JP2849451B2 - Production method of new copolymer latex - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel copolymer latex used for paper coating, carpet backing, fiber bonding or adhesives.

[Conventional technology]

Conventionally, synthetic copolymer latex is, for example, a binder for paper coating, a binder for carpet backsizing,
It is widely used as a binder for bonding fibers such as nonwoven fabric and artificial leather, or as an adhesive for various materials.
When the copolymer latex is used for such a purpose, the copolymer latex is required to have high adhesive strength, and to be excellent in water resistance, blister resistance by drying and heating, and the like.

For example, coated paper has a pigment, such as kaolin clay, calcium carbonate, satin white, talc, titanium oxide, etc., on the surface of the formed base paper for the purpose of improving printability of paper and improving optical properties such as gloss. Coated with a latex as a binder and a water-soluble polymer such as starch, polyvinyl alcohol, carboxymethyl cellulose as a water-retaining agent or an auxiliary binder as a main component, and has been conventionally coated with styrene. And a butadiene as main monomer components, and a styrene-butadiene copolymer latex obtained by emulsion polymerization of these, a so-called SB latex, is generally used as a binder.

By the way, in recent years, the production of coated paper has increased remarkably with the increase in demand for magazines, pamphlets and advertisements printed in color. In particular, with the trend toward high-speed printing in offset printing, the required level for the quality of coated paper and pigment binders is becoming increasingly sophisticated, and therefore, among the quality of coated paper, especially ink pick resistance, so-called pick strength There is a strong demand for improvement. Moreover, this pick strength performance is negatively correlated with other printing properties, such as wet pick strength, blister resistance, halftone dot reproducibility, etc., so further improvements to balance these various properties to a high level have been made. Has been requested. Since these properties of the coated paper greatly depend on the design of the SB latex used as the 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 a solvent such as benzene, toluene, and tetrahydrofuran is a controlling factor of pick strength and blister resistance. Specifically, it has been proposed to exhibit excellent performance by adjusting the composition and gel fraction of the copolymer in the latex to specific ranges (Japanese Patent Publication No. 59-3598). JP-B-60-17879, JP-A-5
No. 8-4894). Although the gel fraction of this latex varies depending on various polymerization factors such as the monomer composition and the polymerization temperature, a method for adjusting the gel fraction to a desired level generally and simply adds a chain transfer agent. As the chain transfer agent, halogenated hydrocarbons typified by carbon tetrachloride, alkyl mercaptans typified by t- or n-dodecyl mercaptan, sulfides and the like have hitherto been used.

However, in general, the pick strength of the coated paper is highest in SB-based latex when its gel fraction is in the range of 75 to 95% by weight, whereas the blister resistance is better as the gel fraction is lower. None of the above techniques are fully satisfactory for simultaneously increasing both pick strength and blister resistance to high levels.

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 pick strength.
It was difficult to make these physical properties high at the same time.

Further, in gravure printing paper, good halftone dot reproducibility and suitability for super calendar stain resistance during the production of coated paper are particularly important. For example, Japanese Patent Application Laid-Open No. 56-70071 discloses a good gravure printing paper. Although a binder is disclosed, since the binder is designed to have a high fraction of butadiene units, the reproducibility of the halftone dot can be sufficiently improved without deteriorating the supercalender stain resistance. Has not been reached.

The adhesive for carpet backsizing is generally a composition in which a filler such as calcium carbonate or aluminum hydroxide and other additives such as a thickener are blended with a copolymer latex. The adhesive composition is used mainly for preventing piles (bushes) from falling off and for bonding to a secondary base fabric such as jute in the production of tufted carpets, needle punch carpets and the like. Therefore, in this case, the improvement of the adhesive strength, which is the most important physical property of the carpet, is one of the biggest technical problems in the industry, and therefore, an improvement from the viewpoint of the blending of the copolymer latex and the composition has been studied. However, in reality, satisfactory levels have not yet been obtained.

Furthermore, pressure-sensitive adhesives have conventionally been produced by dissolving natural rubber or synthetic rubber in an organic solvent, applying the solution to a substrate, and evaporating the organic solvent. Due to the above problems, there has been an increasing trend to use a polymer aqueous dispersion (latex) using water as a dispersion medium, and an aqueous dispersion of a rubber-tackifying resin combination is being developed (Japanese Patent Publication No. 57-28545, JP-A-55-48270, JP-A-Showa
58-160378, JP-A-58-183771). The aqueous dispersion containing the synthetic rubber latex and the tackifier resin generally has a composition in which 50 to 100 parts by weight of a tackifier resin is added to 100 parts by weight of the solid content of the latex, and 20 to 2 parts by weight.
At the measurement temperature of 3 ° C., good adhesive properties are exhibited, but 0
No satisfactory value was obtained for the adhesive strength at a temperature of ° C. In addition, there has been proposed a resin capable of obtaining tackiness with only a polymer of rubber latex without the presence of a tackifier resin (JP-A-56-145909, JP-A-57-57707). However, this has the disadvantage that the adhesion to polyethylene is very low.

[Problems to be solved by the invention]

As described above, the conventional technology cannot cope with a further increase in the speed of printing of coated paper, and the emergence of a copolymer latex as a binder capable of producing high quality coated paper is strongly demanded. It is the present situation. Also, the appearance of a copolymer latex having a high adhesive force has been desired for carpets and adhesives.

[Means for solving the problem]

Under these circumstances, the present invention provides a high-performance co-polymer for improving the balance between pick strength and other performance in coated paper for printing, and further improving the adhesion in carpet backsizing and adhesives. As a result of conducting various studies with the aim of providing a combined latex, a conjugated diene,
In the emulsion polymerization of ethylenically unsaturated carboxylic acids and other monomers copolymerizable therewith, copolymers obtained by using enol ethers derived from aliphatic or alicyclic aldehydes or ketones as chain transfer agents It has been surprisingly found that the combined latex can achieve the above-mentioned object, and has completed the present invention.

That is, the present invention relates to an enol ether derived from an aliphatic or alicyclic aldehyde or ketone as a chain transfer agent in the emulsion polymerization of a conjugated diene, an ethylenically unsaturated carboxylic acid and other monomers copolymerizable therewith. And a method for producing a copolymer latex.

 Hereinafter, the present invention will be described in detail.

A feature of the present invention resides in the use of an enol ether derived from an aliphatic or alicyclic aldehyde or ketone as a chain transfer agent in producing a copolymer latex by emulsion polymerization.

Examples of the chain transfer agent include: (However, R ₁ and R ₂ are hydrogen or a C ₁ -C ₅ alkyl group, and R ₃ is
₁ -C ₂₀ alkyl, C ₅ -C ₂₀ cycloalkyl or C ₇ -C ₂₀
An aralkyl group, R ₄ represents hydrogen or CH ₃ , and R ₅ represents a C ₁ -C ₁₀ alkyl, a C ₅ -C ₁₀ cycloalkyl or a benzyl group. ) And the like.

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

Further, the chain transfer agent can be used in combination with other known chain transfer agents. Examples of other well-known chain transfer agents include thioalkanes such as t-dodecyl mercaptan and n-dodecyl mercaptan; thioalcohols such as mercaptoethanol and mercaptopropanol; thioalkylcarboxylic acids such as thioglycolic acid and thiopropionic acid; dimethyl Sulfides such as sulfide and diethyl sulfide; halogenated hydrocarbons such as carbon tetrachloride and bromoform;

Further, as for the method of using the chain transfer agent, any known method can be used. That is, a batch addition method, a continuous addition method, an intermittent addition method, a concentration gradient addition method in which the addition rate is sequentially changed, and the like.

The copolymer latex is obtained by emulsion-copolymerizing a monomer composed of a conjugated diene, an ethylenically unsaturated carboxylic acid, and other monomers copolymerizable therewith.

The conjugated diene used in the present invention includes butadiene, isoprene, 2-chloro-1,3-butadiene and the like.
The amount used is desirably in the range of 20 to 90% by weight based on the total monomers. Further, in the case of a copolymer latex for coated paper, the more preferable range of the conjugated diene is 20 to 70% by weight.

Examples of the ethylenically unsaturated carboxylic acid used in the present invention include acrylic acid, methacrylic acid, monobasic carboxylic acid such as crotonic acid, itaconic acid, maleic acid, dibasic carboxylic acid such as fumaric acid and monoesters thereof And the like.

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 examples of the monomer used in the present invention, the most typical and effective one is an aromatic (di) vinyl compound, followed by a (meth) acrylate,
And vinyl cyanide compounds and ethylenic amide monomers. Examples of the aromatic (di) vinyl compound include styrene, α-methylstyrene, chlorostyrene, alkylstyrene, divinylbenzene, and the like. (Meta)
As acrylic acid esters, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth)
Acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, and further glycidyl (meth)
Acrylate and ethylene glycol di (meth) acrylate. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. Ethylene amide monomers include (meth)
Acrylamide, N-methylol (meth) acrylamide and the like can be mentioned. Other examples include vinyl halides such as vinyl acetate, ethylenic amine monomers such as aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and diethylaminoethyl (meth) acrylate, and sodium styrenesulfonate. .

The production method of the present invention is produced by a conventionally known ordinary emulsion polymerization method. Generally polymer concentration is 40-60% by weight
Range. The particle size of the copolymer latex can be adjusted by the usage ratio of the surfactant and / or the seed latex. Generally, the higher the usage ratio, the smaller the particle size of the produced copolymer latex.

Here, the preferable range of the particle diameter is 0.05 to 1 μm, and more preferably 0.07 to 0.5 μm.

Examples of the surfactant include anionic surfactants such as fatty acid soap, rosin acid soap, alkyl sulfonate, dialkylaryl sulfonate, alkyl sulfosuccinate, polyoxyethylene alkyl sulfate, and polyoxyethylene alkylaryl sulfate. : Nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene sorbitan fatty acid ester, and oxyethylene oxypropylene block copolymer, and cationic surfactants. The surfactant is usually used in the form of an anionic surfactant alone or in a mixed system of anionic and nonionic surfactants, and is generally used in a proportion of 0.05 to 2% by weight based on all monomers.

The polymerization initiator necessary for the initiation of polymerization is one that initiates addition polymerization of monomers by radical decomposition in the presence of heat or a reducing substance, and is water-soluble or oil-soluble peroxodisulfate, peroxide Products, azobis compounds and the like are generally used. Examples are potassium peroxodisulfate,
There are sodium peroxodisulfate, ammonium peroxodisulfate, hydrogen peroxide, t-butyl hydroperoxide, benzoyl peroxide, 2,2-azobisisobutyronitrile, cumene hydroperoxide and the like, and peroxodisulfate is most preferred. Can be used. The use ratio of the polymerization initiator is usually 0.2 to 1.5% by weight based on all monomers. The polymerization temperature is generally in the range of 60 to 90 ° C., but if it is desired to accelerate the polymerization rate or to carry out the polymerization at a lower temperature, sodium bisulfite, ascorbic acid or a salt thereof, erythorbic acid or a salt thereof, Rongalit, etc. Using a combination of a reducing agent with a polymerization initiator.
A so-called redox polymerization method can be used.

Further, various polymerization additives are often added as desired. For example, sodium hydroxide,
PH adjusters such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate and disodium hydrogen phosphate; and various chelating agents such as sodium ethylenediaminetetraacetate.

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

〔Example〕

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

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

(B) Blister resistance 0.3 ml of printing ink (Webb Zett yellow, manufactured by Dainippon Ink) on both sides of coated paper using RI printing tester (manufactured by Meiji Seisakusho)
Print solid. The printed coated paper is cut into an appropriate size, and the test piece is immersed in a silicone oil thermostat adjusted to a predetermined temperature to observe whether blisters are generated. This test is performed by changing the temperature of the thermostat, and the degree of blistering is compared. The evaluation was performed by a 10-point evaluation method, and the higher the blister resistance, the higher the score.

(B) Dry pick strength Using an RI printing tester, print ink (SD Super Deluxe 50 red B; tack value 18, manufactured by Toka Pigment Co., Ltd.) 0.4 ml five times, and repeat the picking condition that appeared on the rubber roll. Make a backing on the mount and observe the degree. The evaluation was performed by a 10-point evaluation method, and the smaller the picking phenomenon, the higher the score.

EXAMPLES AND COMPARATIVE EXAMPLES 4 parts by weight of an aqueous dispersion of seed particles having a diameter of 0.04 μm (seed solid concentration 25% by weight) were placed in a pressure-resistant reaction vessel equipped with a stirring device and a temperature control jacket, and 70 parts by weight of water were further added. , 0.2 parts by weight of sodium lauryl sulfate and 2.5 parts by weight of itaconic acid, the internal temperature was raised to 80 ° C., and an oily mixture comprising the monomers and chain transfer agent shown in Table 1 was mixed with 15 parts by weight of water, Sodium disulfate 1
Aqueous solution consisting of 1 part by weight, 0.2 part by weight of sodium hydroxide and 0.1 part by weight of sodium lauryl sulfate was added at a constant flow rate over 4 hours and 5 hours, respectively. And 80
After maintaining the temperature at 1 ° C. for 1 hour, the mixture was cooled, and the resulting copolymer latex was adjusted to pH 7 with sodium hydroxide.
Then, unreacted monomers and the like were removed by a steam stripping method, and the mixture was filtered with a filter cloth having a mesh of 75 μm.
In addition, all the copolymer latexes were adjusted so that the solid content concentration was finally 50% by weight.

Application Examples The performance of the copolymer latexes prepared in Examples and Comparative Examples as binders for paper coating was evaluated. Table 4 shows the results.

The coating composition was prepared by a high-speed stirrer with the composition shown in Table 2 and an amount of water at which the nonvolatile content was 63% by weight. The pH of the paint was adjusted to 9.0 with aqueous ammonia. Table 3 shows the preparation conditions of the 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 binder has a highly balanced pick strength and other physical properties.

[Effects of the Invention] According to the present invention, a high-performance copolymer latex capable of further improving the balance between pick strength and other properties in coated paper for printing, and improving the adhesive strength in carpet backsizing and adhesives Can be easily obtained.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C08F 2/00-2 / 60,236 / 00-236/2 2

Claims (1)

(57) [Claims] An enol ether derived from an aliphatic or alicyclic aldehyde or ketone as a chain transfer agent in the emulsion copolymerization of a conjugated diene, an ethylenically unsaturated carboxylic acid and other monomers copolymerizable therewith. A method for producing a copolymer latex, comprising using: