JPH0841784A - Fiber treating agent containing acrylic emulsion as main component - Google Patents

Abstract

PURPOSE:To obtain a fiber treating agent consisting of an emulsion having specific particle diameters obtained by polymerizing an acrylic monomer with a copolymerizable monomer in the presence of a specific amount of a protective colloid substance under specific conditions, free from the generation of migration and capable of imparting fiber article with excellent feeling. CONSTITUTION:An acrylic monomer is subjected to emulsion polymerization with a monomer copolymerizable with the acrylic monomer, in the presence of a protective colloid by using a redox polymerization initiator at <=65 deg.C to obtain an acrylic emulsion having particle diameters of 1.0-3.0mum. Vinyl acetate of <=25% based on the total amount of the monomers is used as the copolymerizable monomer. Cellulose ether protective colloid and/or PVA protective colloid of 2-10wt.% based on the monomers is used as the protective colloid. An excellent fiber product having fine feeling and free from migration during drying is obtained by immersing and treating a fiber into a treating liquid containing the emulsion.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber treating agent for treating fibers to improve physical properties such as texture, strength, water resistance, solvent resistance and chemical resistance. More specifically, the present invention relates to a fiber treatment agent that gives an excellent texture without causing migration where emulsion particles are localized during drying.

[0002]

2. Description of the Related Art Conventionally, solutions and emulsions of synthetic resins have been used for treating fibers. The most important performance required in the processing of fibers is the texture. Treating the fibers with the emulsion obtained with the protective colloid improves the texture of the fibers compared to using the emulsion obtained with the surfactant. However, vinyl acetate emulsions were the main emulsions that could be polymerized using protective colloids, but these emulsions had the drawbacks of poor water resistance and the smell of acetic acid. On the other hand, the acrylic emulsion has no odor of acetic acid and has good water resistance, but it has poor polymerizability and easily aggregates, so that emulsion polymerization cannot be carried out with the protective colloid.
When the fibers are treated with an acrylic emulsion polymerized with a surfactant, the texture is bad, and a balky texture is not obtained in particular. Further, the acrylic emulsion obtained by using the surfactant has a defect that it easily migrates because it is a small particle having a particle size of about 0.5 μm or less. The migration here means that when the base material is impregnated with the emulsion and then forcedly dried by a dryer or the like, the temperature of the base material surface is higher than that of the inside, and water evaporates violently on the surface. As a result of this phenomenon, the resin is localized and moves to the surface, and such a phenomenon adversely affects the strength, feel, printability, water absorption, and the like.

[0003]

DISCLOSURE OF THE INVENTION The present invention solves such problems and provides a fiber treating agent having a good texture, migration-free and acetic acid odor-free.

[0004]

Means for Solving the Problems The present invention provides "1. An acrylic monomer and a monomer copolymerizable with the acrylic monomer in the presence of 2 to 10% by weight of the protective colloid. With a redox type polymerization initiator at a polymerization temperature of 65
Particle size 1.0 to 3.0 μm obtained by emulsion polymerization at ℃ or below
A fiber treatment agent whose main ingredient is acrylic emulsion. 2. The fiber treatment agent according to item 1, wherein vinyl acetate is used as a monomer to be copolymerized with the acrylic monomer in an amount of 25% by weight or less based on all monomers. 3. The fiber treatment agent according to item 1 or 2, wherein the protective colloid is a cellulose ether type and / or a polyvinyl alcohol type. 5. Acrylic monomer is 70 to 99% by weight of all monomers
The used fiber treatment agent according to any one of items 1 to 3. Regarding

[0005]

The first feature of the present invention is to use an acrylic emulsion having a particle size of 1.0 to 3.0 μm, which is polymerized using a protective colloid. The present inventors have studied whether the fibers treated with the vinyl acetate emulsion polymerized with the protective colloid have a good texture, while the fibers treated with the acrylic emulsion polymerized with the surfactant have a poor texture. It was clarified that the size of emulsion particles had a significant effect. That is, if the particle size of the emulsion particles is small, the texture of the fibers deteriorates. If the particle size is not 1.0 to 3.0 μm, a textured and bulky texture cannot be obtained. If it is 1.0 μm or less, migration tends to occur. Particle size is 3.0
If it is more than μm, the dilution stability of the emulsion tends to deteriorate.

A second feature of the present invention is the amount of protective colloid used. The amount of protective colloid is 2 to 10 with respect to the monomer.
Must be% by weight. If it is less than 2% by weight, the particle size of the emulsion will not be 0.5 μm or more. Therefore, the texture of the treated fibers is not good, and migration also occurs. If the protective colloid is more than 10% by weight, thickening occurs and the stability during polymerization is deteriorated,
The stability of the emulsion also deteriorates, and the water resistance also decreases.

A third feature of the present invention is that a redox type initiator is used as a polymerization initiator and polymerization is carried out at 0 ° C to 65 ° C. In order to obtain a good emulsion, the polymerization temperature needs to be 65 ° C. or lower, and for that purpose, it is necessary to use a redox initiator as a polymerization initiator. If the polymerization conditions are not satisfied, the protective colloid and the acrylic monomer are grafted, and the polymerization stability is deteriorated, so that a good emulsion cannot be obtained.

As described above, according to the present invention, the protective colloid is used in an amount of 2 to 10% by weight of the monomer, the redox initiator is used as the polymerization initiator, and the acrylic monomer is added at the polymerization temperature of 65 ° C. or lower. When a monomer copolymerizable with the monomer is polymerized, these conditions act synergistically to obtain an acrylic emulsion having a particle size of 0.5 μm or more, and the emulsion has a texture of treated fibers. And has the effect of preventing migration. It should be noted that vinyl acetate is used as a monomer to be copolymerized with the acrylic monomer. The amount of vinyl acetate used should be 25% by weight or less based on all monomers. This is because if vinyl acetate is used in an amount of 25% by weight or more, the water resistance becomes insufficient and an acetic acid odor is generated.

The raw material used in the present invention will be described. The acrylic monomer used in the present invention,
An alkyl ester having 1 to 12 carbon atoms in the alkyl group and a methacrylic ester having 1 to 12 carbon atoms in the alkyl group. Examples of the monomer copolymerizable with the acrylic monomer and the copolymer used in the present invention include styrene, aromatic vinyl compounds such as methylstyrene, vinyl acetate, and Veova (α-position manufactured by Shell Chemical Co., Ltd. A saturated carboxylic acid branched vinyl ester), acrylic acid, methacrylic acid, itaconic acid, unsaturated carboxylic acid such as crotonic acid, vinyl phosphate, acrylonitrile, acrylamide, N-methylol acrylamide, glycidyl methacrylate, 2-hydroxyalkyl acrylate,
Functional monomers such as polyfunctional silane-based monomers such as alkoxyethyl acrylate, vinyltriethoxysilane, vinyl (2-methoxyethoxy) silane, vinyltrisacetoxysilane, and γ-methacrylopropyltrimethoxysilane, Others include ethylene, vinyl chloride and vinylidene chloride. A monomer having two or more polymerizable unsaturated groups can also be used, and examples thereof include divinylbenzene, divinyl adipate, ethylene glycol di (meth) acrylate, 1,
3-Butyl di (meth) acrylate, diallyl phthalate, etc. are mentioned.

The protective colloid used in the present invention includes cellulose ethers such as carboxymethyl hydroxyethyl cellulose, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose and carboxymethyl cellulose, polyvinyl alcohols such as polyvinyl alcohol and acetoacetylated polyvinyl alcohol,
Polyvinylpyrrolidone, modified polyacrylamide, and the like can be mentioned, and cellulose ethers are preferably used from the viewpoint of polymerization stability.

The redox initiator used in the present invention may be one used in ordinary emulsion polymerization, and examples thereof include potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, and butyl peroxide. A combination of an oxide and a reducing agent is used. In the present invention, a surfactant can be used in combination within 2 times the weight of the protective colloid, if desired, and anionic or nonionic surfactants used in ordinary emulsion polymerization are used. For example, anionic surfactants Examples of the agent include sodium alkylbenzene sulfonate, sodium alkylsulfonate, sodium polyoxyethylene alkylallyl ether sulfonate, and the like, and nonionic surfactants include polyoxyethylene alkyl allyl ether type and polyoxyethylene alkyl ether. Type, polyoxyethylenated polyoxypropylene glycol type and the like. When the surfactant is used in an amount of 2 parts by weight or more of the protective colloid, the particle size does not reach the desired size. Further, if desired, an antiseptic agent, an antifoaming agent, a pigment, a chain transfer agent, a film forming aid, etc. can be added.

[0012]

【Example】

Example 1 65 parts by weight of ethyl acrylate 35 parts by weight of methyl methacrylate 35 parts by weight of 80% aqueous solution of acrylic acid 2.5 parts by weight 2.0 parts by weight of sodium alkylbenzene sulfonate 2.0 parts by weight of water 50 parts by weight of nonyl phenyl ether nonionic surfactant Agent 0.3 parts by weight Water 65 parts by weight Redox initiator of butyl peroxide oxidizer and sodium sulfite reducing agent as the initiator while dropping into a polymerization vessel charged with 20 parts by weight of a 10% aqueous solution of carboxymethyl hydroxyethyl cellulose. Emulsion polymerization was performed at a polymerization temperature of 45 ° C., and pH was adjusted with ammonia. At this time, the amount of carboxymethyl hydroxyethyl cellulose, which is a water-soluble polymer, was 2.0% by weight based on all monomers. The obtained emulsion had a particle size of 1.6 μm and a pH of 5.0.

Example 2 Example 1 was repeated except that the amount of water charged to the polymerization vessel was changed to 40 parts by weight and the amount of the 10% aqueous solution of carboxymethylhydroxyethyl cellulose was changed to 50 parts by weight. At this time, the amount of carboxymethyl hydroxyethyl cellulose, which is a water-soluble polymer, was 5.0% by weight based on all monomers. The obtained emulsion had a particle size of 1.8 μm and a pH of 5.0.

Example 3 The procedure of Example 1 was repeated, except that 20 parts by weight of water charged to the polymerization vessel and 80 parts by weight of a 10% aqueous solution of carboxymethylhydroxyethyl cellulose were used. At this time, the amount of water-soluble polymer carboxymethyl hydroxyethyl cellulose was 8.0% by weight based on all monomers. The obtained emulsion had a particle size of 1.9 μm and a pH of 5.0.

Example 4 Vinyl acetate 15 parts by weight Butyl acrylate 85 parts by weight 80% aqueous solution of acrylic acid 2.5 parts by weight Sodium alkylbenzene sulfonate 2.0 parts by weight Water 50 parts by weight is emulsified to give a nonylphenyl ether type nonion. Surfactant 0.3 parts by weight Water 65 parts by weight Redox of butyl peroxide oxidizing agent and sodium sulfite reducing agent as initiator while dropping into a polymerization vessel charged with 20 parts by weight of 10% aqueous solution of carboxymethyl hydroxyethyl cellulose Emulsion polymerization was carried out at a polymerization temperature of 45 ° C. using a system initiator, and pH was adjusted with ammonia. At this time, the amount of carboxymethyl hydroxyethyl cellulose, which is a water-soluble polymer, was 2.0% by weight based on all monomers. The obtained emulsion had a particle size of 1.6 μm and a pH of 5.0.

Comparative Example 1 (Example of small amount of protective colloid and small particle size) Ethyl acrylate 65 parts by weight Methyl methacrylate 35 parts by weight 80% aqueous solution of acrylic acid 2.5 parts by weight Sodium alkylbenzene sulfonate 2.0 parts by weight 50 parts by weight of water is emulsified, nonyl phenyl ether type nonionic surfactant 0.5 parts by weight Water 50 parts by weight 10% aqueous solution of carboxymethyl hydroxyethyl cellulose 3 parts by weight While adding dropwise to a polymerization vessel, the initiator is added. Emulsion polymerization was carried out at a polymerization temperature of 45 ° C. using a redox initiator of a butyl peroxide oxidizing agent and a sodium sulfite reducing agent, and pH was adjusted with ammonia. At this time, the amount of carboxymethyl hydroxyethyl cellulose, which is a water-soluble polymer, was 0.15% by weight based on all monomers. The obtained emulsion had a particle size of 0.20 μm and a pH of 5.0.

Comparative Example 2 (Example in which Polymerization Stability is Excessive and Polymerization Stability is Poor) 20 parts by weight of water charged to a polymerization vessel, 120 parts by weight of a 10% aqueous solution of carboxymethyl hydroxyethyl cellulose, and 30 parts by weight of water. The procedure of Comparative Example 1 was repeated except that the parts were changed. At this time, the amount of water-soluble polymer carboxymethyl hydroxyethyl cellulose was 12.
0% by weight. In this case, aggregation was remarkable and an emulsion could not be obtained.

Comparative Example 3 (Example of High Copolymerization Ratio of Vinyl Acetate and Poor Water Resistance) Vinyl acetate 40 parts by weight Butyl acrylate 60 parts by weight 80% aqueous solution of acrylic acid 2.5 parts by weight Sodium alkylbenzene sulfonate 2.0 Parts by weight Water 50 parts by weight is emulsified, nonyl phenyl ether type nonionic surfactant 0.3 parts by weight water 50 parts by weight Carboxymethyl hydroxyethyl cellulose 10% aqueous solution 20 parts by weight Start dropping into a polymerization can Emulsion polymerization was performed at a polymerization temperature of 45 ° C. using a redox initiator as a butyl peroxide oxidizing agent and a sodium sulfite reducing agent, and the pH was adjusted with ammonia. At this time, the amount of carboxymethyl hydroxyethyl cellulose, which is a water-soluble polymer, was 2.0% by weight based on all monomers. The obtained emulsion had a particle size of 1.4 μm and a pH of 5.0.

Comparative Example 4 (Example of poor polymerization stability when polymerized at high temperature using a general initiator) The initiator of Example 1 was changed to ammonium persulfate, and polymerization was carried out at a polymerization temperature of 80 ° C. In this case, aggregation was remarkable and an emulsion could not be obtained. (It is considered that grafting proceeds remarkably at 65 ° C or higher.)

<< Hand test >> The rayon web is dipped in an emulsion bath adjusted to a solid content concentration of 3.75% for 1 minute and squeezed with a mangle. This is 80 ° C. × 10 min. dry. After cooling to room temperature, the texture of the obtained nonwoven fabric is evaluated by touch. Balky and good texture ………… ○ Paper-like texture ………… ×

<< Migration resistance test >> Toyo Roshi N
o. 2 pieces were cut into 10 cm × 10 cm, and 5 pieces were taken and numbered 1 to 5. 5% solids concentration
Soak for 1 minute in the emulsion bath adjusted to and squeeze with mangle. Do not remove this, 200 ℃ × 20mi
n. dry. After cooling to room temperature, the amount of resin deposited on each paper is measured and the average amount of coating of five sheets is calculated. The rate of increase / decrease in the amount of each filter paper with respect to this average amount of coverage is calculated. Evaluation The increase / decrease rate of each paper is within 20% ………… ○ The increase / decrease of each paper is 20% or more ………… ×

<< Water Resistance Test >> The tensile strength of the nonwoven fabric obtained in the texture test in the normal state and the tensile strength after immersion in water were measured,
Calculate the retention rate. Normal tensile strength: 50 mm wide test piece at 20 ° C x 65
After standing for 16 hours or more in a thermostatic chamber at% RH, Shimazu Seisakusho's Autograph gripping width 100 mm, pulling speed 200 mm / min. To measure. (Unit: kgf
/ 50 mm) Tensile strength after immersion in water: A test piece having a width of 50 mm is immersed in water at 20 ° C. for 1 hour, and otherwise measured. (Unit: kgf /
50 mm) Retention rate: normal strength / strength after immersion in water × 100 (unit%) Evaluation Retention rate is 15% or more ………… Retention rate is less than 15% …… × Test results are shown in the table. .

[0023]

[Table 1]

In Comparative Example 1, the particle size was small and the texture and the anti-migration property were poor. Comparative Examples 2 and 4 could not be tested because they did not aggregate to form an emulsion. In Comparative Example 3, the texture and migration resistance were good, but the copolymerization ratio of vinyl acetate was high, the water resistance was poor, and there was acetic acid odor.

[0025]

INDUSTRIAL APPLICABILITY The present invention has an excellent effect that a texture is good and migration does not occur by using an acrylic emulsion having a particle size of 0.5 μm or more polymerized under a specific polymerization condition by using a specific amount of protective colloid. Play.

Claims (4)

[Claims] 1. A redox polymerization initiator is used in the presence of an acrylic monomer and a monomer copolymerizable with the acrylic monomer in the presence of 2 to 10% by weight of protective colloid based on the monomer. Particle size 1.0 to 3. obtained by emulsion polymerization at a polymerization temperature of 65 ° C or lower.
A fiber treatment agent whose main ingredient is a 0 μm acrylic emulsion. 2. A vinyl acetate is used as a monomer to be copolymerized with an acrylic monomer in an amount of 25% by weight or less of all monomers.
The fiber treatment agent according to claim 1. 3. The protective colloid is cellulose ether-based and / or polyvinyl alcohol-based.
Or the fiber treatment agent described in 2. 4. The acrylic monomer is 70 to 9 of all monomers.
The fiber treating agent according to any one of claims 1 to 3, which is used in an amount of 9% by weight.