JP2002363228A - Latex composition and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymer latex composition which is less likely to generate fine coagulated products during a copolymerization reaction and is excellent in mechanical stability and chemical stability. When used for RFL, a polymer latex composition having high stability and excellent heat resistance as well as initial adhesion is obtained. SOLUTION: A sulfonate of an aromatic vinyl compound (a)
In the presence of vinyl pyridine, styrene, butadiene,
A copolymer latex composition obtained by copolymerizing a (meth) acrylamide compound (b) and a (meth) acrylate compound (c).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinylpyridine, styrene, butadiene terpolymer latex composition and a method for producing the same. The copolymer latex composition of the present invention has less occurrence of fine coagulated material during the copolymerization reaction, and
The produced latex composition has excellent mechanical stability and chemical stability. This copolymer latex composition is mainly used for adhesives, and is particularly useful as an adhesive or binder between fibers and rubber contained in rubber products such as tires, conveyor belts, belts and hoses. , Carpet backing agents and paints,
It is also suitably used for adhesives for various industrial and household uses.

[0002]

2. Description of the Related Art Generally, in the production of a copolymer latex composition, if the reaction system does not have sufficient stability, the reaction system may be mechanically sheared by stirring of the reactant or contact with the monomer. The rubber component therein precipitates to produce a coagulated product. When such coagulated material adheres to the inner wall of the reactor, it greatly affects the control of the polymerization temperature and the polymerization rate. For this reason, it is necessary to frequently remove the coagulated matter adhering to the inner wall of the reactor, which significantly reduces productivity.

[0003] Further, if the stability of the produced latex with respect to the mechanical shear (mechanical stability) is insufficient,
Problems such as latex becoming unstable due to shear in the pipe or shear by a pump, causing coagulation to precipitate and causing problems such as clogging, or changing the particle size of the latex, resulting in impaired product quality There is. In order to improve the stability of the latex, a method of increasing the amount of surfactant during or after polymerization is generally used.However, a problem arises in the foaming properties of the latex, and other performances are often reduced. No results have been obtained.

Also, tires, conveyor belts, belts,
For reinforcing rubber products such as hoses, reinforcing materials are used in the form of filaments, cords, cables, cord fibers and canvas. The adhesiveness (bonding property) between the reinforcing material and the rubber affects not only the physical properties of the rubber product but also greatly affects the product life of the rubber product. For such applications,
In order to obtain an adhesive force between a reinforcing material and rubber, an adhesive composition in which a specific resin is dissolved or mixed in latex is used. Examples of such a specific resin include a resorcin-formaldehyde resin and a urea-formaldehyde resin, and one or two or more of these resins are used in combination. In particular, resorcin-formaldehyde resin is most commonly used.

The latex includes vinyl pyridine-styrene-butadiene terpolymer latex, styrene-butadiene copolymer latex, natural rubber latex and the like, and one or more of these may be mixed. Used. Especially vinylpyridine-styrene-
Butadiene terpolymer latex is most commonly used. That is, an adhesive (hereinafter abbreviated as RFL) that combines a vinylpyridine-styrene-butadiene terpolymer latex and a resorcin-formaldehyde resin is most widely used for bonding rubber and a reinforcing material.

[0006] Such a method of using RFL generally involves applying an adhesive to a fibrous material, performing heat treatment to bond the adhesive and the fibrous material, and then embedding the fibrous material in a compounded rubber. At the same time as sulfurizing, the compounded rubber and the fiber material are combined.

On the other hand, in producing a vinylpyridine-styrene-butadiene terpolymer latex composition,
The amount of the surfactant to be used must be suppressed to an appropriate amount or less from the viewpoint of the foaming properties of the latex and RFL, and also the adhesive force between the rubber and the reinforcing material (fiber). However, when a vinylpyridine-styrene-butadiene terpolymer latex composition is produced by a conventional method, aggregates are generated during the production of the latex as described above, and the mechanical stability and the mechanical stability of the obtained latex composition There were various problems in productivity such as low chemical stability.

[0008] If the obtained copolymer latex composition has low mechanical stability and low chemical stability, it causes a decrease in the stability when RFL is prepared, and not only adhesive compositions but also various rubber products can be obtained. There is also a problem in terms of workability during manufacturing. For example, if the stability of RFL is low, RFL aggregates adhere to the squeezing roll in the dipping step, which is a serious problem in terms of productivity. For this reason, improvement in stability has been attempted by adding a surfactant or a stabilizer, and blending of a carboxy-modified SBR latex and a vinylpyridine-based latex has been attempted as disclosed in JP-A-63-57685. But not yet enough.

In recent years, the weight of tires and the like has been reduced from the viewpoint of energy saving, and the heat or dynamic action on reinforcing fibers embedded in rubber and its adhesives has been increasingly increased, and various materials constituting products have been developed. Improvements in strength, modulus, and the like are desired, and improvements in fiber-rubber adhesion are also required.

In order to solve such a problem in the conventional vinylpyridine-styrene-butadiene terpolymer latex composition, for example, an attempt was made to change the mixing ratio with a resorcinol-formaldehyde resin so as to firmly bind to the fiber side. Then, the bonding force on the rubber side is reduced, while increasing the bonding force on the rubber side causes a disadvantage that the bonding force on the fiber side is reduced.

Also, among the reinforcing materials, polyester fibers have a smaller elongation and a very excellent dimensional stability as compared with polyamide fibers. Therefore, polyester fibers have begun to be widely used mainly for applications such as carcass cords for radial tires. I have.

However, since polyester fibers are inactive compared to polyamide fibers, rayon fibers and the like, there has been a problem that the adhesion (initial adhesion) between the fibers and rubber immediately after vulcanization is reduced. In addition, polyester fiber has poor heat resistance, after high-temperature vulcanization and after high-temperature history (for example, after high-speed running)
In this case, there was a problem that the fiber-rubber adhesive strength (heat-resistant adhesive strength) and the fiber strength were reduced.

For this reason, for example, Japanese Patent Application Laid-Open No. 3-163181
No., JP-A-11-29755, JP-A-11-92730
In the publication, the initial adhesion is achieved by forming the polymer into a double structure by a two-stage polymerization method, and further regulating the copolymer composition ratio within a predetermined range, or regulating the gel / sol ratio by toluene immersion extraction. Although efforts are being made to improve strength and heat-resistant adhesive strength, it is still not enough.

[0014]

With the recent improvement in tire performance or high-temperature vulcanization, the demand for heat-resistant adhesive strength is becoming increasingly severe, and further improvement of the copolymer latex composition is required. That is, there is a need for a copolymer latex composition for a fiber-rubber adhesive that improves the stability of RFL and has excellent initial adhesive strength and heat resistant adhesive strength.

[0015]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems. As a result, in producing a vinylpyridine-styrene-butadiene terpolymer latex composition, a sulfonate of an aromatic vinyl compound (hereinafter sometimes referred to as (a)), a (meth) acrylate compound The copolymer latex composition using (hereinafter sometimes referred to as (b)) is excellent in mechanical stability and chemical stability, and the generation of fine coagulated material is small even during the production of the copolymer latex. Further, when such a copolymer latex composition is used for an adhesive such as RFL widely used for bonding between fiber and rubber, the stability of the adhesive composition is improved, and excellent heat-resistant adhesive strength is obtained. It has been found that the present invention is obtained, thereby completing the present invention.

That is, the present invention relates to a method for producing 2-vinylpyridine, styrene, butadiene and (meth) acrylate compounds in the presence of a sulfonate (a) of an aromatic vinyl compound.
It is intended to provide a copolymer latex composition obtained by copolymerizing (b). In the copolymer latex composition of the present invention, the component (a) is a styrene sulfonate,
The component (b) is preferably glycidyl methacrylate.

The preferred copolymer latex composition of the present invention comprises 5 to 20 parts by weight of 2-vinylpyridine,
The monomer mixture (I) composed of 5 to 75 parts by weight, 5 to 60 parts by weight of 1,3-butadiene is polymerized, and then 5 to 20 parts by weight of 2-vinylpyridine, 5 to 35 parts by weight of styrene, Polymerization is performed by polymerizing a monomer mixture (II) composed of 45 to 90 parts by weight of 1,3-butadiene to obtain a copolymer latex composition having copolymers having different composition ratios in the particles.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a method for producing a copolymer latex composition of the present invention will be described in detail.

In the present invention, when a monomer mixture is emulsion-polymerized to produce a vinylpyridine-styrene-butadiene copolymer latex composition, (a) a sulfonate of an aromatic vinyl compound, (b) ( It is essential to use a (meth) acrylate compound. The monomer used in the production of such a copolymer latex composition is most preferably 2-vinylpyridine as the vinylpyridine, styrene as the styrene-based monomer, and 1.3 as the butadiene-based monomer. -Butadiene is preferred.

The typical composition and polymerization operation of vinylpyridine, styrene and butadiene used in the production of the copolymer latex composition of the present invention are as follows. That is, in 100 parts by weight of the monomer mixture (I), 5 to 20 parts by weight, preferably 10 to 15 parts by weight of 2-vinylpyridine; 35 to 75 parts by weight, preferably 45 to 70 parts by weight of styrene.
Parts by weight; and 5 to 60 parts by weight of 1,3-butadiene, preferably 15 to 45 parts by weight, is polymerized, and then 100 parts by weight of the monomer mixture (II), 5 to 20 parts by weight of vinylpyridine, preferably 7 to 18 parts by weight; 5 to 35 parts by weight of styrene, preferably 10 to 30 parts by weight; and 45 to 90 parts by weight of 1,3-butadiene, preferably 52 to 83 parts by weight. Is carried out to obtain a copolymer having a different composition ratio in the particles.

In the production of the copolymer latex composition, if the 2-vinylpyridine content of the monomer mixture (I) is less than the above range, the obtained copolymer latex composition may be used as an RFL. In some cases, the adhesive strength between the fiber and the rubber may be poor. On the other hand, when it exceeds this range, the stability of the latex decreases, and when it is used as RFL, the stability at RFL is poor and the vulcanization reaction of latex is accelerated, which is not preferable. If the styrene content is less than the above range, the strength of the latex particles decreases, leading to a decrease in adhesive strength. On the other hand, if it exceeds the above range, the latex particles become too hard, and there is a possibility that the adhesive strength may be reduced when the product is used under high strain. When the 1,3-butadiene content is less than the above range, the crosslinking is reduced, which causes a decrease in adhesive strength. On the other hand, if it exceeds the above range, crosslinking of the latex becomes too large, which is not preferable.

Next, when the 2-vinylpyridine content of the monomer mixture (II) is less than the above range, RFL
When used, the adhesive strength between fiber and rubber may be poor. On the other hand, if it exceeds the above range, the adhesive becomes brittle, which is not preferable.

When the styrene content is less than the above range, the strength of the latex particles decreases, which leads to a decrease in adhesive strength. On the other hand, when it exceeds the above range, the co-vulcanizability of the adhesive layer and the adhesive rubber is reduced, and the adhesive strength may be reduced.

When the 1,3-butadiene content is less than the above range, the crosslinking becomes too small and the adhesive strength is reduced. On the other hand, when it exceeds the above-mentioned range, the crosslinking may become too large, and the adhesive strength and the durability may be reduced.

The weight ratio of the copolymer obtained from the monomer mixture (I) to the copolymer obtained from the monomer mixture (II) is 80/20 to 40/60, preferably 75/20. 25
４５45/55. When the amount of the copolymer obtained from the monomer mixture (I) is smaller than this, the initial adhesive strength is good, but the heat resistant adhesive strength is reduced. On the other hand, the monomer mixture (I)
If the copolymer obtained from the above is more than this, the crosslinking between the particles in the adhesive layer and between the particles and the polymer in the rubber is reduced, and as a result, the adhesive strength may be reduced.

As the emulsion polymerization method of the present invention, either a seed polymerization method using a seed or a non-seed polymerization method without a seed can be adopted.

In the seed polymerization method, a part of the monomers to be used is reacted in advance in a polymerization reactor to prepare a seed, and in the presence of the seed, the remaining monomer is added to the polymerization reactor. There are an (internal) method and an external (external) method in which a latex having an ultrafine particle diameter is prepared in advance, a predetermined amount of the latex is charged into a polymerization reactor as a seed, and then a monomer is added thereto.

On the other hand, in the non-seed polymerization method, a predetermined amount of an emulsifier is added to a polymerization reactor in advance without using a seed.
In this method, a monomer is added to carry out emulsion polymerization.

These charging methods include a monomer batch charging method in which monomer components are collectively added to a polymerization system,
There are a divided charge polymerization method in which a monomer component is divided and added to a polymerization system, and a monomer continuous addition charge polymerization method. In the present invention, it is indispensable to carry out the polymerization by a divided charge polymerization method or a charge polymerization method by continuous addition of monomers.

In the present invention, it is important to carry out the polymerization of the monomer mixture (II) after the polymerization conversion of the monomer mixture (I) reaches 80% or more, preferably 80 to 95%. . If the polymerization conversion of the monomer mixture (I) does not reach 80%, it is difficult to obtain a two-layer structure of the copolymer particles, so that the heat resistance may be reduced. When producing the copolymer latex composition of the present invention, usually 0 ~ 100 ℃
At a temperature of 90% until the conversion of the monomers reaches 90%, preferably 95% or more.

(A) Sulfonate of Aromatic Vinyl Compound In the present invention, the sulfonic acid salt of (a) the aromatic vinyl compound includes styrene sulfonic acid (salt), α-methylstyrene sulfonic acid (salt), vinyl toluene sulfone Acids (salts), p-methylstyrenesulfonic acid (salts), vinylnaphthalenesulfonic acid (salts) and the like are exemplified, and styrenesulfonic acid (salts) is particularly preferably used. Sodium, potassium and ammonia are used as alkalis constituting these salts, and sodium is particularly preferable. The sulfonates of the aromatic vinyl compounds may be used alone or in combination of two or more.

The amount of these used is 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, more preferably 0.1 to 1 part by weight based on 100 parts by weight of the total monomers. If the amount is less than this, the effect of suppressing the generation of fine coagulates during latex production is small, and the obtained copolymer latex composition and RFL may be inferior in mechanical stability or chemical stability. . Conversely, if it exceeds the above range, the foamability of the obtained copolymer latex composition and RFL is too high or is not preferable in terms of cost.

(B) (Meth) acrylic acid ester compound In the present invention, (b) (meth) acrylic acid ester compound includes methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (Meth) acrylic acid 2-
Examples thereof include hydroxyethyl and glycidyl (meth) acrylate, and glycidyl (meth) acrylate is particularly preferably used. These (meth) acrylate compounds may be used alone or in combination of two or more. These are used in an amount of 0.1 to 100 parts by weight of all monomers.
5 parts by weight, preferably 0.5 to 3 parts by weight. If the amount used is less than this, when used as RFL, the adhesive force between the fiber and rubber after high-temperature vulcanization and after high-temperature history (heat-resistant adhesive force)
May be inferior. On the other hand, if it exceeds the above range, the obtained copolymer latex composition and RFL may be poor in mechanical stability or chemical stability. This ingredient
(b) is preferably added to at least the monomer mixture (I).

(Production of Copolymer Latex Composition) In order to produce the copolymer latex composition of the present invention, a conventionally known emulsion polymerization method, that is, a method of preparing a monomer latex in an aqueous medium such as water, A method of performing emulsion polymerization by adding a body mixture, a polymerization chain transfer agent, a polymerization initiator, an emulsifier, and the like is used.

(I) Polymerization chain transfer agent As the polymerization chain transfer agent, an ordinary chain transfer agent generally known in emulsion polymerization can be used. As such a polymerization chain transfer agent, for example, mercaptocarboxylic acid such as 2-mercaptopropionic acid or a salt thereof (e.g., ammonium mercaptoacetate), for example, mercaptodicarboxylic acid such as mercaptosuccinic acid or a salt thereof (e.g., Mercaptans having a hydroxyl group in the molecule such as 2-mercaptoethanol, for example, mercaptans having an amino group in the molecule such as 2-mercaptoethylamine, for example, thioglycolic acid, 3 Monosulfides having a carboxyl group in the molecule such as 3,3'-thiodipropionic acid or a salt thereof, for example, monosulfides having a hydroxyl group in the molecule such as β-thiodiglycol, such as a molecule such as thiodiethylamine Having an amino group within De include, for example, dithiodiglycolic acid,
Disulfides having a carboxyl group in the molecule such as 2,2′-dithiodipropionic acid or a salt thereof, for example, monosulfides and disulfides such as thiodiglycolic anhydride, and the like, for example, D
-, A disulfide having a carboxyl group and an amino group in the molecule such as L- or DL-cystine, and a halogenated hydrocarbon having a hydroxyl group in the molecule such as chloromethanol and 2-chloroethanol; , Monochloroacetic acid, dichloroacetic acid, chlorofumaric acid,
Halogenated hydrocarbons having a carboxyl group in the molecule such as chloromaleic acid and chloromalonic acid or salts thereof, for example, acid anhydrides of halogenated hydrocarbons such as chloromaleic anhydride, for example, hexyl mercaptan Octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, etc., monothiols such as 1,10-decanediol, trithiol such as triglycol dimercaptan, trithiol such as trimethylolpropane tristhioglycolate, pentaerythritol Polythiols having at least two mercapto groups in the molecule, such as tetrathiols such as tetrakisthioglycolate, for example, xanthos such as dimethyl xanthogen disulfide, diethyl xanthogen disulfide, etc. Gendisulfide, for example, thiuram disulfide such as tetramethylthiuram disulfide, and halogenated hydrocarbon such as carbon tetrachloride and carbon tetrabromide, for example, mercaptoacetic acid 2-ethylhexyl ester, mercapto such as mercaptopropionate tridecyl ester Carboxylic acid alkyl esters, for example, mercaptoacetic acid methoxybutyl ester, mercaptopropionic acid methoxybutyl ester and the like mercaptocarboxylic acid alkoxyalkyl esters, for example,
Carboxylic acid mercaptoalkyl esters such as octanoic acid 2-mercaptoethyl ester and α-methylstyrene dimer, terpinolene, α-terpinene, γ-
Examples thereof include terpinene, dipentene, anisole, and allyl alcohol.

These polymerization chain transfer agents are used alone or in combination of two or more. In the present invention, monothiol, polythiol, xanthogen disulfide, thiuram disulfide, 2-ethylhexyl mercaptoacetate, 2-mercaptoethyl octanoate, methoxybutyl mercaptoacetate, methoxybutyl mercaptopropionate, α-methylstyrene dimer, Terpinolene and the like are preferably used, and monothiol is most preferably used.

The amount of the polymerization chain transfer agent to be used is generally in the range of 0.05 to 20 parts by weight, preferably 0.1 to 15 parts by weight, most preferably 0.1 to 15 parts by weight, per 100 parts by weight of the monomer mixture. 0.2 to 10 parts by weight.

When the amount of the chain transfer agent is less than 0.05 parts by weight, the Mooney value of the obtained copolymer latex composition is high, so that the rubber elasticity is poor and RF
When used as L, the adhesive strength between fiber and rubber may be poor. On the other hand, when the amount exceeds 20 parts by weight, the effect of suppressing the generation of fine coagulates during the production of latex is small, and the obtained latex composition and RFL may be poor in mechanical stability or chemical stability. .

(Ii) Polymerization initiator As the polymerization initiator, an ordinary polymerization initiator generally known in emulsion polymerization can be used. As such a polymerization initiator, for example, potassium persulfate, sodium persulfate, inorganic persulfates such as ammonium persulfate, for example, cumene hydroperoxide, benzoyl peroxide, organic peroxides such as isopropylbenzene peroxide, for example, And an azo initiator such as azoisobutyronitrile. These may be used alone or in combination of two or more.For example, sulfites, bisulfites, pyrosulfites, nitrites, nitrites, thiosulfates, such as formaldehyde sulfonate, It can also be used as a so-called redox initiator which is combined with a reducing sulfoxylate such as benzaldehyde sulfonate, for example, a reducing agent such as ferrous sulfate, ferrous ammonium sulfate and cuprous naphthenate. In the present invention, inorganic persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate are particularly preferably used from the viewpoint of polymerization stability.

The amount of the polymerization initiator to be used is usually 0.1 to 5 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of all the monomers.
It is in the range of 2 to 2 parts by weight.

(Iii) Emulsifier As the emulsifier, a usual emulsifier generally known in emulsion polymerization can be used. Such emulsifiers include, for example, alkali metal salts of fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid (especially sodium and potassium salts), sodium lauryl sulfate, sodium lauryl sulfonate, dodecylbenzene sulfone Anionic surfactants such as sodium silicate, sodium dodecyl diphenyl ether sulfonate, sodium dialkyl succinate sulfonate, alkali metal salts of rosin acid (particularly sodium and potassium salts), formaldehyde condensed sodium naphthalene sulfonate,
For example, nonionic surfactants such as polyoxyethylene alkyl esters and polyoxyethylene alkyl aryl ethers, for example, alkyl betaine-type salts such as lauryl betaine and stearyl betaine salts, lauryl-
Amino acid type surfactants such as β-alanine, lauryldi (aminoethyl) glycine, octyldi (aminoethyl) glycine and the like can be used in combination.

The amount of the emulsifier used is 10
The amount is usually 0.1 to 8 parts by weight, preferably 1 to 6 parts by weight with respect to 0 parts by weight.

(Iv) pH adjuster A pH adjuster can be used as needed in the production of the copolymer latex composition of the present invention. As such a pH adjuster, for example, an alkaline substance such as ammonia, sodium hydroxide, or potassium hydroxide is used. The pH of the copolymer latex composition is usually 9-1.
2, preferably in the range of 10-11. When the pH value is lower than 9, the stability of the RFL-mixed liquid may decrease, and when the pH value exceeds 12, the adhesive strength may decrease.

(V) Other Components In the method of the present invention, the emulsion polymerization is carried out in the presence of a chelating agent such as sodium ethylenediaminetetraacetate, a dispersant such as a polycarboxylate, or an inorganic salt such as a phosphate. You may go to. Also, if necessary, for example, antioxidants such as styrenated phenol, hindered phenol, imidazoles, paraphenylenediamine, etc., for example, fragrances such as acetophenone, cinnamaldehyde, panillin, lavender oil, for example, thiabendazole ,
Preventol, antibacterial agents such as binazine, for example, silicon-based, higher alcohol-based antifoaming agents, for example, dimethyldithiocarbamate, NN dimethylhydroxyamine, a reaction terminator such as thiourea, for example, ethylene glycol, diethylene glycol, An additive such as an antifreezing agent such as urea may be appropriately added.

(Adhesive Composition) The adhesive composition containing the copolymer latex composition of the present invention is used for bonding fibers and rubber contained in rubber products such as tires, conveyor belts, belts and hoses. In addition to being useful as an agent or a binder, it can also be suitably used as a carpet backing agent or paint, and an adhesive according to various industrial and household uses. It can be used, and is particularly useful for tire cords.

When the copolymer latex composition of the present invention is used for bonding rubber and fibers, the copolymer latex composition has an average particle diameter of 70 to 150 nm, preferably 90 to 120 nm, and a gel content of 80 to 150 nm. % By weight, preferably 60% by weight or less, and the Mooney viscosity is 10 to 100, preferably 20 to 80.

The average particle size is set to a suitable range by controlling the emulsifier and the like, and the gel content and Mooney viscosity of the polymerization chain transfer agent and the like by a known method, that is, by controlling the amount or addition method. Can be.

To prepare the adhesive composition, the copolymer latex composition of the present invention is mixed with, for example, a phenol resin. The phenolic resin used in the present invention can be obtained from phenols such as phenol, cresol, xylenol, and resorcinol and aldehydes such as formaldehyde, acetaldehyde and furfural, but depending on the purpose of use, phenol-formaldehyde resins and phenol-furfural resins. Resins and resorcin-formaldehyde resins are preferably used.

The adhesive composition of the present invention is particularly preferably a resorcinol-formaldehyde resin. The resorcin-formaldehyde resin is described in, for example,
Resins and the like disclosed in JP-A-5-142635 can be used, but are not particularly limited. The amount of the phenol resin used in the adhesive composition is usually from 10 to 40 parts per 100 parts by weight of the solid content of the latex.
Parts by weight (dry weight) are mixed. Further, in order to enhance the adhesive strength, 2,6-bis (2,4-dihydroxyphenylmethyl)-, which has been conventionally used as a fiber pretreatment agent, is used.
It may be used in combination with a compound such as 4-chlorophenol, a polyepoxide compound and / or a blocked polyisocyanate compound.

The organic fiber to which the adhesive composition of the present invention can be applied is not particularly limited, and can be used for nylon fiber, rayon fiber, vinylon fiber, polyester fiber, aramid fiber, polyurethane fiber and the like. Any form such as a woven fabric, a cord, a cable, a canvas, a short fiber, a thread and the like may be used.

The method of using the adhesive composition of the present invention is not particularly limited. That is, the known phenolic resin
It can be applied in the same manner as the adhesive composed of the latex composition. For example, a method of dipping a fiber material in an adhesive composition liquid,
Any method such as a method of applying with a doctor knife or a brush, or a method of spraying with a spray or the like may be used.
Usually, the adhesive composition is prepared at a concentration of 10 to 30% by weight,
After immersing the fiber in the desired form, drying and heat treatment,
By forming and vulcanizing with an unvulcanized rubber compound,
A method of bonding fiber and rubber has been adopted.

[0052]

Next, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to these examples. In Examples and Comparative Examples,
“Parts” and “%” are based on weight unless otherwise specified.

Example 1 (1) Preparation of Copolymer Latex Composition In a 5-liter autoclave purged with nitrogen, water 14 was added.
0 parts, potassium rosinate 1.5 parts, formalin condensate of sodium naphthalenesulfonate 1.0 part, sodium styrenesulfonate 0.1 part, 2-vinylpyridine 7.5
Parts, styrene 35.1 parts, 1,3-butadiene 16.5
Parts, 0.9 part of glycidyl methacrylate, 0.2 part of t-dodecylmercaptan and 0.3 part of sodium persulfate were charged and reacted at 50 ° C. with stirring. Monomer mixture
After the polymerization conversion of (I) reaches 80 to 90%, subsequently, 2.0 parts of potassium rosinate and 6.2 parts of 2-vinylpyridine.
0 parts, styrene 6.0 parts, 1,3-butadiene 28 parts, t
0.4 parts of dodecyl mercaptan were added and the polymerization was continued.

After the polymerization conversion (based on all monomers) reached 95% or more, the obtained copolymer latex composition was heated to 30 ° C.
The polymerization was stopped by adding 0.1 part of hydroquinone. Next, the pH of the copolymer latex composition obtained with 6% potassium hydroxide was adjusted to 10.0 to 11.0, unreacted monomers were removed under reduced pressure, and the solid content was reduced to 40%. A copolymer latex composition was obtained.

Preparation of resorcinol-formaldehyde-latex (RFL) adhesive composition A mixture having the following composition was prepared and aged at 25 ° C. for 24 hours.
An (RFL) adhesive composition was obtained.

Water 564.2 parts by weight Resorcinol 16.5 parts by weight Formalin (37%) 20.1 parts by weight Sodium hydroxide (10%) 12.0 parts by weight Copolymer latex composition 387 prepared with (1) .2 parts by weight

(In Table 1, the monomer mixture (I)
And parts representing the composition of (II), each monomer mixture (I) or
(II) The value is based on 100 parts by weight. )

[Examples 2 to 5] Emulsion polymerization was carried out in the same manner as in Example 1 except that the polymerization was carried out with the monomer composition shown in Table 1, to obtain a copolymer latex. In particular, in Examples 2 to 4, the weight ratio of the copolymer (I) to the copolymer (II) was 60/40, and in Example 5, the weight ratio was 50/50. Subsequently, the obtained copolymer latex composition was prepared in the same manner as in Example 1 to prepare a resorcinol-formaldehyde resin solution and a resorcinol-formaldehyde-latex (RFL) adhesive composition to obtain an RFL adhesive composition. Was.

Comparative Examples 1 to 4 Emulsion polymerization was carried out in the same manner as in Example 1 except that the polymerization was carried out using the monomer compositions shown in Table 1, to obtain copolymer latex compositions. However, in Comparative Examples 1 and 2, emulsion polymerization was performed without adding sodium styrenesulfonate as the component (a), and in Comparative Example 3 with glycidyl methacrylate as the component (b). In Comparative Example 4, emulsion polymerization was performed without adding all of the components (a) and (b). Subsequently, the obtained copolymer latex was prepared in Example 1.
Preparation of resorcinol-formaldehyde resin liquid and resorcinol-formaldehyde-latex (RFL)
An adhesive composition was prepared, and an RFL adhesive composition was obtained.

Comparative Example 5 Polymerization was carried out using the monomer compositions shown in Table 1. In Comparative Example 5, the polymerization was carried out by a batch charging method without employing the split charging polymerization method. That is, this is an example in which copolymers having different composition ratios do not exist in the same particle. Subsequently, the obtained copolymer latex was prepared in the same manner as in Example 1 to prepare a resorcinol-formaldehyde resin solution and a resorcinol-formaldehyde-latex (RFL) adhesive composition to obtain an RFL adhesive composition.

(Evaluation Method) The physical properties of the obtained copolymer latex composition were measured by the following methods.

(1) Average particle size Coulter counter Model N4 + (Coulter
(Manufactured by K.K.).

(2) Toluene Insoluble Content (Gel Content) The obtained copolymer latex composition was poured into a glass mold to prepare a 0.3 mm thick film. This film was cut into a 2-3 mm square, and 0.4 g was precisely weighed. The sample is immersed in 100 ml of toluene and shaken in a shaking thermostat at 30 ° C. for 6 hours. Thereafter, the mixture was filtered through a 100-mesh wire gauze, the solid content of the filtrate was obtained, and the gel content was calculated from the solid content of the sol.

Mooney viscosity 50 g of 20% sodium chloride is added to the obtained copolymer latex (200 g), and the mixture is stirred with a commercial juice mixer until the solution becomes transparent. The deposited rubber mass has a diameter of 5
It is loosened to a size of about mm and vacuum-dried until there is no cloudy part. Then, according to JISK-6300,
Mooney viscosity (ML 1 _{+ 4} 100 ° C) was measured.

(4) Mechanical stability According to the method shown in JIS K6387-1982,
The test was performed under the conditions of a load of 10 kg and a rotation time of 5 minutes, and the solidification rate (%) was determined. According to the obtained solidification rate (%), the following three-stage evaluation was performed. ... less than 0.2% ... 0.2% or more and less than 1% x ... 1% or more

Chemical stability To 100 g of the obtained copolymer latex, 5 ml of 10% calcium chloride was added dropwise over 2 minutes, and the mixture was filtered through a 100-mesh wire gauze. (%) Was determined. According to the obtained solidification rate (%), the following three-stage evaluation was performed. ... less than 0.2% ... 0.2% or more and less than 1% x ... 1% or more

RFL Liquid Mechanical Stability In the same manner as in the measurement of the mechanical stability of the copolymer latex composition, a test was carried out under the conditions of a load of 10 kg and a rotation time of 5 minutes in accordance with the method described in JIS K6387-1982.
The coagulation rate (%) was determined. According to the obtained solidification rate (%), the following three-stage evaluation was performed. ... less than 0.2% ... 0.2% or more and less than 1% x ... 1% or more

Initial adhesive strength, heat-resistant adhesive strength A 1670 dtex filament of polyethylene terephthalate is twisted with a twist of 40 times / 10 cm and a lower twist of 40 times / 10 cm, and this cord is 98.64 parts by weight of water diglycerol triglycidyl 1.20 parts by weight of ether 0.02 parts by weight of sodium dioctylsulfosuccinate 0.14 part by weight of sodium hydroxide Dipped in an adhesive composition having a composition of 0.14 parts by weight, dried at 160 ° C. for 1 minute, and then 1.5 hours at 240 ° C. Heat treatment was performed for minutes. Thereafter, the treatment code was immersed in the obtained resorcin-formaldehyde-latex (RFL) adhesive composition,
After drying at 60 ° C. for 1 minute, heat treatment was performed at 240 ° C. for 1.5 minutes. Subsequently, the cord obtained by the above treatment was sandwiched between rubber compounds manufactured according to the following compounding recipe, and vulcanization conditions were 130 ° C. for 20 minutes under the vulcanization condition in the initial adhesive force measurement, and vulcanization in the heat resistance adhesive force measurement. Sulfurization conditions 20 at 170 ° C
After press vulcanization, ASTM D-2138-67 (H
The adhesive force was measured according to the pull test method).

(Rubber Compounding Formula) Natural rubber 70.0 (part) SBR 30.0 (part) SRF carbon 20.0 (part) HAF carbon 20.0 (part) Pine tar 5.0 (part) Styrenated phenol 2.0 (parts) Stearic acid 2.5 (parts) Zinc white 4.5 (parts) Vulcanization accelerator CZ * 1.2 (parts) Sulfur 2.4 (parts) (*; N-cyclohexyl-2- (Benzothiazolyl-sulfenamide)

[0070]

[Table 1]

[0071]

Industrial Applicability The copolymer latex composition of the present invention has a small amount of fine coagulation during the copolymerization reaction, and the obtained copolymer latex composition has excellent mechanical stability and chemical stability. I have. When used as RFL, R
High stability in FL and excellent heat resistance as well as initial adhesion. Therefore, tires, conveyor belts, belts,
It is useful as an adhesive between fibers and rubber in rubber products such as hoses.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09J 133/06 C09J 133/06 139/08 139/08 161/06 161/06 (72) Inventor Yuichiro Kajiwara Takeda Pharmaceutical Co., Ltd. Chemicals Company 2-72-17-85, Jusanhoncho, Yodogawa-ku, Osaka (72) Inventor Shigeo Suzuki 2--17-85 Jusanhoncho, Yodogawa-ku, Osaka Takeda Pharmaceutical Co., Ltd. Within the Chemicals Company (72) Inventor Masaaki Tsuji 2-17-18, Jusanhoncho, Yodogawa-ku, Osaka Takeda Pharmaceutical Company Limited Chemicals Company (72) Inventor Yuki Taniguchi 3-3-Ogawa Higashicho, Kodaira, Tokyo 8-109 (72) Inventor Kozo Sasaki 2-224-1-509 F Sakuragaoka, Higashiyamato City, Tokyo F-term (reference) 4J011 BB01 BB06 BB07 BB09 KA04 KA06 KA21 KA25 4J026 AA17 AA19 AA45 AA48 AA61 AA6 2 AA68 AC24 AC26 BA05 BA06 BA08 BA27 BA30 BA40 BA46 BB04 DA04 DA07 DA12 DA14 DA15 DA16 DB04 DB08 DB12 DB14 DB15 DB16 DB23 DB26 FA07 GA09 4J040 CA081 DB051 DF031 DF061 EB031 EB061 EC231 EH021 GA11 MA05 NA10 MA06 NA08 LA08 AB02P AB07T AL03S AL09S AL10S AQ12R AS02Q BA56T CA03 CA29 EA07 FA20 FA27 FA37 JA03

Claims (8)

[Claims] 1. A method comprising (a) copolymerizing 2-vinylpyridine, styrene, 1,3-butadiene and (b) a (meth) acrylate compound in the presence of a sulfonate of an aromatic vinyl compound. Copolymer latex composition represented by the formula: 2. The composition according to claim 1, wherein the component (a) is a styrene sulfonate,
The copolymer latex composition according to claim 1, wherein the component (b) is glycidyl methacrylate. 3. 2- 100 parts by weight of the monomer mixture (I)
A monomer mixture composed of 5 to 20 parts by weight of vinylpyridine, 35 to 75 parts by weight of styrene and 5 to 60 parts by weight of 1,3-butadiene is polymerized, and then a monomer mixture (II) 1
5 to 20 parts by weight of 2-vinylpyridine, 5 to 35 parts by weight of styrene, 45 to 90 parts by weight of 1,3-butadiene
The copolymer latex composition according to claim 1 or 2, wherein copolymers having different composition ratios are obtained in the particles obtained by performing a division polymerization for polymerizing a monomer mixture composed of parts by weight. . 4. The copolymer according to claim 3, wherein component (a) is 0.01 to 5 parts by weight and component (b) is 0.1 to 5 parts by weight based on 100 parts by weight of all monomers. Latex composition. 5. The weight ratio of the copolymer obtained from the monomer mixture (I) to the copolymer obtained from the monomer mixture (II) is 8:
The copolymer latex composition according to claim 3, which is 0/20 to 40/60. 6. An adhesive composition comprising the latex composition according to claim 1. 7. The adhesive composition according to claim 6, further comprising a phenol resin. 8. The adhesive composition according to claim 6, wherein the phenol resin is a resorcin-formalin resin.