JPH0441507A - Production of new copolymer latex - Google Patents

Abstract

PURPOSE:To produce a new copolymer latex improved in adhesiveness and being useful for paper coating, carpet backing, etc., by emulsion-copolymerizing a conjugated diene with an ethylenically unsaturated carboxylic acid and another monomer, in the presence of a specified chain transfer agent. CONSTITUTION:40-60wt.% monomer mixture of a particle diameter of 0.05-1mum comprising 20-90wt.% conjugated diene (e.g. butadiene), 0.5-10wt.% ethylenically unsaturated carboxylic acid (e.g. itaconic acid) and another comonomer (e.g. styrene) is emulsion-copolymerized at 60-90 deg.C in a solvent in the presence of 0.2-20 pts.wt., per 100 pts.wt. monomer mixture, chain transfer agent which comprises an azobenzene derivative of the formula (wherein X and Y are each -H, -OH, -O-R, -R-OH, -O-R-OH or halogen; and R is 1-6C alkyl) and may optionally contain another known chain transfer agent, a surfactant and a polymerization initiator.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel copolymer latex used for paper coating, carpet backing, fiber bonding, or adhesives.

[Conventional technology]

Conventionally, synthetic copolymer latexes have been widely used, for example, as binders for paper coating, binders for carpet hack sizing, binders for binding fibers such as nonwoven fabrics and artificial leather, and adhesives for various materials. When a copolymer latex is used for such purposes, it is required that the copolymer latex has high adhesive strength and is excellent in water resistance, blistering resistance due to dry heating, and the like.

For example, coated paper uses pigments such as kaolin clay, calcium carbonate, satin white, talc, and titanium oxide on the surface of the base paper to improve the paper's printability and optical properties such as gloss. They are coated with paints whose main components are copolymer latex as a binder and water-soluble polymers such as starch, polyvinyl alcohol, and carboxymethyl cellulose as water-retaining agents or auxiliary binders, and conventionally styrene A styrene-butadiene-based copolymer latex obtained by emulsion polymerization of and butadiene as main monomer components, so-called SB-based latex, is commonly used as a binder.

Incidentally, in recent years, the production of coated paper has increased significantly as demand for color-printed magazines, pamphlets, and advertisements has increased. In particular, with the trend towards higher speed printing in offset printing, the quality requirements for coated paper and pigment binders are becoming increasingly sophisticated. There is a strong need for improvement. Moreover, this pick strength performance is not related to other print properties, namely wet pick strength,
Since there is a negative correlation with blister resistance, halftone dot reproducibility, etc., there is a growing need for improvements that balance these physical properties to a high level.

Since these properties of coated paper are particularly strongly dependent on the design of the SB latex used as a pigment binder, various studies have been made on the performance of the SB latex.

For example, it has been confirmed that the proportion of the insoluble portion of a copolymer latex film in solvents such as benzene, toluene, and tetrahydrofuran is the controlling factor for pick strength and blister resistance, so various studies have been conducted from this aspect. Specifically, it has been proposed that excellent performance can be achieved by adjusting the composition and gel fraction of the copolymer in latex to a specific range (Japanese Patent Publication No. 59-3598). , Japanese Patent Publication No. 60-17879, Japanese Patent Application Publication No. 58-4894). The gel fraction of this latex varies depending on various polymerization factors such as monomer composition and polymerization temperature, but a common and simple method for adjusting it to a desired level is to add a chain transfer agent.

Conventionally, halogenated hydrocarbons represented by carbon tetrachloride, alkyl mercaptans represented by t- or n-dodecyl mercaptan, sulfides, and the like have been used as chain transfer agents.

However, for boat fishing, the pick strength of coated paper is highest when the gel fraction is in the range of 75 to 95% by weight for SB latex, whereas the blister resistance is lower as the gel fraction is lower. It is recognized that it will be good,
None of the above techniques are fully satisfactory in order to simultaneously improve both pink strength and blister resistance to a high level.

In addition, the optimal butadiene unit fraction for wet pick strength in offset printing is 34% by weight or less, which is different from the optimal butadiene unit fraction for pink strength.
It was difficult to achieve high levels of both physical properties at the same time.

In addition, good halftone dot reproducibility and super calendar stain resistance during coated paper production are particularly important for gravure printing paper. However, since this product is designed to have a high butadiene unit fraction, halftone reproducibility has been improved to a sufficient degree without impairing supercalendar stain resistance. not present.

Additionally, carpet hack sizing adhesives are generally compositions of copolymer latex blended with fillers such as calcium carbonate or aluminum hydroxide and other additives such as thickeners. This adhesive composition is used in the production of tufted carpets, needle punch carpets, etc., mainly to prevent piles from falling off and to bond with primary base fabrics such as jute. Therefore, in this case, improving the adhesive strength, which is the most important physical property of Carpet 7, is one of the biggest technical challenges in this industry, and therefore, improvements are being considered from the aspect of blending copolymer latex and compositions. However, the reality is that so far nothing has been achieved to a satisfactory level.

Furthermore, the adhesive side has traditionally been manufactured by dissolving natural rubber, synthetic rubber, etc. in an organic solvent, coating it on a base material, and evaporating the organic solvent, but in recent years, it has become more expensive due to the risk of fire and labor. Due to hygienic issues, there is increasing momentum to use polymer aqueous dispersions (latex) using water as a dispersion medium, and aqueous dispersions of rubber-tackifying resin combinations are being developed (Japanese Patent Publication No. 5728545, JP-A-55-48270, JP-A-58160378, JP-A-58-1
83771). This aqueous dispersion containing synthetic rubber latex and tackifier resin has a solid content of 1
A composition in which 50 to 100 parts by weight of a tackifier resin is added to 00 parts by weight is common, and shows good adhesive properties at a measurement temperature of 20 to 23°C, but shows good adhesive properties at a temperature of 0°C. As for the force, a satisfactory value was not obtained. In addition, there have been proposed products in which adhesive properties can be obtained only by using a rubber latex polymer without the presence of a tackifying resin (Japanese Patent Application Laid-Open Nos. 56-145909 and 57-57707). However, this material has the drawback of extremely low adhesion to polyethylene.

[Problem to be solved by the invention]

As described above, the conventional technology cannot cope with the ever-increasing printing speed of coated paper, and there is a strong need for the emergence of copolymer latex as a binder that enables the production of high-quality coated paper. The current situation is that In addition, copolymer latexes with high adhesive strength are also desired for carpets, adhesives, and adhesives.

[Means to solve the problem]

Under these circumstances, the present invention has been developed to develop a high-performance co-sponsor to further improve the balance between bulk strength and other properties in coated printing papers, as well as the adhesive strength in carpet pack sizing and adhesives. As a result of various studies aimed at providing polymer latex, we found that conjugated diene,
A copolymer latex obtained by using an azobenzene derivative as a chain transfer agent in emulsion polymerization of ethylenically unsaturated carboxylic acids and other monomers copolymerizable with these has surprisingly achieved the above objectives. This discovery led to the completion of the present invention.

That is, the present invention uses an azobenzene derivative represented by the following general formula as a chain transfer agent (where X, Y are respectively -H, -OH, -C1-RR-OH, -〇-R-
Indicates either OH or a halogen element. Here, R represents an alkyl group having 1 to 6 carbon atoms.

The present invention will be explained in detail below.

A feature of the present invention is that when producing a copolymer latex by emulsion polymerization, an azobenzene derivative represented by the following general 2 is used as a chain transfer agent (wherein, X and Y are -H, -OH, -0-R, respectively). .

117-OH, -0-R-0)1. Indicates any of the halogen elements. Here, R represents an alkyl group having 1 to 6 carbon atoms.

Examples of the chain transfer agent include azobenzene, hydroxyazohenzene, methoxyazobenzene, hydroxymethylazohenzene, and the like.

The preferred amount of the chain transfer agent used is 0.2 to 20 parts by weight, more preferably 0.3 to IO parts by weight, based on 100 parts by weight of the monomer.

The chain transfer agent can also be used in combination with other well-known chain transfer stoppers. Examples of other well-known chain transfer agents include thioalkanes such as t-dodenormer butane, n-dodenormer butane; thioalcohols such as mercaptoethanol and mercaptopropanol; thioalkyl carboxylic acids such as thioglycolic acid and thiopropionic acid. Acids; sulfides such as dinotyl sulfide and diethyl sulfide; halogenated hydrocarbons such as carbon tetrachloride and bromoform; and the like.

Furthermore, any known method can be used for using the chain transfer agent. i.e. - peduncle addition method;
These include a continuous additional addition method, an intermittent additional addition method, and a concentration gradient type addition method in which the addition rate is sequentially changed.

The copolymer latex is obtained by emulsion copolymerization of monomers composed of a conjugated diene, an ethylenically unsaturated carboxylic acid, and other monomers copolymerizable with these.

Conjugated dienes used in the present invention include butadiene, isoprene, 2-chloro-1,3-butadiene, and the like.

The amount used is preferably in the range of 20 to 90% by weight based on the total monomers. Furthermore, in the case of a copolymer latex for coated paper, the preferred range of this conjugated diene layer is 20
~70% by weight.

Examples of ethylenically unsaturated carboxylic acids used in the present invention include monobasic carboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dibasic carboxylic acids such as itaconic acid, maleic acid, and fumaric acid; Examples include esters.

The amount of the ethylenically unsaturated carboxylic acid used is preferably in the range of 0.5 to 10% by weight based on the total monomers.

Among the other monomers used in the present invention, aromatic (di)vinyl compounds are most typically and effectively used, followed by (meth)acrylic acid esters, vinyl cyanide compounds, and ethylenic amide monomers. etc. Examples of aromatic (di)vinyl compounds include styrene, α-
Methylstyrene, chlorostyrene, alkylstyrene,
Examples include divinylbenzene. (Meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, hydroxyethyl (meth)acrylate, and , glycidyl (meth)acrylate, ethylene glycol di(meth)acrylate, etc. Examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile.

Examples of the ethylenic amide monomer include (meth)acrylamide, N-methylol (meth)acrylamide, and the like. In addition, vinyl esters such as vinyl acetate, vinyl chloride, vinyl halides such as vinylidene chloride, ethylenic amine monomers such as aminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, Examples include sodium styrene sulfonate.

The production method of the present invention is produced by a conventionally known normal emulsion polymerization method. - For boat fishing, the polymer concentration ranges from 40 to 60% by weight. The particle size of the copolymer latex can be adjusted by the proportion of surfactant and/or seed latex used, and in general, the higher the proportion used, the smaller the particle size of the produced copolymer latex.

Here, the preferred range of particle size is 0.05 to 1 μm, more preferably 0.07 to 0.5 μm.

Examples of surfactants include fatty acid soaps, rosin acid soaps, anionic surfactants such as alkyl sulfonates, dialkylaryl sulfonates, alkyl sulfosuccinates, polyoxyethylene alkyl sulfates, and polyoxyethylene alkylaryl sulfates. : There are nonionic surfactants and cationic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxysorbitan fatty M ester, and oxyethylene oxypropylene bronze copolymer. The surfactant is usually used as an anionic surfactant alone or as a mixed anionic/nonionic system, and its usage ratio based on the total monomers is generally in the range of 0.05 to 2% by weight.

Polymerization initiators required to initiate polymerization are those that initiate addition polymerization of monomers by radical decomposition in the presence of heat or reducing substances, such as water-soluble or oil-soluble beroxonisulfate, peroxide, etc. , azobis compounds, etc. are commonly used. Examples include potassium peroxonisulfate, sodium peroxonisulfate, ammonium peroxonisulfate, hydrogen peroxide, L-butyl hydroperoxide, benzoyl peroxide, 2,2-azobisisobutyronitrile, cumene hydroperoxide, etc. Sulfates are most preferably used. The proportion of the polymerization initiator used is usually 0.2 to 1.5% by weight based on the total monomers. The polymerization temperature is generally in the range of 60 to 90°C, but when it is desired to accelerate the polymerization rate or polymerize at a lower temperature, sodium bisulfite, ascorbic acid or its salts, erythorbic acid or its salts, Rongalite are used. The so-called Redo Nox polymerization method can be used, in which a reducing agent such as the following is used in combination with a polymerization initiator.

Furthermore, various polymerization regulators are often added as desired. For example, sodium hydroxide,
These include p)I regulators such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, and disodium hydrogen phosphate, and various chelates such as sodium ethylenediaminetetraacetate.

The use of the copolymer latex produced according to the invention as a binder for paper coatings can be carried out in the usual manner. That is, inorganic pigment and/or organic pigment, water-soluble polymer,
This is an embodiment in which a copolymer latex is mixed with various additives to form a uniform dispersion. This paint can be applied to the base paper using a conventional method such as various blade coaters or roll coaters.

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to these examples in any way.

In addition, each characteristic was calculated|required as follows.

(a) Blister resistance Using an R1 printing tester (manufactured by Mei Seisakusho), 0.3 d of printing ink (Webb Zett yellow, manufactured by Dainippon Ink Co., Ltd.) was printed on both sides of the coated paper. This printed coated paper is cut to an appropriate size, and the test piece is immersed in a silicone oil constant temperature bath adjusted to a predetermined temperature to observe whether or not blisters occur. This test is performed by changing the temperature of the thermostatic chamber, and the degree of blistering is compared.

The evaluation was performed using a 10-point evaluation method, and the better the blister resistance, the higher the score.

(b) Printing ink (SD Susu--Deluxe 50 Beni B; tank value 18, manufactured by Shuso Shiki Co., Ltd.) using a Drybic strength R1 printing tester.
4d Perform overprinting 5 times, trace the picking state that appears on the rubber roll onto another mount, and observe the extent of the picking state. The evaluation was performed using a 10-point evaluation method, and the fewer the picking phenomenon, the higher the score.

Examples and Comparative Examples 4 parts by weight of an aqueous dispersion of seed particles with a diameter of 0.04 μM (seed solid content concentration 25% by weight) was placed in a pressure-resistant reaction vessel equipped with a stirring device and a temperature control jacket, and 70 parts by weight of water was added. parts, 0.2 parts by weight of sodium lauryl sulfate,
2.5 parts by weight of itaconic acid was charged, the internal temperature was raised to 80°C, and then an oil mixture consisting of 100% salt and a chain transfer agent shown in Table 1, 15 parts by weight of water, and sodium peroxonisulfate was added. 1 part by weight, 0.2 part by weight of sodium hydroxide,
An aqueous solution consisting of 0.1 part by weight of sodium lauryl sulfate was added at a constant flow rate over 4 hours and 5 hours, respectively. The temperature of 80"C was maintained for one hour and then cooled. The pH of the resulting copolymer latex was adjusted to 7 with sodium hydroxide, and unreacted monomers were removed by steam stripping. and mesh 75
It was filtered through a μm filter cloth.

Note that all copolymer latexes were adjusted so that the final solid content concentration was 50% by weight.

Application example Copolymer lattes prepared in Examples and Comparative Examples.

The performance of the paper coating binder was evaluated. The results are shown in Table 4.

The coating material had the formulation shown in Table 2 and was prepared using a high-speed stirrer with an amount of water that gave a nonvolatile content concentration of 63% by weight. The pH of the paint was adjusted to 9.0 with aqueous ammonia. Table 3 shows the conditions for preparing coated paper using this paint.

From Table 4, it is understood that the coated paper using the copolymer latex of the present invention as a coating has a highly balanced pick strength and other physical properties.

Table 1 and Table 1 (Table 1) (Effects of the Invention) According to the present invention, the balance between bulk strength and other properties in coated printing paper, as well as the adhesive strength in carpet bank sizing and adhesives, can be further improved. It is possible to easily obtain a high-performance copolymer latinx with high moisture content.

Patent applicant: Asahi Kasei Industries, Ltd.

Claims (1)

[Claims] In the emulsion copolymerization of conjugated dienes, ethylenically unsaturated carboxylic acids, and other monomers copolymerizable with these, an azobenzene derivative represented by the following general formula is used as a chain transfer agent ▲ Numerical formula, chemical formula, There are tables, etc. ▼ (However, X and Y are -H, -OH, -O-
Indicates either R, -R-OH, -O-R-OH, or a halogen element. Here, R represents an alkyl group having 1 to 6 carbon atoms.