JPH038896A - Production of copolymer latex and composition using same - Google Patents

Abstract

PURPOSE:To obtain the title latex developing no fine flocs, excellent in mechanical stability by emulsion polymerization, in the presence of specific disulfide compound, of a monomer mixture comprising a conjugated diene monomer, ethylene-based unsaturated monomer and ethylene-based unsaturated carboxylic acid monomer at specified proportion. CONSTITUTION:The objective latex can be obtained by emulsion polymerization, in the presence of at least one disulfide compound selected from dimethyl xanthogen disulfide, diethyl xanthogen disulfide and thiuram disulfide, of a monomer mixture comprising (A) 10-70 (pref. 0-65) wt.% of a conjugated diene monomer (pref. butadiene), (B) 20-89.5 (pref. 20-79.5) wt.% of am ethylene-based unsaturated monomer (pref. styrene, methyl methacrylate or acrylonitrile) and (C) 0.5-10 (pref. 1-7) wt.% of an ethylene-based unsaturated carboxylic acid monomer [e.g. (meth)acrylic acid].

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 scale applications that utilize this function. Such uses include, for example, paper coating compositions, carpet backing compositions, various adhesive compositions, cement modifiers, asphalt modifiers, and the like.

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 properties of fine coagulation, mechanical stability, blister resistance, and adhesive strength, and it is necessary to utilize the adhesive function of copolymer latexes. There are problems in the application in which the performance specific to the application is 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 disulfide compound has extremely few fine coagulates and is mechanically resistant. The present inventors have discovered that the 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 provides: (a) Conjugated diene monomer 10 to 7 OffQ% (
b) Ethylenically unsaturated monomer 20 to 89.51% by weight (c) Ethylenically unsaturated carboxylic acid monomer 0.5 to 10%
The monomer containing 1ffi% of dimethylxanthogen disulfide,
The present invention relates to a method for producing a copolymer latex, which comprises carrying out emulsion polymerization in the presence of at least one disulfide compound selected from diethylxanthogen disulfide and thiuram disulfide.

The second invention of the present invention is a pigment 100. The present invention relates to a paper coating composition comprising: iTf parts and 3 to BCJ mm parts (solid content) of the copolymer latex of claim (1).

The third 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 the copolymer latex.

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
~], 0 weight 1 part and the copolymer latex shown below 5~
20 parts by weight (solid content), 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 30-83.5ffl2% (c) Ethylenically unsaturated carboxylic acid monomer 0.5-10
Weight% (d) Vinyl cyanide monomer A monomer containing 1 to 30% by weight is emulsion polymerized in the presence of at least one disulfide compound selected from dimethylxanthogen disulfide, diethylxanthogen disulfide, and thiuram disulfide. 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 10-70m2% (b)
Ethylenically unsaturated monomer 0-40% by weight) Ethylenically unsaturated carboxylic acid monomer 0.5-10%
Weight) Aromatic vinyl monomer 10-65% by weight (f)
Amide vinyl monomer and/or hydroxyalkyl-containing (meth)acrylate monomer 0.1 to 10fff
% monomer containing dimethylxanthogen disulfide,
A copolymer latex obtained by emulsion polymerization in the presence of at least one disulfide compound selected from diethylxanthogen disulfide and thiuram disulfide.

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 Monomers containing 0 to 8% by weight of dimethylxanthogen disulfide,
The present invention relates to a method for producing a copolymer latex, characterized in that emulsion polymerization is carried out in the presence of at least one disulfide compound selected from diethylxanthogendisulfide and thiuram disulfide.

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 to third inventions 1-(a) Conjugated diene monomer Specific examples of the conjugated diene monomer include butadiene, isoprene, 2- Examples include chloro-1,3-butadiene and 2-methyl-1,3-butadiene. −
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. Alkyl ester compounds of acrylic acid or methacrylic acid such as 2-hydroxyethyl, 2-hydroxyethyl methacrylate, glycidyl methacrylate, ethylenically unsaturated compounds such as acrylamide, methacrylamide, N,, N-dimethylacrylamide, N-methylolacrylamide, etc. Acrylamide or methacrylamide compounds of carboxylic acids, vinyl carboxylic esters such as vinyl acetate, vinyl cyanide compounds such as 2-cyanoethyl acrylate, acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, dimethylaminoethyl (
Examples include basic monomers such as meth)acrylate, diethylaminoethyl (meth)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 the range of 20 to 79.5% by weight. If the amount used is less than 2% by weight of OffI, the water resistance will be poor, while if it exceeds 89.5% by weight, the copolymer will become too hard and the adhesive strength will decrease, which is not preferable.

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 of methyl maleate, methyl itaconate, and β-methacryloxyethyl acid hexahydrophthale-1.kasa.

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 1.0% based on the total monomers. omm%, preferably 1-7% by weight
selected from the range. If the amount used is less than 0.5 wt.26, the adhesive strength and mechanical stability of the hem-coalesced latex will decrease; If it exceeds 6, the viscosity of the copolymer latex becomes high, making it difficult to handle and handling, which is not preferable.

(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.

If the amount used is less than 15% by weight, sufficient adhesive strength will not be obtained, while if it exceeds 55% by weight, water repellency 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 mentioned above in 1-(b) except for the vinyl cyanide compound. be able to. The amount of such ethylenically unsaturated monomer used is 30 to 83.
5% by weight, preferably 30-73.5% by weight. If the amount used is less than 30% by weight, water resistance will be poor;
．． If it exceeds 5% by weight, the adhesive strength will be poor.

2-(c) Ethylenically unsaturated carboxylic acid monomer This ethylenically unsaturated carboxylic acid monomer is 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 Kal-(c).

2-(d) Vinyl cyan monomer This vinyl cyan monomer includes the above-mentioned 1-(b)
Compounds similar to the vinyl cyanide compounds exemplified as 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
), (o), (f),
Specific examples thereof include compounds similar to the above-mentioned 1-(b) except that the aromatic vinyl compound, amide compound, and hydroxyalkyl-containing (meth)acrylate compound are removed. 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,
The purpose of the present invention cannot 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 t-(b) above, and styrene is preferred. The amount of the aromatic vinyl monomer to be used is 10 to 65% by weight, preferably i;!, based on the total monomers. It is 30-60fflEt%. 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.

3-(r) Amide vinyl monomer and/or hydroxyalkyl-containing (meth)acrylate monomer Examples of the amide vinyl monomer include acrylamide, methacrylamide, N-methylolacrylamide, diacetone acrylamide, and crotonamide. , itaconamide,
Examples include dialkyl (meth)acrylamides such as methyl itaconamide, maleic acid monoamide, methylene diacrylamide, dimethyl acrylamide, diethyl acrylamide, dimethyl methacrylamide, and diethyl methacrylamide, among which acrylamide, methacrylamide, N-methylolacrylamide, 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 methacrylate, 2,3,4,
5.6-pentahydroxyhexyl acrylate, 2,
Examples include 3,4゜5.6-pentahydroxyhexyl methacrylate, 2,3,4.5-tetrahydroxypentyl acrylate, 2,3,4.5-tetrahydroxypentyl methacrylate, among which 2-hydroxyethyl Acrylate, 2-hydroxyethyl methacrylate is preferably used.

As component 3-(r), 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. Acrylates may be used alone or in combination, or two or more types may be used in combination. In particular, component 3-
As (r), it is preferable to use an amide vinyl compound alone or as a mixture of two or more thereof.

The amount of component 3-(1') used is 0.1 to 0.1 to the total monomer.
10% by weight, preferably 1-8% by weight. If this usage ratio is less than 0.1% by weight, an appropriate viscosity cannot be obtained,
Coating runnability is poor, and the effects of improving post-processing performance such as blister pack suitability and sizing properties, as well as printing gloss, are insufficient.On the other hand, if it exceeds 10% by weight, the viscosity of the composition becomes too high, leading to poor runnability. This is not preferable because it reduces the

(4) Sixth invention 4-<g) Components include 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 in component 1-(a) above.

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. As an ester, hexyl methacrylate 2
Examples include 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%. 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 agent composition. Furthermore, the adhesive strength such as peel strength and suture removal strength is low, and the blister resistance is also poor.

4-(b) Ethylenically 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, the aromatic vinyl compounds and vinyl cyanide compounds include the same compounds (1) as shown in component t-(b) above.These components 4-(
+)) 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, causing problems in handling and construction, and resulting in poor adhesive strength. , furthermore, the blister resistance deteriorates.

4-(c) Ethylenically unsaturated carboxylic acid monomer The ethylenically unsaturated carboxylic acid monomer mentioned in 1. Ta1
- Compounds similar to (c) can be mentioned. These ethylenically unsaturated carboxylic acid monomers can be used alone or in combination of two or more types, but a combination of appropriate amounts of acrylic acid and methacrylic acid is preferred. The amount of component 4-(c) used is 0 to 8% by weight, preferably 0.5 to 4.5% by weight, based on the total monomers. When the amount used exceeds 8% by weight, the viscosity of the obtained latex becomes high and it becomes impractical.

(Polymerization chain transfer agent) The present invention is characterized in that (A) at least one compound selected from dimethylxanthogen disulfide, diethylxanthogen disulfide, and thiuram disulfide (
A polymeric chain transfer agent (hereinafter referred to as (A)), preferably this polymeric chain transfer agent (A) and another polymeric chain transfer agent, such as a compound of at least IF selected from alkyl mercaptans and carbon tetrachloride, are used. At the point.

Although it is known that xanthogen disulfides can be used as polymerization chain transfer agents, generally only diisopropyl xanthogen disulfide is used (see, for example, JP-A-50-107030). However, according to the research conducted by the present inventors, for the purpose of the present invention to obtain a copolymer latex with even better adhesive strength and blister resistance, among the xanthogen disulfides, dimethylxanthogen disulfide and diethyl xanthogen disulfide is more effective than diisopropylxanthogen disulfide and dimethylxanthogen disulfide and/or as a polymerization chain transfer agent.
Alternatively, by using diethylxanthogen disulfide, the purpose of the present invention is to achieve extremely low generation of fine coagulates, excellent mechanical stability, and adhesive strength.
It has been found that a copolymer latex with excellent blister resistance can be obtained.

Furthermore, it is known that thiuram sulfides can also be used as polymerization chain transfer agents in emulsion polymerization, but generally only tetraethylthiuram monosulfide or dipentamethylene lentithuram hexasulfide is used (for example, in particular Publication No. 57-153012, Publication No. 61-207694, Publication No. 81-6379
(Refer to Publication No. 4), thiuram disulfide can be used as a polymerization chain transfer agent, and when used as a polymerization chain transfer agent, the generation of fine coagulates is extremely small and mechanical stability is improved, which is the objective of the present invention. There is no mention in any of these documents that a copolymer latex with excellent adhesive strength and blister resistance can be obtained. By using this thiuram disulfide, the generation of fine coagulation is extremely small, which is the objective of the present invention.
The present inventors have newly discovered that it is possible to obtain a co-m combination latex which has excellent mechanical stability and even better adhesive strength and blister resistance.

The thiuram disulfide used in the present invention has the following general formula (
I): (Here, R is an alkyl group having 1 to 6 carbon atoms and may be the same or different, and two R's bonded to the same nitrogen atom are bonded to each other to form a ring having 1 to 5 carbon atoms. Specific examples thereof include tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, and dipentamethylenethiuram disulfide. Among these, tetraethylthiuram disulfide is particularly preferably used.

The polymer chain transfer agent to be used in combination with the polymer chain transfer agent (A) is not particularly limited, but examples include octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-tetradecyl mercaptan, t-
Examples include alkyl mercaptans such as tetradecyl mercaptan and n-hexadecyl mercaptan, carbon tetrachloride, α-methylstyrene dimer, and turbinolene, which may be used alone or in combination of two or more.

Specific examples of combinations when the polymerization chain transfer agent (A) and other polymerization chain transfer agents are used together include, for example, diethylxanthogen disulfide/tetraethylthiuram disulfide, diethylxanthogen disulfide/carbon tetrachloride, diethylxanthogen disulfide/l -Dodecylmercaptan, tetraethylthiuram disulfide/
Carbon tetrachloride, tetraethylthiuram disulfide/1-
Examples include dodecyl mercaptan.

Particularly preferred are tetraethylthiuram disulfide/carbon tetrachloride and tetraethylthiuram disulfide/l-dodecylmercaptan.

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, the blister resistance will be poor, and if it exceeds 2 parts by weight, a large amount of coagulation will occur during emulsion polymerization, making it difficult to produce the copolymer latex. becomes difficult.

In addition, the polymerization chain transfer agent (A) may be used alone, or when the polymerization chain transfer agent (A) and another polymerization transfer agent (B) are used together, the usage ratio of (B) is the total polymerization chain transfer agent. 5-9
5% by weight, preferably 10-90% by weight. (B)
If the amount is less than 5% by weight or exceeds 95% by weight, no effect of the combined use will be obtained, and the objectives of the present invention, such as improvements in mechanical stability, adhesive strength, and blister resistance, will not be achieved.

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 9 Additives during Polymerization) The copolymer latex in the present invention can be produced by a conventionally known emulsion polymerization method, except that the above-mentioned monomers and polymerization chain transfer agents are used. That is, it is obtained by adding a monomer mixture, a polymerization initiator, an emulsifier, a 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, such as cumene hydroperoxide, diisopropylbenzene hydroperoxide,
Hydroperoxides such as paramenthane hydroperoxide, peroxides such as benzoyl peroxide and lauroyl peroxide, and organic polymerization initiators such as azo compounds such as azobisisobutyronitrile, as well as potassium persulfate and peroxide. Inorganic polymerization initiators such as persulfates such as sodium sulfate and ammonium persulfate 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 1.0
It is usually 0.1 to 5 parts by weight, preferably 0.5 to 2 parts by weight per 0 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, Nonionic surfactants such as polyethylene glycol alkyl ester, alkylphenyl ether, and alkyl ether types can be used. In addition, as amphoteric surfactants, carboxylates, sulfate ester salts, sulfonates, phosphates, and phosphate ester salts are used as the anionic moiety, and amine salts and quaternary ammonium salts are used as the cationic moiety. I can list things I have. Specifically, alkyl betaine salts include lauryl betaine, stearyl betaine, cocoamidopropyl betaine, and 2-undecylhydroxyethylimidazolium betaine salts, and amino acid types include lauryl-β-alanine and stearyl-β. -alanine,
Lauryl di(aminoethyl)glycine, octyldi(aminoethyl)glycine, dioctyldi(aminoethyl)
Mention may be made of the salts of glycine.

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 sulfate ester salts of higher alcohols, sulfonate salts of aliphatic carbonic acid esters, or alkyl esters, alkyl ethers, and alkyl esters of polyethylene glycol. 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 divided 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, preferably 0.1% by weight of the ethylenically unsaturated crosslinkable monomer. 1
~40% by weight.

The amount of 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 mashing method, the desired effects of the present invention can be further improved.

The ethylenically unsaturated crosslinkable monomer is preferably divinylbenzene, ethylene glycol dimectarylate and trimethylolpropane trimethacrylate, more preferably divinylbenzene.

Furthermore, as another polymerization method, 10 monomers or more of all the 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 and polymerized. In addition, a polymerization method can be employed 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.

(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, It is effectively used as a surface coating agent for inorganic materials and metal materials, a modifier for bituminous substances such as cement and asphalt, and foam rubber.

(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 fully withstand the harsh conditions for improving productivity and quality in the printing process of coated paper manufacturing process C1, and has both adhesive strength and blister resistance. Excellent coated paper is obtained.

As the pigment, inorganic pigments such as kaolin clay talc, barium sulfate, titanium oxide (rutile anatase), calcium carbonate, aluminum hydroxide, zinc oxide, and 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 birophosphate,
Sodium hexametaphosphate, etc.), antifoaming agents (polyglyfur, fatty acid esters, phosphate esters, silicone oil, etc.), leveling agents (funnel oil, dicyandiamide, urea, etc.), preservatives, water resistance agents (formalin, hexamine, melamine resin, urea resin, glyoxal, etc.)
, a mold release agent (calcium stearate, paraffin emulsion, etc.), a fluorescent dye, a color retention improver (carboxymethyl cellulose, sodium alginate, etc.), etc. can be added as necessary.

The paper coating composition of the present invention can be applied by a conventionally known method using, for example, an air knife coater, blade coater, roll coater 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 performance requirements of the 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 monomer rods and the amount thereof are limited within the scope of the copolymer latex according to the first invention. The invention uses 5 to 20 parts by weight (solid content) of this limited copolymer latex.
, 1 part of a water-soluble polymer from 0.01 to 10IIIj, and at least 30ff of calcium carbonate! amount%, preferably 5
Contains 100 parts by weight of a pigment containing 0 to 90% by weight,
The paper coating composition also has a solid content concentration of 60% by weight or more.

The coating composition for filter paper according to the fourth aspect of the invention can be coated well even when used at a high solid content concentration. Part 1 - This paper coating composition is used in the manufacturing process or printing process of coated paper.
It can sufficiently withstand harsh conditions for improving productivity or improving quality, and can provide coated paper with excellent adhesive strength and blister resistance, and further improved gloss.

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 as IFIi or a 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.

Pigments, binders, and other additives are the same as in the second invention.

(5) Fifth invention The copolymer latex in the fifth invention is one in which the monomer g and its amount are limited within the scope of the copolymer latex according to the first invention. The invention uses 3 to 30 parts by weight (solid content) of this limited copolymer latex.
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, printing gloss, ink retardation, sizing properties, and blister back suitability can be obtained, making it useful for paper coating compositions for paperboard or gate roll coating. It is.

Pigments, binders, 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 latte sox 10 of the sixth invention.
0 parts by weight (solid content) and 30 to 800 parts by weight of inorganic filler,
Preferably, the carpet backing agent composition contains 100 to 700 parts by weight.

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 mainly contains a copolymer latex and an inorganic filler, but if necessary, it may further include a dispersant, an antifoaming agent, a crosslinking agent, a foaming agent, a coloring agent, Flame retardants, preservatives, anti-aging agents, stabilizers, vulcanization accelerators, antistatic agents, pi adjusters, 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 (
It is an adhesive composition containing 10 to 90% by weight, or 35 to 65% by weight, of a thermoplastic polymer (solid content) and a thermoplastic polymer.

The adhesive composition according to the eighth invention can sufficiently withstand severe conditions for improving the workability of the coating process, has extremely low occurrence of viscosity change and blistering resistance, and has excellent coating properties. Furthermore, since it has excellent adhesive strength, it can be usefully used as an adhesive for various materials such as plywood and 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.

Additives such as a PL+ adjuster, a filler, a viscosity modifier, a curing agent, and an antioxidant can be added to the adhesive composition of the present invention, if necessary. These include, for example, slaked lime, wood flour, wheat flour, casein, ammonium chloride, phenolic antioxidants, and the like.

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 exhibits extremely little deterioration in quality even under severe conditions for improving the workability of the coating process, and furthermore has excellent properties such as oozing contamination prevention [warming resistance, joint strength, dry cracking resistance, etc.] It has generally improved properties 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 per 100 parts by weight of the thermosetting resin and copolymer latex.
．． 05-5 parts by weight are used.

(Hereafter, margin) [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 16). Comparative Examples 1 to 8> (Production of copolymer latex A-P, ah) 1001
After charging 150 parts of water into a pressure-resistant reactor, and further charging the first-stage components shown in Table 1 (monomer 1 polymer chain transfer agent 1 m polymerization initiator, emulsifier), the reactor was heated at 70°C in a nitrogen atmosphere for 2 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.

In addition, 5 hours after the start of the addition, one component of the emulsifier was added in two stages at once.After that, in order to complete the polymerization, three additional emulsifiers were added.
The reaction was continued for a period of time, 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 adjusted to 50% by heating and vacuum distillation. A polymer latex A-Pa-h was obtained. Copolymer latex A-P belongs to the first invention,
Copolymer latexes a to h do not belong to the first invention.

Then, the amount of coagulated material and gel content of the obtained copolymer latex were measured by the following method. The results are shown in Table 2.

Coagulation amount: Filter 1 kg of copolymer latex through a 200-mesh wire mesh, measure the amount of coagulation remaining on the wire mesh, calculate the ratio to the amount of copolymer latex used (in terms of solid content), and evaluate on the following three levels. did.

0: 0.05% or less (less) △: 0.05
~0.1% (slightly high) X: Over 0.1% (
After adjusting the gel content to pi 8.0, the copolymer latex was coagulated with isopropanol, washed, and dried.

Next, a sample of about O, S fr was taken, and after immersed in 100 ml of toluene for 20 hours, the toluene insoluble content was measured, and the ratio (%) to the sample was determined to be the gel content.

(Preparation of paper coating composition) The above copolymer latex A-P, a = h
A paper coating composition (paint) was prepared using the following formulation.

Mixed recipe Clay 80 parts Calcium charcoal 20 parts Copolymer latex 10 parts Oxidized starch 5 parts Sodium birophosphate 0.5 parts Water
The paint obtained in an amount with a total solids content of 60% was evaluated by the following test method. The results are shown in Table 2. The coated paper used in the test was obtained by applying the paint to a base paper with a basis weight of 64 g/rrr using a coating blade at a coating weight of 20 g/rrf'.

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

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

■ Mechanical stability The paint was kneaded between rubber rolls using a gum-up tester, mechanical shear was applied, and the time (minutes) until coagulation appeared on the rubber roll was measured and evaluated on the following three scales.

O: 30 minutes or more 6120 to less than 30 minutes was gotten. On the other hand, Comparative Examples 1 to 8 were paper coating compositions that did not belong to the second invention, and resulted in insufficient results in any of the properties.

<Example 17.18> Using the polymerization recipe shown in Table 1, polymerization was carried out in the same manner as for copolymer latex A in Example 1 to produce copolymer latexes Q and R. The gel content of these copolymer latexes was 95% for copolymer latex Q and 90% for copolymer latex R.

(Preparation of paper coating composition) Using each of the copolymer latexes Q and R obtained in this way, a gravure printing paper coating composition was prepared according to the following formulation.

Compounding recipe Kaolinite clay (manufactured by J, M, IIuber, Hydrosperse) 100 Partial dispersant (manufactured by Toagosei ■, Aron T-40) 0.2 parts Sodium hydroxide 0.1 part Carboxymethyl cellulose (Daiichi Kogyo Seiyaku) 0.3 parts copolymer latex 8 parts water (appropriate amount added so that the total solids content is 60%) To these compositions, an appropriate amount of sodium hydroxide aqueous solution was further added. The pH of each composition was adjusted to 9.0.

(Preparation of coated paper) Each of the obtained compositions was applied to coated base paper of 54 kg/rrr using an electric blade coater (manufactured by Kumagai Riki Co., Ltd.).
The coating was applied in an amount of 13±0.5 g/rrf on one side, and dried for 15 seconds in an open gear at 120°C. 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/ry? The following tests were carried out by performing super calendering four times at a roll temperature of 50°C. 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 - Warp-resistant Super Calender is made by stacking 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 aluminum sheet, and then applying the aluminum sheet. Decreased glossiness of sheet dirt (%)
It was displayed in The smaller the number, the less dirt there is.

Examples 17 and 18 belong to the third invention, and these gravure printing paper coating compositions gave good results in each property.

(2) Fourth invention <Example 19.20> Using the polymerization recipe in Table 4, polymerization was carried out in the same manner as for copolymer latex 8 in Example 1 to obtain copolymer latex S and T. Ta.

(Preparation of coated paper) Pigment as the coating composition components shown in Table 5, water-soluble polymer compound 1 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 with a blade coater to form a coating layer of 16 g/rrr, dried, and then finished with a super calendar to obtain coated paper for measuring the physical properties of coated paper. Ta.

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 viscosity old (60 rpm, No., 4 spindles)
The initial viscosity was measured.

■ High shear viscosity Vercules-Beisher viscometer (HOOr
pm, F Bob).

■　Print gloss It was determined using a 75'' Murakami gloss meter.

■ Dry pick Same method as described above.

■ Using a Wet Vic R1 printing machine, water is supplied onto the test piece using a Molton roll, and immediately after that, tack k16 is applied to print, 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.

■ Painting quality 60 using a Kumagai Riki Kogyo blade coater.

Coating was performed at a speed of 1 minute, 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, O: Good.

Δ: Inferior. ×: Very poor Examples 19 and 20 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 21.22> Using the polymerization recipe in Table 4, polymerization was carried out in the same manner as copolymer latex A of Example 1 to obtain co-m polymer latexes U and V. Ta.

These copolymer latexes U and V 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.

Blending recipe Clay 60 parts Calcium carbonate 40 parts Copolymer latex (solid content)
16 parts casein 5 parts water was added so that the solid content concentration 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-painted drying: Gya oven, 120°C, 30 seconds Calendar Nigelos Calender, 120°C.

80 kg/cm, 1 pass base paper; commercially available thick board (220 g/sheet) The properties of the obtained coated paperboard were measured by the following method.

■ Dry pick Same as the method described above.

■ Wet big Same method as described above.

■ White paper gloss Measured using a Murakami gloss meter (75°75').

■　Print gloss Same method as described above.

(2) Ink receptivity Using a Molton roll on an RI printing machine, the degree of ink transfer when dampening water is applied is determined by determining 71P1. The higher the concentration, the better. 7It1 is expressed as the average value of 6 times.

■Apply a 1:1 mixture of blister bag adhesive #11 and L juicer (both manufactured by Arayo Toyo Kogyo Co., Ltd.) to a uniform thickness on white paper and printed coated paper with a coating rod. After drying, a fixed area of hard vinyl chloride sheet for blister bag was placed on this side, and the back side was 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 adhesion 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 value of the scores of 12 test pieces. The printed surface is a solid surface printed using an R1 printing machine using offset indigo ink.

■ Adhesive property Apply Lifebond AV-650 (manufactured by Nichiei Kako Co., Ltd.) to the surface of the coated paper using a spacer so that the width is 5 mm, the length is 80 mm, and the thickness is 0.2 mm. They were stacked so that the uncoated corrugated surfaces faced each other, pressed together under a load of 2 kg for 1 minute, and after the pressure was removed, they were 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 21 and 2.2 belong to the fifth invention, and good results were obtained in all characteristics.

(4) Sixth and seventh inventions <Example 23.24> (Production of copolymer latex W,
Copolymer latex W belonging to the sixth invention was prepared by charging it into a pressure-resistant reactor and reacting at a polymerization temperature of 40 to 60°C for 20 hours.
, got X. These copolymer latexes W and X were evaluated using the following evaluation method. The evaluation results are shown in Table 8.

(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 with Brookfield viscometer, BM type No., 4-6 rpm),
The solid content was adjusted to 73% with a thickener and water, 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 (wet)/trr to a gray fabric made by tufting nylon crimped yarn to 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 (2) 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.

The above results can be summarized as follows.

Examples 23 and 34 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 25.26> (Production method of copolymer latex Y, Z) 100! In a pressure-resistant reactor, 80 parts of water, 2 parts of sodium dodecylbenzenesulfonate, 1.5 parts of potassium persulfate, and 20% of the total monomers and 20% of the total polymerization chain transfer agent shown in Table 7 were added. The mixture was charged 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 for 5 hours to react, and then the reaction was further carried out at 80°C for 5 hours to complete the polymerization. Copolymer latexes Y and Z belonging to the invention No. 6 were obtained.

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

(Preparation of adhesive composition) Isobutylene-maleic anhydride copolymer (■Kuraray Co., Ltd.)
Kuraraisoban-06) 55 parts, sodium hydroxide 1.
After mixing 0 parts and 65 parts of water, the mixture was heated and dissolved at 65°C. To this solution, 100 parts of slaked lime and 45 parts of water were sequentially added and stirred, and then 45 parts of copolymer latex Y and Z were each added as a 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 by the following screening 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.

Coating with the O varnish bulleter was uniform and the coating properties were good × Coating with the varnish bulleter was not uniform and the coating properties were poor ■ Adhesive strength test The obtained adhesive composition was tested by the method shown below. It was applied to an adherend to prepare a test piece for measuring adhesive strength.

Thickness 1, Et adjusted to a moisture content of 11 to 13% on the adherend
Using a lauan veneer of 11 m/l, the adhesive composition is applied onto the lauan veneer at a rate of 20 g/i using a hand roll, and the same lauan veneer is bonded thereon. Furthermore, the same amount of the adhesive composition was similarly applied thereon and the same lauan veneer was laminated thereon to create the old three-ply plywood.

The obtained plywood was pressed at room temperature at 10 kg/c-(for plywood) x 5 minutes, and then further pressed at 120°C at 10 kg/c4(
1 for board a. ) Heat pressure was applied for 3 minutes.

After curing at room temperature for 20 hours, the test piece was cut into dimensions stipulated by the Japanese Agricultural Standards for ordinary plywood, and used as test pieces.

The test is specified in the Japanese Agricultural Standards for ordinary plywood.

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 speed was also 50 μ/min.

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

Wood splintering refers to the state in which wood splinters from the adherend stick to the peeling surface and peel off when measuring adhesive strength, and the value is the ratio of the wood splinter area to the adhesive area (%). The larger the value, the better the adhesive strength.

Examples 25 and 26 are adhesive compositions that fall within the scope of the eighth invention, and good results were obtained in all properties.

(6) Ninth Invention (Example 27.28) Using the copolymer latexes Y and Z shown above, evaluation was performed by the following evaluation method, and the evaluation results are shown in Table 10.

Copolymer latex Y or 255 parts (solid content), 45 parts of a resin mixture containing urea resin and urea melamine resin at a ratio (%) of 9010, 1 part of wheat flour, 30 parts of water, and 20 parts of water (5 parts, and ammonium chloride Add 0.5 part,
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 sample) The obtained adhesive composition was applied to a 4 m1 thick 3-ply lauan plywood board in an amount corresponding to the test items below, and a veneer veneer board with a thickness of 0.8n+n was placed on the coated surface. After stacking within 5 minutes and depositing for another 10 minutes, the pressing pressure was 5 kg/am,
Hot pressing was carried out under conditions of a pressing temperature of 110° C. and a pressing 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.

Coverage 10g/900cm and 15g/900cd
(Test item: Prevention of seepage contamination.

Type 2 immersion peeling test) 12 g / 900 d (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 is observed △: Slightly observed ×: There is oozing ■ Dry cracking resistance test (cold heat return test)
It was conducted in accordance with the Japanese Agricultural Standards regarding compatible boards. 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.

0; No cracks observed Δ: Slightly observed ×: Quite acceptable ■ Adhesive strength test Same as (5) ■ above.

Examples 27 and 28 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. paper coating compositions and carpet backing agent compositions that have excellent adhesive strength and blister resistance when used in various applications utilizing these functions, and further improve 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)

[Scope of 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 A monomer containing 0.5 to 10% by weight of dimethylxanthogen disulfide,
A method for producing a copolymer latex, comprising carrying out emulsion polymerization in the presence of at least one disulfide compound selected from diethylxanthogen disulfide and thiuram disulfide. (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 the 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 1 to 30% by weight monomer containing dimethylxanthogen disulfide,
A copolymer latex obtained by emulsion polymerization in the presence of at least one disulfide compound selected from diethylxanthogen disulfide and thiuram disulfide. (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 10% by weight (e) 10 to 65% by weight of aromatic vinyl monomer (f) 0.1 to 10% by weight of amide vinyl monomer and/or hydroxyalkyl-containing (meth)acrylate monomer body, dimethylxanthogen disulfide,
A copolymer latex obtained by emulsion polymerization in the presence of at least one disulfide compound selected from diethylxanthogen disulfide and thiuram disulfide. (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 Monomers containing 0 to 8% by weight of dimethylxanthogen disulfide,
A method for producing a copolymer latex, comprising carrying out emulsion polymerization in the presence of at least one disulfide compound selected from diethylxanthogen disulfide and thiuram disulfide. (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.