylenically unsaturated monomer is monomer 2-(
c) and (d), specific examples include compounds similar to the ethylenically unsaturated monomers of L-(b) mentioned above except for vinyl cyanide compounds. be able to. The amount of such ethylenically unsaturated monomer used is 30 to 83.5% by weight based on the total monomers.
, preferably 30 to 73.5% by weight. Usage amount is 3
If it is less than 0% by weight, water resistance will be poor, while if it exceeds 83.5% by weight, adhesive strength will be poor.

2-(c) Ethylenically unsaturated carboxylic acid monomer This ethylenically unsaturated carboxylic acid monomer includes the above-mentioned 1-
Compounds similar to those shown in (c) can be mentioned. The amount of the ethylenically unsaturated carboxylic acid monomer used is also the same as that of the ethylenically unsaturated carboxylic acid monomer in 1-(c) above.

2-(d) Vinyl cyan monomer This vinyl cyan monomer includes the above-mentioned 1-(b)
Compounds similar to the vinyl cyanide compounds exemplified in the ethylenically unsaturated monomer can be mentioned. The amount of vinyl cyanide monomer used is 1 to 30% by weight, preferably 3 to 25% by weight. If the amount used is less than 1% by weight, print gloss and white paper gloss will be poor;
If it exceeds this, the adhesive strength will decrease.

(3) Fifth invention 3-(a) Conjugated diene monomer This conjugated diene monomer includes the above-mentioned 1-(a)
Compounds similar to the above can be mentioned, and the scope of use thereof is also the same.

3-(b) Ethylenically unsaturated monomer This ethylenically unsaturated monomer is the following monomer 3-(c
), (e), and (f), and specific examples thereof include the above-mentioned 1-(b) excluding aromatic vinyl compounds, amide compounds, and hydroxyalkyl-containing (meth)acrylate compounds. Compounds similar to can be mentioned. The amount of the ethylenically unsaturated monomer used is 0 to 40% by weight, preferably 5 to 30% by weight, based on the total monomers. If the amount used exceeds 40% by weight, the amount of other monomers used will be outside the scope of the present invention, and the object of the present invention will not be achieved.

3-(c) Ethylenically unsaturated carboxylic acid monomer This ethylenically unsaturated carboxylic acid monomer includes the above-mentioned 1-
Compounds similar to (c) can be mentioned, and the range of use is also the same.

3-(e) Aromatic vinyl monomer Examples of the aromatic vinyl monomer include the same aromatic vinyl compounds as in 1-(b) above, and styrene is preferred. The amount of the aromatic vinyl monomer used is 10 to 65% by weight, preferably 30 to 60% by weight, based on the total monomers. If the amount used is less than 10% by weight, water resistance is achieved.

Adhesive strength is poor, and if it exceeds 60% by weight, polymerization stability decreases and coating operability decreases.

8-(1') Amide vinyl monomer and/or hydroxyalkyl-containing (meth)acrylate monomer Examples of the amide vinyl monomer include acrylamide, methacrylamide, N-methylolacrylamide, diacetone acrylamide, and croton. Dialkyl (meth)acrylamides such as amide, itaconamide, methyl itaconamide, maleic acid monoamide, methylene diacrylamide, dimethyl acrylamide, diethyl acrylamide, dimethyl methacrylamide, diethyl methacrylamide, etc., among which acrylamide, methacrylamide, N -Methyloacrylamide, N, N'
-dimethylacrylamide is preferred.

Hydroxy (meth)acrylate monomers are hydroxy-containing acrylates or methacrylates, such as 2-hydroxyethyl acrylate, 2-hydroxymethacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl acrylate,
-Hydroxypropyl methacrylate, 2,3,4,5
．． 6-pentahydroxyhexyl acrylate, 2,3
．． 4゜5.6-pentahydroxyhexyl methacrylate
), 2,3.4.5-tetrahydroxypentyl acrylate, 2,3,4.5-tetrahydroxypentyl methacrylate, etc. Among these, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are preferably used. .

As component 3-(f'), at least one compound selected from the above-mentioned amide vinyl monomers and hydroxy(meth)acrylate monomers is used, but of course, amide vinyl compounds and hydroxy(meth)acrylate monomers are used. ) The acrylates may be used alone or in combination, or two or more of them may be used in combination. In particular, component 3
As -(f), it is preferable to use an amide vinyl compound alone or as a mixture of two or more thereof.

The amount of component 3-(f) used is 0.1 to 1 based on the total monomer.
0% by weight, preferably 1-8% by weight. If the usage ratio is less than 0.1% by weight, an appropriate viscosity cannot be obtained, coating operability is poor, and the effects of improving post-processing performance such as blister pack suitability and pasting properties, as well as printing gloss, are not sufficient.
On the other hand, if it exceeds 10% by weight, the viscosity of the composition becomes too high and the operability deteriorates, which is not preferable.

(4) Sixth invention 4-(g) component is a conjugated diene, an acrylic acid alkyl ester having an alkyl group having 2 to 10 carbon atoms, and a (meth)acrylic acid having an alkyl group having 6 to 14 carbon atoms. It is composed of at least one monomer selected from alkyl esters.

Examples of the conjugated diene monomer include the same compounds as those exemplified for component 1-(a).

Examples of acrylic acid alkyl esters having an alkyl group having 2 to 10 carbon atoms include ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate, and alkyl methacrylates having an alkyl group having 6 to 14 carbon atoms. Examples of the ester include hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, and lauryl methacrylate.

These conjugated diene monomers, acrylic acid alkyl esters, and methacrylic acid alkyl ester monomers can be used alone or in combination of two or more types.

These components 4-(g) are essential components for imparting appropriate flexibility and adhesive strength to the obtained copolymer,
The amount used is 2 to 70% by weight based on the total monomer,
Preferably it is 20 to 65% by weight. If the proportion is less than 2% by weight, the copolymerization flexibility and adhesive strength will be poor, while if it exceeds 70% by weight, the adhesive strength will be poor, and the resulting carpet will be too soft, especially when used in a carpet backing composition. In addition, adhesive strengths such as peel strength and suture removal strength are low, and blister resistance is also poor.

4-(b) Ethyl unsaturated monomer component 4-(b) excludes the alkyl ester compound of 4-(g) above and the monomer of 4-(c) below, for example, Examples include aromatic vinyl compounds, vinyl cyanide compounds, vinyl acetate, acrylamide, and methacrylic acid esters having an alkyl group having 1 to 5 carbon atoms, preferably methyl methacrylate.

Among these, examples of the aromatic vinyl compound and vinyl cyanide compound include the same compounds as those shown in component t-(b) above. These components 4-(b
) may be used alone or in combination of two or more. In particular, copolymerization using methyl methacrylate is preferred because polymerization stability can be significantly improved.

The amount of component 4-(b) used is 2
2 to 98% by weight, preferably 25 to 80% by weight.

If the amount used is less than 2% by weight, the copolymer latex will become too soft, while if it exceeds 98% by weight, it will become too hard, which will not only cause problems in handling and construction, but also result in poor adhesive strength. , furthermore, the blister resistance deteriorates.

4-(c) Ethylenically unsaturated carboxylic acid monomer This ethylenically unsaturated carboxylic acid monomer is the above-mentioned 1-
Compounds similar to (c) can be mentioned. These ethylenically unsaturated carboxylic acid monomers can be used alone or in combination of two or more, but a combination of appropriate amounts of acrylic acid and methacrylic acid is preferred. This ingredient 4
- The amount of (c) used is 0 to 8% by weight based on the total monomer,
Preferably it is 0.5 to 4.5% by weight. When the amount used exceeds 8% by weight, the viscosity of the obtained latex becomes high and it becomes impractical.

(Polymerization chain transfer agent) A feature of the present invention is that a specific unsaturated heterocyclic compound is used as a polymerization chain transfer agent during emulsion polymerization of the above monomer.

The specific unsaturated heterocyclic compound of the present invention (hereinafter referred to as "polymerization chain transfer agent (A)") usually has 4 to 20 carbon atoms, such as 2,5-dihydrofuran, α-bilane, γ
-bilane, 3,6-sihydro-2H-pyran, 2H-chromene, 4H-chromene, xanthine, phthalane, 3H
Examples include indole.

Among these polymerization chain transfer agents (A), those in which one specific carbon atom is directly connected to two carbon-carbon double bonds are particularly preferred, and examples include 4H chromene and xanthine. .

The polymer chain transfer agent (A) has a carbon number of 1 to 10, such as a methyl group, an ethyl group, or a butyl group. Preferably 1-4
may be substituted with an alkyl group.

The above polymer chain transfer agents (A) may be used alone or in combination of two or more.

In the present invention, compounds other than the polymerization chain transfer agent (A) can be used in combination as the polymerization chain transfer agent.

Other polymerization chain transfer agents (hereinafter referred to as "polymerization chain transfer agents (B)") that can be used in combination with the polymerization chain transfer agent (A) include known polymerization chain transfer agents used in general emulsion polymerization. Transfer agents can be used. in particular,
For example, mercaptans such as octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, and t-tetradecyl mercaptan; Disulfides; thiuram disulfides such as tetramethylthiuram disulfide, tetraethylthiuram disulfide, and tetrabutylthiuram disulfide; halogenated hydrocarbons such as carbon tetrachloride and ethylene bromide; hydrocarbons such as pentaphenylethane;
and acrolein, methacrolein, allyl alcohol, 2-ethylhexylthioglycolate, terpinolene, α-terpinene, γ-terpinene, dipentene,
α-methylstyrene dimer (2-4-diphenyl-4-
(preferably 50% by weight or more of methyl-1-pentene), 1,4-dihydronaphthalene, 1,4,5.8-
Tetrahydronaphthalene, 9.10-dihydroanthracene, 1,2,3.4-tetrahydronaphthalene, 1.
4-cyclohexadiene, 1,2-butadiene, 1.4
-hexadiene, etc. These can be used alone or in combination of two or more. Among these, mercaptans, xanthogen disulfides, thiuram disulfide, carbon tetrachloride and the like are preferably used.

The amount of polymerization chain transfer agent used in the present invention is 10
Usually 0.05 to 20 parts by weight, preferably 0
．． It is 1 to 10 parts by weight, more preferably 0.2 to 7 parts by weight. If the amount of the polymerization chain transfer agent used is less than 0.05 parts by weight, blister resistance will be poor, and if it exceeds 20 parts by weight, a large amount of coagulation will occur during emulsion polymerization, making it difficult to produce copolymer latex. becomes difficult.

The proportion of the polymeric chain transfer agent (A) in the polymeric chain transfer agent is usually 2 to 100% by weight, preferably 3 to 100% by weight, and more preferably 5 to 95% by weight.

If the proportion of this polymer chain transfer agent (A) is less than 2% by weight,
It is not possible to obtain a copolymer latex that has excellent adhesive strength and blister resistance, has little generation of fine coagulums, and has excellent mechanical stability. Furthermore, by using the polymerization chain transfer agent (A) in combination with another polymerization chain transfer agent (B), the reactivity during polymerization can be increased.

In the present invention, by using the above-described polymerization chain transfer agent during polymerization of the copolymer latex, the resulting copolymer latex has very little generation of fine coagulation and has good mechanical stability. When used in applications that utilize adhesive functions, it provides excellent adhesive strength and blister resistance, and has the effect of further improving various performances specific to the application.

(Polymerization method 1 Additives during polymerization) The copolymer latex in the present invention can be produced by a conventionally known emulsion polymerization method, except for using the above-mentioned monomers and polymerization chain transfer agent. That is, it is obtained by adding a monomer mixture, a polymerization initiator, an emulsifier 1 polymerization chain transfer agent, etc. to an aqueous medium (usually water) and carrying out emulsion polymerization.

There are no particular limitations on the polymerization initiator used in the emulsion polymerization of the present invention, and examples include hydroperoxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, and para-menthane hydroperoxide;・Organic polymerization initiators such as peroxides such as peroxide, lauroyl peroxide, and azo compounds such as azobisisobutyronitrile, and inorganic persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate. A system polymerization initiator can be used.

In the present invention, when an organic polymerization initiator is used alone, the mechanical stability of the copolymer latex obtained is poor;
Furthermore, since a large amount of coagulated material is generated during polymerization, it is preferable to use an inorganic polymerization initiator alone or in combination with an organic polymerization initiator.

The above polymerization initiator can also be used as a so-called redox polymerization initiator in combination with a reducing agent such as sodium bisulfite.

Among these polymerization initiators, persulfates such as potassium persulfate and ammonium persulfate, a combination of these with azobisisobutyronitrile or benzoyl peroxide, and further a combination of these with a reducing agent are preferably used. be done.

The amount of polymerization initiator used in the present invention is 100% of the total monomer.
It is usually 0.1 to 5 parts by weight, preferably 0.5 to 2 parts by weight. When an inorganic polymerization initiator and an organic polymerization initiator are used together, the proportion of the organic polymerization initiator is preferably 70% by weight or less, more preferably 50% by weight or less of the total polymerization initiator. If the proportion of the organic polymerization initiator exceeds 70% by weight, problems similar to those caused when the organic polymerization initiator is used alone are undesirable.

The emulsifier used in the emulsion polymerization in the present invention is not particularly limited, and any of anionic, nonionic and amphoteric surfactants can be used. These can be used alone or in combination of two or more. For example, anionic surfactants such as sulfate ester salts of higher alcohols such as sodium lauryl sulfate, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, sulfonates of aliphatic carboxylic acid esters such as sodium dioctyl sulfosuccinate, polyethylene Nonionic surfactants such as glycol alkyl ester type, alkylphenyl ether type, and alkyl ether type can be used. In addition, as amphoteric surfactants, carboxylates, sulfate ester salts, sulfonates, phosphates, phosphate ester salts are used as anionic moieties, and amine salts, phosphate ester salts are used as cationic moieties.
Examples include those having quaternary ammonium salts. Specifically, alkyl betaine salts include lauryl betaine, stearyl betaine, cocoamidopropylhetaine, and 2-undecylhydroxyethylimidazolium betaine salts, and amino acid types include lauryl-β-alanine and stearyl-betaine. Salts of β-alanine, lauryl di(aminoethyl)glycine, octyldi(aminoethyl)glycine, and dioctyldi(aminoethyl)glycine can be mentioned.

Among these emulsifiers, alkylbenzene sulfonates are particularly preferably used. More specifically, sodium dodecylbenzenesulfonate and the like are particularly preferably used. This alkylbenzene sulfonate can be used with other surfactants, such as anionic surfactants such as higher alcohol sulfate ester salts, aliphatic carboxylic acid ester sulfonates, or polyethylene glycol alkyl ester, alkyl ether, and alkyl esters. It may be used in combination with a nonionic surfactant such as a phenyl ether type surfactant.

The amount of emulsifier used is usually 0 per 100 parts by weight of total monomers.
．． 0.05 to 2 parts by weight, preferably 0.05 to 1 part by weight. If the amount of emulsifier used exceeds 2 parts by weight, the water resistance will be poor and the paper coating composition will foam significantly, causing problems during coating. In addition, when an alkylbenzene sulfonate is used in combination with another anionic or nonionic surfactant, the proportion of the alkylbenzene sulfonate used is preferably 50% by weight or more of the total emulsifier.

There are no particular limitations on the emulsion polymerization method and conditions in the present invention, and the emulsion polymerization can be carried out under conventionally known methods and conditions.

For example, the method of adding the polymer chain transfer agent may be a batch addition method, a partial addition method, a continuous addition method, or a combination thereof.

The method of adding the monomer mixture may be a batch addition method, a divided addition method, a continuous addition method, or a combination thereof. Among these methods, the divided addition method or the continuous addition method is preferable from the viewpoint of reducing the formation of coagulum and removing the heat of reaction. Furthermore, 10 to 50% by weight of the monomer mixture containing all or a part of the ethylenically unsaturated carboxylic acid monomer is polymerized in the first stage, and 50 to 90% by weight of the remaining monomer mixture is polymerized in the second stage. According to the two-stage polymerization method in which emulsion polymerization is carried out by continuously adding % of the coagulate, the formation of coagulum in the polymerization process can be further reduced, and the paper coating composition targeted by the present invention can be effectively obtained. Therefore, it is preferable to carry out the emulsion polymerization of the present invention by this two-stage polymerization method. In this method, the polymer chain transfer agent may be added to either the first stage or the second stage, or to both stages. When a polymer chain transfer agent is used in the second stage, it is preferably added continuously.

As another polymerization method, a so-called seed polymerization method may be employed in which the monomer of the present invention described above is polymerized in the presence of a seed latex and a polymerization chain transfer agent of the present invention. The monomer composition of the seed latex is preferably from 0.1 to 1-(c) of the monomer component 1-(c).
10% by weight, 50-99.9% by weight of the monomer components 1-(a) and/or 1-(b) and 0-40% by weight of the ethylenically unsaturated crosslinkable monomer, preferably 0.1 ~
It is 40% by weight.

The amount of the seed latex used is preferably 0.05 to 20 parts by weight (solid content) per 100 parts by weight of the monomer polymerized in the presence of the seed latex. When the copolymer latex of the present invention is synthesized by a seed polymerization method,
The desired effects of the present invention can be further improved.

The ethylenically unsaturated crosslinkable monomer is preferably divinylbenzene, ethylene glycoldimectarylate, and trimethylolpropane trimethacrylate,
More preferred is divinylbenzene.

Furthermore, as another polymerization method, 10% by weight or more of the total monomers of the copolymer latex of the present invention and 5% by weight or more of the polymerization chain transfer agent of the present invention are continuously added. It is possible to adopt a polymerization method in which the monomer and the polymerization chain transfer agent are added so that the weight ratio per unit time of the monomer and the polymerization chain transfer agent is continuously changed, and emulsion polymerization is carried out. can.

(Applications of the invention, additives, and others) (1) First invention The copolymer latex according to the first invention can be used in various applications that require an adhesive function, such as gravure printing paper, offset Paper coating compositions for various printing papers such as (rotary) printing paper, letterpress printing paper, and flexo printing paper, paperboard, and cast paper.

In addition to paper coating compositions such as thermal paper, pressure-sensitive paper, and inkjet recording paper, and other various paper coating compositions, carpet backing agent compositions, various adhesives or adhesive compositions, paints, organic materials, Inorganic materials, surface coating agents for metal materials, cement.

Effectively used as a modifier for bituminous materials such as asphalt, foam rubber, etc.

(2) Second invention The second invention is a paper coating composition containing 100 parts by weight of a pigment and 3 to 30 parts by weight (solid content) of the copolymer latex of the first invention. This paper coating composition can sufficiently withstand severe conditions for improving productivity or improving quality in the manufacturing process or printing process of coated paper.
Furthermore, coated paper with excellent adhesive strength and blister resistance can be obtained.

Examples of the pigment include kaolin clay and talc.

Barium sulfate, titanium oxide (rutile anatase).

Calcium carbonate, aluminum hydroxide, zinc oxide.

Inorganic pigments such as satin white and organic pigments such as polystyrene latex can be used. These can be used alone or in combination of two or more.

Examples of binders other than the copolymer latex include natural binders such as starch, oxidized starch, soybean protein, and casein, and synthetic latexes such as polyvinyl alcohol, polyvinyl acetate latex, and acrylic latex.

The paper coating composition of the present invention may further contain various commonly used auxiliaries, such as dispersants (sodium pyrophosphate,
sodium hexametaphosphate, etc.), antifoaming agents (polyglycol, fatty acid ester, phosphate ester, silicone oil, etc.), leveling agents (funnel oil, dicyandiamide,
urea, etc.), preservatives, water resistance agents (formalin, hexamine, melamine resin, urea resin, glyoxal, etc.), mold release agents (calcium stearate, paraffin emulsion, etc.), fluorescent dyes, color retention improvers (carboxymethylcellulose) , sodium alginate, etc.) may be added as necessary.

The paper coating composition of the present invention can be applied by a conventionally known method, for example, using an air knife coater, a plate coater, a roll coater, an applicator, or the like.

(3) Third invention The third invention is a gravure printing paper coating composition containing 100 parts by weight of a pigment and 3 to 30 parts by weight (solid content) of the copolymer latex of the first invention.

This paper coating composition can withstand harsh conditions for improving productivity and quality in the manufacturing process or printing process of coated paper, has excellent adhesive strength, and is suitable for coating gravure printing paper. A coated paper for gravure printing can be obtained which has further improved resistance to calendar roll staining during calendering, which is one of the properties required of a composition, and which has extremely few missed dots during gravure printing.

The pigment, binder, and other additives are the same as in the second invention.

(4) Fourth invention The copolymer latex according to the fourth invention is one in which the type and amount of monomers are limited within the scope of the copolymer latex according to the first invention, and the copolymer latex according to the fourth invention is The invention consists of 5 to 20 parts by weight (solid content) of this limited copolymer latex.
, contains 0.01 to 10 parts by weight of a water-soluble polymer and 100 parts by weight of a pigment containing at least 30% by weight, preferably 50 to 90% by weight of calcium carbonate, and has a solid content concentration of 60% by weight or more. A paper coating composition.

The paper coating composition according to the fourth invention allows good coating even when used at a high solid content concentration. This paper coating composition can withstand harsh conditions for improving productivity and quality in the manufacturing process or printing process of coated paper, and has both adhesive strength and blister resistance. A coated paper of excellent quality and further improved gloss is obtained.

Examples of the water-soluble polymer include modified starch such as oxidized starch, starch, and casein.

Polyvinyl alcohol, sodium alginate carboxymethylcellulose, methylcellulose.

Natural or synthetic water-soluble polymer compounds such as hydroxycellulose can be mentioned, and modified starch is particularly preferred. These water-soluble polymer compounds can be used alone or in combination of two or more.

The calcium carbonate preferably has an average particle size of 5
Calcium carbonate having a particle size of 1 μm or less and soft calcium carbonate having an average particle size of 1 μm or less are used.

The pigment, binder, and other additives are the same as in the second invention.

(5) Fifth invention The copolymer latex according to the fifth invention is one in which the type and amount of monomers are limited within the scope of the copolymer latex according to the first invention, and the copolymer latex according to the fifth invention The invention is based on this limited copolymer latex from 3 to 30 parts by weight (solid content).
and 100 parts by weight of a pigment. This paper coating composition has excellent coating workability in high-concentration coating, and can fully withstand severe conditions for improving productivity and quality in the coated paper manufacturing process or printing process. Furthermore, coated paper with excellent adhesive strength, blister resistance, print gloss, ink receptivity, sizing properties, and blister back suitability can be obtained, making it useful as a paper coating composition for paperboard or gate roll coating. be.

The pigment, binder, and other additives are the same as in the second invention.

(6) Sixth invention The copolymer latex according to the sixth invention can be used in various applications requiring an adhesive function, such as carpet backing agent compositions, various adhesives, or adhesive compositions. including various paper coating compositions, paints,
organic materials, inorganic materials.

Effectively used as a surface coating agent for metal materials.

(7) Seventh invention The seventh invention is the copolymer latex 100 of the sixth invention.
A carpet backing agent composition containing parts by weight (solids) and 30 to 800 parts by weight, preferably 100 to 700 parts by weight, of an inorganic filler.

This carpet backing agent composition can sufficiently withstand the harsh conditions required to increase productivity in the carpet manufacturing process, has extremely low blistering, has excellent texture, and has excellent peel strength and thread removal strength in carpets. A carpet backing agent composition having even better adhesive strength properties such as the following can be obtained.

Next, the inorganic fillers used in the present invention include calcium carbonate, aluminum hydroxide, magnesium hydroxide,
Examples include, but are not limited to, clay, barium sulfate, silicic acid, silicate, titanium oxide, magnesium carbonate, calcium carbonate, and the like.

These inorganic fillers can be used alone or in combination of two or more.

As described above, the carpet backing agent of the present invention contains a copolymer latex and an inorganic filler as components, and if necessary, a dispersant and an antifoaming agent.

Crosslinking agent 1 blowing agent 1 coloring agent, flame retardant, preservative, anti-aging agent, stabilizer, vulcanization accelerator, antistatic agent, pH adjuster, etc. can be added.

(8) Eighth invention The eighth invention is the copolymer latex 10 to 10 of the sixth invention.
90% by weight (solids), preferably 35-65% by weight (
- solid content) and a thermoplastic polymer in an amount of 10 to 90% by weight, preferably 35 to 65% by weight.

The adhesive composition according to the eighth invention can sufficiently withstand severe conditions for improving the workability of the coating process, has extremely little viscosity change and occurrence of blister resistance, etc., and has excellent coating properties. Due to its excellent adhesive strength, it can be usefully used as an adhesive for various materials such as plywood, woodworking, paper and cardboard, cement, and metal.

Examples of the thermoplastic polymer include maleic anhydride/α-olefin copolymer and polyvinyl acetate.

Examples include polyvinyl alcohol, acrylic polymers, thermoplastic polyurethanes, and maleic anhydride/α-olefin copolymers are particularly preferred.

The maleic anhydride/α-olefin copolymer is
It is a product obtained by copolymerizing maleic anhydride with an α-olefin monomer copolymerizable with maleic anhydride, and the α-olefin monomer is preferably an α-olefin having 3 to 10 carbon atoms. α-olefins having 3 to 10 carbon atoms include isobutylene, propylene, 1-butene, 1-pentene, 2
Examples include -hexene, 4-methyl-1-pentene, 1-octene, 1-decene, styrene, and mixtures thereof. Particularly preferred among these α-olefin monomers are styrene and isobutylene.

The adhesive composition of the present invention may optionally include a pH adjuster,
Additives such as fillers, viscosity modifiers, curing agents, and antioxidants can be added. These include, for example, slaked lime;
These include wood flour, wheat flour, casein, ammonium chloride, and phenolic antioxidants.

Slaked lime (pH adjuster and filler) is usually 20 to 60 parts by weight, and ammonium chloride (curing agent) per 100 parts by weight of the copolymer latex (solid content) and thermoplastic polymer.
is usually used in an amount of 0.05 to 0.7 parts by weight per 100 parts by weight of the copolymer latex (solid content) and thermoplastic polymer.

(9) Ninth invention The ninth invention is the copolymer latex 10 to 10 of the sixth invention.
90% by weight (solids), preferably 35-65% by weight (
It is an adhesive composition containing 10 to 90% by weight, preferably 35 to 65% by weight of a thermosetting resin.

The adhesive composition according to the ninth invention shows extremely little deterioration in quality even under severe conditions for improving the workability of the coating process, and further has properties such as oozing contamination prevention property, adhesive strength, and cracking resistance. It has been improved in general and is useful as an adhesive for wood materials.

Examples of the thermosetting resin include melamine resin, urea resin, urea-melamine resin, phenol resin, and epoxy resin, particularly urea resin.

Urea melamine resins are preferred. These can be used alone or in combination of two or more.

Furthermore, the adhesive composition of the present invention can contain the same additives as in the eighth aspect. At this time, the amount of known curing agents such as ammonium chloride and chlorine is usually 0.
05-5 parts by weight are used.

[Example] Hereinafter, the present invention will be explained in more detail with reference to Examples.

Note that "%" and "part" in the examples are based on weight.

(1) First to third inventions (Examples 1 to 8). Comparative Examples 1 to 5> (Production of copolymer latex A-H, ae) 1001
A pressure-resistant reactor was charged with 150 parts of water, and the first-stage components shown in Table 1 (monomer, polymer chain transfer agent, polymerization initiator, emulsifier) were charged, and the mixture was heated at 70°C in a nitrogen atmosphere for 2 hours. Polymerized for hours.

Next, a monomer as a second stage component and a polymerization chain transfer agent were continuously added over 8 hours to carry out polymerization.

Incidentally, the emulsifier as the second stage component was added at once to the mouth 5 hours after the start of addition. Thereafter, in order to complete the polymerization, the reaction was continued for an additional 3 hours, and the polymerization was completed at a polymerization conversion rate of 98%.

After adjusting the pH of the obtained copolymer latex to 7.5 using sodium hydroxide, unreacted monomers were removed by blowing in water vapor, and the solid content concentration was further adjusted to 50% by heating and vacuum distillation. , copolymer latex A-H,a-
I got e. Copolymer latexes A to H belong to the first invention, and copolymer latexes a to e do not belong to the first invention.

Then, the state of generation of fine coagulum and the gel content of the obtained copolymer latex were measured by the following method. The results are shown in Table 2.

Filter 1 kg of the finely coagulated copolymer latex through a 200-mesh wire mesh, measure the amount of coagulated material remaining on the wire mesh, calculate the ratio to the amount of copolymer latex used (in terms of solid content), and perform the following three steps: evaluated.

0: 0.05% or less (less) △: 0.05
~0.1% (slightly more) x more than 0.1% (quite a lot) Gel content After adjusting the copolymer latex to pH 8.0, it was coagulated with isopropanol, washed, and dried.

Next, about 0.3 g of sample was taken and immersed in 100 ml of toluene for 20 hours, and then the toluene insoluble content was measured, and the ratio (%) to the sample was calculated as the gel content.

(Preparation of paper coating composition) A paper coating composition (paint) was prepared using the above copolymer latexes A-H and ae according to the following formulation.

Blended recipe Clay: 80 parts Calcium carbonate 20 parts Copolymer latex
10 parts oxidized starch 5 parts sodium pyrophosphate 0.5 parts water (total solids 6
The resulting paint was evaluated using the following test method. The results are shown in Table 2. The Koto paper used in the test was coated with 20 go of paint using a coating blade on base paper with a basis weight of 64 g/rrr.
It was obtained by coating with d.

(2) Dry picking (indicator of adhesive strength) The degree of picking when printed with the R1 printing machine was visually judged and evaluated using a 5-point scale. The higher the score, the better. The score was expressed as the average value of 6 measurements.

■ Blister resistance After the double-sided printed coated paper was conditioned to humidity (approximately 6%), it was thrown into a heated oil bath and the lowest temperature at which blistering occurred was determined.

(2) Mechanical stability The paint was kneaded between rubber rolls using a gum-up tester, and the time (minutes) until a coagulum was formed on the rubber roll was measured by applying mechanical shear, and evaluated on the following three scales.

O: 30 minutes or more △: 20 minutes or more and less than 30 minutes Good results were obtained. On the other hand, Comparative Examples 1 to 5 were paper coating compositions that did not belong to the second invention, and resulted in insufficient results in any of the properties.

<Example 9.10> Using the polymerization recipe shown in Table 1, polymerization was carried out in the same manner as copolymer latex A of Example 1 to produce copolymer latex (1) belonging to the first invention.

The gel content of this copolymer latex and the state of generation of fine coagulum were examined by the method described above. Table 3 shows the results.
Shown below.

(Preparation of paper coating composition i!) Using the copolymer latex thus obtained! and the same copolymer latex H as in Example 8, a gravure printing paper coating composition was prepared according to the following formulation. I prepared something.

Compounding formula Kaolinite clay (J, M, manufactured by Huber, Hedrosparse)
100 Partial dispersant (manufactured by Toagosei ■, Aron T-40) 0.2 parts Sodium, hydroxide 0.1 part Carboxymethyl cellulose (manufactured by Daiichi Kogyo Seiyaku ■, Celogen PR) 0.3 parts Copolymer latex 8 Part water (added in an appropriate amount so that the total solid content was 60%) Further, an appropriate amount of aqueous sodium hydroxide solution was added to these compositions, and the pH of each composition was adjusted to 9.0. did.

(Preparation of coated paper) Each of the obtained compositions was coated on 54 kg/d coated base paper using an electric blade coater (manufactured by Kumagai Moriage Co., Ltd.) so that the coating amount was 13 ± 0.5 g/rrr on one side. Coat it so that it becomes
Dry in a gear oven at 120°C for 15 seconds. The obtained coated paper was left at room temperature of 20°C and relative humidity of 65% for a day and night, and then subjected to a linear pressure of 250 kg/d and a roll temperature of 50°C.
Super calender treatment was performed four times at ℃, and the following tests were conducted. The results are shown in Table 3.

■ Misdot rate (indicator of suitability for gravure printing) A test piece was printed using a gravure printing testing machine of the Ministry of Finance's Printing Bureau (manufactured by Kumagai Riki Co., Ltd.) using halftone gravure as an illustration. The number of misdots that occurred was defined as a percentage of the number of wire mesh points, and expressed as a percentage. The smaller the numerical value, the better.

■ Drivic (adhesive strength index) Same method as described above.

■ Calendar Roll Stain Resistance Super Calendar is made by overlaying an aluminum sheet on the coated surface of the previous coated paper, passing it through a calendar at 60℃ and 250 kg/cm, then peeling off the coated paper and the aluminum sheet to remove the aluminum sheet. Dirt level and gloss reduction (%)
It was displayed in The smaller the number, the less dirt there is.

Examples 9 and 10 belong to the third invention, and these gravure printing paper coating compositions gave good results in each property.

(2) Fourth invention <Example 11. '12> Using the polymerization recipe shown in Table 4, polymerization was carried out in the same manner as for copolymer latex A in Example 1 to obtain copolymer latexes J and K.

(Preparation of coated paper) Pigments as coating composition components shown in Table 5, water-soluble polymer compound 9 dispersant, copolymer latex, and water for each coating solid content concentration were placed in a Coles dispersion machine. and mixed to obtain a paper coating composition.

These paper coating compositions were coated using a blade coater to form a coating layer of 16g1rd, dried, and then finished using a super calendar to obtain coated paper for measuring the physical properties of coated paper.

The physical properties of the coating composition (paint physical properties) and the physical properties of the coated paper were measured using the following test methods. The test results are shown in Table 5.

■ Viscosity BM type viscometer (60 rpm, No., 4 spindles)
The initial viscosity was measured.

■ High shear viscosity Vercules High Shear Viscometer (8800
rpw+, F bob).

■　Print gloss Measured using a 75″ Murakami gloss meter.

■ Drivic Same method as described above.

■ Using a Wetpick RI printing machine, water is supplied onto the test piece using a Molton roll, and immediately after that, the test piece is printed with tack Nα16, and the degree of picking is visually judged using a 5-point method.

The higher the number, the better.

■ Blister resistance After the double-sided printed coated paper was conditioned to humidity (approximately 6%), it was thrown into a heated oil bath and the lowest temperature at which blistering occurred was determined.

■ Coating properties Coating was performed at a speed of 600 m/min using a blade coater manufactured by Kumagai Riki Kogyo ■, and the difficulty in controlling the coating amount and the degree of streak occurrence were visually judged.

The judgment results were evaluated in the following four stages.

◎: Very good, ○: Good.

△: Inferior. ×: Very poor Examples 11 and 12 are paper coating compositions within the scope of the fourth invention, and the viscosity and high shear viscosity of the paper coating composition are within a range suitable for coating operability. In addition, the desired effects of the present invention were obtained in terms of coatability and physical properties of coated paper.

(3) Fifth invention <Example 13.14> Using the polymerization recipe in Table 4, polymerization was carried out in the same manner as copolymer latex A in Example 1 to obtain copolymer latexes L and M. Ta.

These copolymer latexes L and M were evaluated by the following evaluation method, and the evaluation results are shown in Table 6.

(Preparation of paper coating composition) A coating composition for paperboard was prepared according to the following formulation.

Mixed recipe Clay 60 parts Calcium carbonate 40 parts Copolymer latex (solid content) 16 parts Casein
5 parts water (appropriate amount added so that the total solid content was 60%) (Preparation of coated paper) This coating composition for paperboard was applied under the following conditions to obtain coated paper.

Method Two-rod hand-coated drying: Gear open, 120°C, 30 seconds Calendar Nigelos Calender, 120°C.

80 kg/cm, 1 pass Base paper: Commercially available thick board (220 g/rrr) The properties of the obtained coated paperboard were measured by the following method.

■ Dry pick Same method as described above.

■ Wet Bi Tsuku Same method as described above.

■ White paper gloss It was measured using a Murakami gloss meter (75°75°).

■　Print gloss Same method as described above.

(2) Ink receptivity Determination is made by measuring the degree of ink transfer when dampening water is applied using a Molton roll on an RI printing machine. The higher the concentration, the better. The average value of 6 measurements was displayed.

■ Blank paper suitable for blister bags and printed coated paper are coated with a 1:1 mixture of blister pack adhesive #11 and L juicer (both manufactured by Arayo Toyo Kogyo Co., Ltd.) to a uniform thickness using a coating rod. After coating and further drying, a fixed area of a hard vinyl chloride sheet piece for blister packs is placed on this side, and the back side is pressed with a heat sealer at 150° C. for 5 seconds.

The vinyl chloride sheets were peeled off from a total of 12 test pieces, 6 on the blank side and 6 on the printed side, and the adhesive strength between the coated side of each test piece and the vinyl chloride sheet piece was judged with the naked eye using a 5-point method. Blister bag suitability was expressed as the average score of the test pieces. The printed surface is a solid surface printed using an offset type ink on an RI printing machine.

■ Use a spacer to apply Lifebond AV-650 (manufactured by 8 Eikako Co., Ltd.) to the surface of adhesive coated paper so that the width is 5 mm, the length is 80 m, and the thickness is 0.2 + nm. The same paper was stacked so that the uncoated corrugated surface faced each other, and a load of 2 kg was applied for 1 minute to press the paper, and after removing the pressure, it was left at a constant temperature and humidity of 20° C. and 60% humidity for 24 hours. Thereafter, the coated paper was peeled off, and the adhesive strength was determined visually using a 5-point method based on the state of destruction near the crimped surface, and the average score of the 6-point measurements was expressed as stickiness.

Examples 13 and 14 belong to the fifth invention, and good results were obtained in all characteristics.

(4) Sixth and seventh inventions <Example 15.16> (Production of copolymer latex N, O) The components of the polymerization recipe shown in Table 7 and 150 parts of water were mixed in 1001
200℃ at a polymerization temperature of 40 to 60℃.
The mixture was reacted for a period of time to obtain copolymer latexes N and O belonging to the sixth invention. These copolymer latexes N and O were evaluated by the following evaluation method. Table 8 shows the evaluation results.
It was shown to.

(Preparation of carpet backing agent composition) Copolymer latex 100 parts Sodium tripolyphosphate 1.0 parts Polyoxyethylene nonylphenol ether 0.5 parts Styrenated phenol 1.0 parts Heavy calcium carbonate 350 parts (added last) These After thoroughly dispersing the formulation, the viscosity is 25.0.
00 to 30.000 cps (measured under the conditions of Brookfield viscometer, BM type positive, 4-6rp11), adjusted with thickener and water so that the solid content was 73%, and evaluated using the following various tests. .

■ Peel strength Measured according to JIS L-1021 rug test method.

That is, a backing composition with a solid content concentration of 73% was applied at 1 kg (Net)/rd to a gray fabric made by tufting nylon crimped yarn onto a primary base fabric made of polypropylene, and then 73% of the backing composition was applied as a secondary base fabric. The ounce jute was bonded together by pressure, and after drying at 120° C. for 20 minutes, the peel strength between the secondary base fabric and the gray fabric was measured.

(2) Thread removal strength The pullout strength of one pile was measured according to JIS L-1021 under the same conditions as (2) above.

(2) Texture A carpet prepared under the same conditions as (1) above in accordance with JIS L-1201 was measured using an Olsen type bending tester. The smaller the value, the softer the texture of the carpet.

Examples 15 and 16 are both within the scope of the seventh invention, and a carpet backing agent composition with a soft texture and excellent peel strength and thread extraction strength was obtained.

(5) Sixth and eighth inventions <Example 17.18> (Method for producing copolymer latexes P and Q) 100! Into a pressure-resistant reactor, 80 parts of water, 2 parts of sodium dodecylbenzenesulfonate, 1.5 parts of potassium persulfate, and Table 7
20% of the total monomers and 20% of the total polymerized chain transfer agent shown in
and reacted at 80°C for 3 hours. Next, at a reaction temperature of 80°C, a mixture of the remaining monomers and a polymerization chain transfer agent was continuously added and reacted over 5 hours, and then the reaction was further carried out at 80°C for 5 hours to complete the polymerization. Copolymer latexes P and Q belonging to the invention were obtained.

These copolymer latexes P and Q were evaluated by the following evaluation method, and the evaluation results are shown in Table 9.

(Preparation of adhesive composition) Isobutylene-maleic anhydride copolymer (manufactured by Ripure)
Kurarayisoban-06) 55 parts, sodium hydroxide 1.
After mixing 0 parts and 65 parts of water, the mixture was heated and dissolved at 65°C. After sequentially adding 100 parts of slaked lime and 45 parts of water to this solution and stirring, 45 parts of copolymer latex P and Q were each added in solid content to this solution, and further 0.3 parts of ammonium chloride was added.
The two adhesive compositions were obtained by mixing the two adhesive compositions. This adhesive composition was evaluated using the following evaluation method.

(2) Spreadability (tent method) According to the method for measuring changes in viscosity over time, 500 g of the adhesive composition is charged into a sprayer, rotated at a constant speed, and changes in viscosity over time and workability are measured.

The evaluation criteria are as follows.

O Coating with a Nispletter is uniform, and the coating properties are good. The adhesive was applied to an adherend to prepare a test piece for measuring adhesive strength.

A thickness of 1.8I adjusted to a moisture content of 11 to 13% on the adherend
Using a lauan veneer of l/g, the adhesive composition is applied onto the lauan veneer at a rate of 20 g/rrr using a hand roll, and the same lauan veneer is bonded thereon. Further, the same amount of the adhesive composition was similarly applied thereon and the same lauan veneer was laminated thereon to create a total of three plywood sheets.

The obtained plywood was pressed at room temperature at 10 kg/cd (for plywood) x 5 minutes, and then pressed at 120°C at 10 kg/c4 (
Heat pressure was applied to the plywood for 3 minutes.

After curing at room temperature for 20 hours, the test piece was cut into dimensions stipulated in the Japanese Agricultural Standards for general purpose boards, and used as test pieces.

The test is specified in the Japanese Agricultural Standards for general purpose boards.

a) Ordinary state adhesion test b) Type 1 immersion peel test (boiling water) c) Type 2 immersion peel test (hot water at 70°C) The test machine used was a plywood tensile tester manufactured by Toyo Shinken Co., Ltd. The peeling was also carried out at a peeling rate of 50 mm/min.

In addition, the state of wood damage was examined during the above tests a) to C).

Wood chips refer to a state in which wood chips from the adherend stick to the peeling surface and peel off when measuring adhesive strength.The value is expressed as a ratio (%) of the area of the wood chips to the adhesive area. , the larger the value,
Indicates excellent adhesive strength.

Examples 17 and 18 are adhesive compositions that fall within the scope of the eighth invention, and good results were obtained in all properties.

(6) Ninth invention <Example 19.20> Copolymer latex P belonging to the sixth invention shown above,
Evaluation was performed using Q using the following evaluation method, and the evaluation results are shown in Table 10.

Copolymer latex P or Q 55 parts (solid content), 45 parts of a resin mixture containing urea resin and urea melamine resin at a ratio (%) of 90=10, 30 parts of wheat flour, and 20 parts of water were mixed, and further chlorinated. Add 0.5 part of ammonium,
Two types of adhesive compositions were obtained by mixing these. Physical property tests were conducted on these adhesive compositions by the method shown below, and the test results are shown in Table 10.

(Preparation of test samples) The obtained adhesive composition was applied to a 4 mm thick 3-braira one plywood board in an amount corresponding to the following test items, and the coated surface was coated with veneer panels in order of thickness of 0.3 mm. The plates were stacked within 5 minutes, and after being deposited for an additional 10 minutes, they were hot pressed under the conditions of a compacting pressure of 5 kg/cm, a compacting temperature of 110° C., and a compacting time of 60 seconds. This was further cured at room temperature for 20 hours, and the resulting decorative plywood veneer was cut into dimensions specified in the Japanese Agricultural Standards to obtain test pieces.

Application weight 10 g/900 c- and 15 g/90
0 cd (Test item: Prevention of oozing contamination.

Type 2 immersion peeling test) 12 g/900 cd (Test item: Cold/heat cycling test) The following physical property tests were conducted on these test pieces.

(2) Test for preventing oozing contamination The oozing state of the adhesive composition on the surface of the veneer veneer of the test piece was visually evaluated. The evaluation criteria are as follows.

O: No oozing Δ: Slight oozing ×: There is oozing ■ Drought cracking resistance test (cold/heat cycling test) This test was conducted in accordance with the Japanese Agricultural Standards for ordinary plywood. That is, after fixing the test piece cut to a size of 15 cm square with a metal frame, it was left in a thermostat at 80 ± 3°C for 2 hours, and then left in a thermostat at -20 ± 3°C for 2 hours. .

Evaluation is done by visually observing the dry cracks on the surface. The evaluation criteria are as follows.

O: No cracks observed △: Slightly observed X: Quite acceptable ■ Adhesive strength test Same as evaluation method (5) above.

Examples 19 and 20 are within the scope of the ninth invention, and good results are obtained in each characteristic.

[Effects of the Invention] The copolymer latex of the present invention obtained by polymerization in the presence of a specific polymerization chain transfer agent has extremely low generation of fine coagulation, excellent mechanical stability, and good adhesive function. Because of this, when used in various applications utilizing this function, it has excellent adhesive strength and blister resistance, and further improves the performance specific to various applications. objects, various adhesives,
Paints, cement improvers, asphalt improvers, foam rubber sealants, inorganic materials, organic materials.

It is useful as a coating agent for materials such as metals.

Claims (1)

[Claims] (1) (a) Conjugated diene monomer 10 to 70% by weight (b) Ethylenically unsaturated monomer 20 to 89.5% by weight (c) Ethylenically unsaturated carboxylic acid monomer 0.5 to 10% by weight of an unsaturated heterocyclic compound having a carbon-carbon double bond in the heterocycle, the unsaturated heterocyclic compound having a carbon-carbon double bond in the heterocycle. A copolymer which is emulsion polymerized in the presence of a compound having at least one saturated carbon atom constituting a heterocycle adjacent to a bond, and in which the saturated carbon atom has at least one hydrogen atom. Method of manufacturing coalesced latex. (2) A paper coating composition comprising 100 parts by weight of a pigment and 3 to 30 parts by weight (solid content) of the copolymer latex of claim (1). (3) A gravure printing paper coating composition comprising 100 parts by weight of a pigment and 3 to 30 parts by weight (solid content) of the copolymer latex of claim (1). (4) Contains 100 parts by weight of a pigment containing at least 30% by weight of calcium carbonate, 0.01 to 10 parts by weight of a water-soluble polymer, and 5 to 20 parts by weight (solid content) of a copolymer latex shown below. A paper coating composition having a solid content concentration of 60% by weight or more. Copolymer latex; (a) Conjugated diene monomer 15-55% by weight (b) Ethylenically unsaturated monomer 30-83.5% by weight (c) Ethylenically unsaturated carboxylic acid monomer 0. 5 to 10% by weight (d) Vinyl cyanide monomer A monomer containing 1 to 30% by weight is an unsaturated heterocyclic compound having a carbon-carbon double bond in the heterocycle, The ring compound is
A compound obtained by emulsion polymerization in the presence of a compound having at least one saturated carbon atom constituting a heterocycle adjacent to a carbon-carbon double bond, and in which the saturated carbon atom has at least one hydrogen atom. copolymer latex. (5) 100 parts by weight of pigment and the following copolymer latex 3
30 parts by weight (solid content). Copolymer latex; (a) Conjugated diene monomer 10 to 70% by weight (b) Ethylenically unsaturated monomer 0 to 40% by weight (c) Ethylenically unsaturated carboxylic acid monomer 0.5 to 70% by weight Monomer containing 10% by weight (e) aromatic vinyl monomer 10 to 65% by weight (f) amide vinyl monomer and/or hydroxyalkyl-containing (meth)acrylate monomer 0.1 to 10% by weight at least one unsaturated heterocyclic compound having a carbon-carbon double bond in the heterocycle, wherein the unsaturated heterocyclic compound is adjacent to the carbon-carbon double bond and constitutes a heterocycle. A copolymer latex obtained by emulsion polymerization in the presence of a compound having one saturated carbon atom, and the saturated carbon atom having at least one hydrogen atom. (6) (g) Conjugated diene, acrylic acid alkyl ester having an alkyl group having 2 to 10 carbon atoms, and 6 to 1 carbon number
2 to 70% by weight of at least one monomer selected from methacrylic acid alkyl esters having an alkyl group (b) 22 to 98% by weight of an ethylenically unsaturated monomer (c) ethylenically unsaturated carboxylic acid A monomer containing 0 to 8% by weight of a monomer is an unsaturated heterocyclic compound having a carbon-carbon double bond in the heterocycle, wherein the unsaturated heterocyclic compound has a carbon-carbon double bond in the heterocycle. A copolymer that undergoes emulsion polymerization in the presence of a compound having at least one saturated carbon atom constituting a heterocycle adjacent to and in which the saturated carbon atom has at least one hydrogen atom. Latex manufacturing method. (7) A carpet backing composition comprising 100 parts by weight (solid content) of the copolymer latex according to claim 6 and 30 to 800 parts by weight of an inorganic filler. (8) An adhesive composition comprising 10 to 90% by weight (solid content) of the copolymer latex of claim (6) and 10 to 90% by weight of a thermoplastic polymer. (9) An adhesive composition comprising 10 to 90% by weight (solid content) of the copolymer latex of claim (6) and 10 to 90% by weight of a thermosetting resin.