JP2001348781A - Sizing agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sizing agent composition giving good touch feeling to clothing after sized, slight in sizing loss in laundering such clothing and thereby capable of maintaining such clothing's touch feeling, thus practically highly useful for sizing fabrics including garments. SOLUTION: This sizing agent composition is characterized by comprising an emulsion of an acrylic copolymer having a glass transition temperature of -40 to 80 deg.C which is produced by polymerizing a monomer mixture containing a monomer selected from (meth)acrylic esters using, as the protective colloid, a polyvinyl alcohol or a modified product thereof 70-98 mol% in degree of saponification and 300-3,000 in average degree of polymerization.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention can provide an object to be treated such as clothing after gluing with a good texture, and
The present invention relates to a paste composition which is excellent in adhesive removal during washing and is suitably used for sizing clothes and the like.

[0002]

2. Description of the Related Art
Starch has been used as a paste for clothing and the like, but as a result of various improvements to make it easier to use, an aqueous solution of carboxymethylcellulose, polyvinyl alcohol, or the like is now used in addition to starch. However, these materials have a very high glass transition temperature, and when used as a paste, there are inconveniences such as the treated clothes having a very hard texture and causing contact dermatitis at the contacting parts. Is seen. Furthermore, these aqueous solutions have the disadvantage that they have high viscosity even at low concentrations and are difficult to handle.

Therefore, polyvinyl acetate emulsions have been used to improve these drawbacks, and proposals as pastes have been made, for example, in JP-A-52-53086 and JP-A-53-1.
No. 0793, No. 53-70191, No. 53-9468
No. 8, No. 54-160884, No. 55-103309
Nos. 53-103369 and 56-110709
Nos. 58-4875 and 58-65073.

[0004] However, these pastes mainly composed of polyvinyl acetate emulsion are poor in degreaseability in a washing cycle due to insolubility in water and a hard texture.
There is a problem that glue is deposited on clothing to cause hardening and the like, and when a plasticizer such as dibutyl phthalate is added for the purpose of adjusting texture, there may be a problem of safety or the like.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and can provide a good texture to an object to be processed such as clothing after gluing, and is excellent in desizing at the time of washing. An object of the present invention is to provide a paste composition useful for sizing clothing and the like.

[0006]

Means for Solving the Problems and Embodiments of the Invention The present inventors have made intensive studies to achieve the above object, and as a result, have found that a monomer containing a (meth) acrylic ester can be converted to a specific saponification degree and Obtained by polymerizing polyvinyl alcohol having an average degree of polymerization or a modified product thereof as a protective colloid, using an emulsion of an acrylic copolymer having a glass transition temperature in a specific range as a sizing agent, after sizing. It gives a good texture to clothes and the like, and also has excellent adhesive removal property from the clothes in the washing cycle, and does not harden the clothes and the like due to accumulation, and is preferably used for gluing the clothes and the like. The present inventors have found that a paste composition which can be obtained can be obtained, and have accomplished the present invention.

Accordingly, the present invention provides a monomer mixture containing a monomer selected from (meth) acrylic acid esters having a saponification degree of 70 to 98 mol% and an average polymerization degree of 300 to 98%.
It is characterized by comprising an emulsion of an acrylic copolymer having a glass transition temperature of -40 to 80 ° C, obtained by polymerizing using 3,000 polyvinyl alcohol or a modified product thereof as a protective colloid. A paste composition is provided.

Hereinafter, the present invention will be described in more detail. The sizing composition of the present invention comprises, as a sizing agent, a monomer mixture containing a monomer selected from (meth) acrylic acid esters as a protective colloid of a specific polyvinyl alcohol. An acrylic copolymer emulsion obtained by polymerization is blended.

The (meth) acrylate used herein includes, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and the like having 1 to 18 carbon atoms. (Meth) acrylate with an alcohol having an alkyl group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, glycidyl (meth) ) Acrylate, allyl (meth) acrylate, monomethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, t-butylaminoethyl (meth) acrylate, Glycol di (meth)
Examples thereof include acrylate, diethylene glycol di (meth) acrylate, and trimethylpropane tri (meth) acrylate. In the present invention, one kind of monomer selected from these (meth) acrylates may be used alone, but usually two or more kinds of monomers are used in combination. Note that (meth) acrylate is a general term for acrylate and methacrylate.

Further, in the present invention, a copolymerizable ethylenically unsaturated monomer can be used in combination as a monomer, if necessary, in order to impart physical properties that cannot be exhibited only with the above (meth) acrylate. Examples of the ethylenically unsaturated monomer include acrylonitrile, vinyl acetate, vinyl propionate, styrene, acrylic acid, methacrylic acid, (meth) acrylamide, N-methylol (meth) acrylamide, and N-methoxydimethyl (meth).
Acrylamide, N-butoxydimethyl (meth) acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, glycidyl allyl ether and the like can be mentioned.

The amount of the copolymerizable ethylenically unsaturated monomer used is not more than 15% by weight, especially 1 to 5% by weight of the total amount of the monomers used so as not to impair the object of the present invention.
It is preferable that

The emulsion of the copolymer used in the present invention can be produced by a known emulsion polymerization method using the above monomers. Specifically, the monomers to be used may be mixed, a protective colloid, a polymerization initiator, etc. may be added thereto, and emulsion polymerization may be performed in an aqueous system. Various methods such as a method of performing polymerization while supplying can be applied.

In this case, in the present invention, a specific polyvinyl alcohol or a modified product thereof is used as a protective colloid.
It is essential that the content be で 98 mol%, preferably 75-85 mol%. If the saponification value of the polyvinyl alcohol is too small, it will not be dissolved in water, the emulsifying power will be reduced, and polymerization will not be possible. When the saponification value is too large, when the emulsion obtained by polymerization is used as a sizing agent, the film formed on the surface of the object to be treated has too strong water resistance, and the sizing agent is deposited during washing. However, the texture of the object to be treated is impaired.

Further, the average degree of polymerization of polyvinyl alcohol is 300 to 3,000, preferably 300 to 1,000.
It is in the range of 0. When the average degree of polymerization is too small, the water resistance of the film is significantly reduced, and when the obtained emulsion of the copolymer is used as a sizing agent, the texture of the treated clothes is changed due to rain or the like, and the average degree of polymerization is reduced. If it is too large, the viscosity at the time of dissolution is so high that it becomes impossible to stir, and gelation occurs during the polymerization.

In the present invention, a modified polyvinyl alcohol in which a carboxyl group, an alkyl group, a cationic group or the like has been introduced into polyvinyl alcohol can be used as long as the saponification degree and the average degree of polymerization are in the above ranges.

The amount of these polyvinyl alcohols or modified products thereof is the total amount of the monomers used (the total of the monomers selected from (meth) acrylates and the ethylenically unsaturated monomers used as necessary). The amount used is preferably 5 to 50 parts by weight, particularly preferably 10 to 30 parts by weight, per 100 parts by weight. If the amount of the polyvinyl alcohol or the modified product thereof is too small, the effect as a protective colloid may not be sufficiently exhibited.

In the present invention, when sufficient emulsification performance and chemical stability cannot be obtained by using the above-mentioned polyvinyl alcohol alone, a cationic and / or nonionic emulsifier is used in combination with the above-mentioned polyvinyl alcohol. Is possible.

Examples of the cationic emulsifier include lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, alkyldimethylammonium chloride, alkyldihydroxyethylmethylammonium chloride, amine oxide derivatives, and alkyltrimethyldiamine acetate. Can be

Examples of the nonionic emulsifier include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene laurylamine ether, polyoxyethylene nonylphenyl ether, and polyethylene. Polyoxyethylene alkyl ethers such as glycol lauric acid monoester and sorbitan monolaurate, polyoxyethylene alkylamine ether, polyoxyethylene alkylphenyl ether, polyethylene glycol fatty acid esters, higher alcohol fatty acid esters, and nonions having a vinyl group in the molecule And a reactive emulsifier.

The amount of the cationic and / or nonionic emulsifier is preferably 1 to 10 parts by weight, more preferably 2 to 5 parts by weight, based on 100 parts by weight of the total amount of the monomers.

In the present invention, various polymerization initiators can be used, for example, persulfates such as potassium persulfate and ammonium persulfate, aqueous hydrogen peroxide, t-butyl hydroperoxide, azobis Water-soluble types such as hydrochloride of amidinopropane, and oil-soluble types such as benzoyl peroxide, diisopropyl peroxydicarbonate, cumyl peroxy neodecanoate, cumyl peroxy octoate, and azobisisobutyronitrile. . The amount of these polymerization initiators may be about 0.01 to 3 parts by weight based on 100 parts by weight of the total amount of the monomers.

If necessary, a redox system using a reducing agent such as sodium acid sulfite, Rongalit, L-ascorbic acid, saccharide, amine or the like can also be used.

The polymerization reaction is usually carried out at a temperature of 35 to 90 ° C. with stirring, and the reaction time can be usually about 3 to 40 hours.

By adjusting the pH by adding a basic substance at the start or end of the emulsion polymerization, the storage stability, freezing stability, chemical stability and the like of the emulsion can be further improved. In this case, the pH is preferably adjusted so that the resulting emulsion has a pH of 5 to 9, specifically, ammonia, ethylamine, diethylamine, triethylamine, ethanolamine, triamine, or the like so as to have a pH in this range. Ethanolamine,
An appropriate amount of a basic substance such as dimethylethanolamine, caustic soda and caustic potash can be used.

In the present invention, the glass transition temperature of the copolymer obtained by such polymerization must be in the range of -40 to 80 ° C., preferably -30 to 20 ° C. If the glass transition temperature is too low, the resin film becomes too soft, the surface tack becomes strong, and problems such as blocking occur. On the other hand, if the temperature is too high, the texture becomes hard, which impairs the texture of cloth such as clothing. This glass transition temperature Tg is determined by the following equation based on the monomer used.

1 / Tg = Σ (Wi / Tgi) Tg: glass transition temperature of copolymer (indicated by absolute temperature) Tgi: glass transition temperature of homopolymer of monomer component (i) (indicated by absolute temperature) Wi : Weight fraction of monomer component (i) in copolymer The acrylic emulsion of the copolymer having the above glass transition temperature in the present invention has a solid content of 20 to 50% by weight,
In particular, it is preferably 25 to 40% by weight, and the viscosity is 2
50 to 20,000 mPa · s at 5 ° C., especially 50
It is preferably from 0 to 20,000 mPa · s.

The sizing composition of the present invention is obtained by blending the above-mentioned acrylic emulsion as a sizing agent. If necessary, optional components generally incorporated in the sizing composition can be added. . In this case, the optional components include additives for general polymer emulsions, for example, antifreezing agents such as ethylene glycol, propylene glycol, and ethanol, other fragrances, antibacterial agents, preservatives, fluorescent dyes, pigments, and the like. Can be added in a range that does not hinder the effect of the above. In addition, as an antibacterial agent, a quaternary ammonium salt,
Undecylenic acid, alkyl polyaminoethyl glycine,
Chlorhexine, dodecylguanidine hydrochloride, polyhexamethylene guanidine hydrochloride, acrylonitrile-copper sulfide complex, α-bromocinnamaldehyde, 2- (3,
5-dimethylpiazolyl) 4-hydroxy-6-phenylpyridine, didecyldimethylammonium chloride and the like. The amount of the antibacterial agent to be added is preferably 0.5 to 10 parts by weight, particularly preferably 1 to 5 parts by weight based on 100 parts by weight of the solid content in the emulsion.

[0028]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the following examples, parts and% indicate parts by weight and% by weight, respectively.

Synthesis Example 1 (Synthesis of Emulsion P1) In a polymerization vessel equipped with a stirrer, a condenser, a thermometer and a nitrogen gas inlet, 238 parts of deionized water and PVA-403 were added.
(Kuraray brand name, polyvinyl alcohol ken value 8
8 mol%, average polymerization degree 300)
C. and cooled to 60.degree. Next, deionized water 5
46 parts, methyl methacrylate 144 parts, butyl acrylate 144 parts, methacrylic acid 12 parts, Superlite C
(Mitsubishi Gas Co., Ltd., Rongalit) A liquid obtained by mixing and emulsifying 0.6 part with a homogenizer and 11% perbutyl H-
11 parts of an aqueous solution of 69 (trade name, manufactured by NOF CORPORATION, t-butyl hydroperoxide) were separately added dropwise to the above polymerization vessel at 80 ° C. for 4 hours under stirring with stirring, and further 8 parts were added.
The reaction was carried out at 0 ° C. for 4 hours to complete the polymerization. After cooling, 2
The pH was adjusted to 6 by adding 5% aqueous ammonia.

The obtained copolymer emulsion (hereinafter abbreviated as P1) had a solid content of 30.2%. Tables 1 and 2 show the amounts (%) of charged monomers and the like. Further, the glass transition temperature of the obtained copolymer emulsion,
Table 1 shows the solid content concentration, viscosity and pH.

[Synthesis Examples 2 to 12] (Emulsion P2
Synthesis of P12) The type and charge amount (%) of the monomer and the type and charge amount of polyvinyl alcohol as shown in Tables 1 and 2 were used, optionally using an emulsifier, and copolymerized in the same manner as in Synthesis Example 1 to obtain a solid. A copolymer emulsion (P2 to P12) having a concentration of 29.0 to 40.5% was obtained. Tables 1 and 2 show the glass transition temperature, solid content concentration, viscosity and pH of the obtained copolymer emulsion.

[0032]

[Table 1]

[0033]

[Table 2]

*: Charged amount (%) based on the total amount of monomers used * 1: Glass transition temperature (° C.) of monomer homopolymer * 2: Polyvinyl alcohol PVA403: manufactured by Kuraray Co., Ltd. (Ken value: 88 mol%, Average polymerization degree 300) C-506: Kuraray Co., Ltd. (Ken value: 76 mol%, average polymerization degree: 600) C-17: Shin-Etsu Chemical Co., Ltd. (Ken value: 98.5 mol%, Average polymerization degree: 1700) LM -24: manufactured by Kuraray Co., Ltd. (65% by mole, average polymerization degree: 250) * 3: Emulsifier Cation F2-50: manufactured by NOF Corporation (cocoalkyldimethylbenzylammonium chloride) Esoguard C-12: manufactured by Lion Corporation Nonoxy HS-220: manufactured by NOF Corporation (polyoxyethylene nonylphenyl) Ether) nonionic LP-20R: manufactured by NOF Corporation (sorbitan monolaurate) Emal O: manufactured by Kao Corporation (sodium lauryl sulfate) in the table, polyvinyl alcohol, the amount of emulsifier is the number of copies for the total monomers 100 parts. * 4: Viscosity (25 ° C)

Example 1 Emulsion P1 obtained by mixing emulsion P1 obtained in Synthesis Example 1 with antibacterial cation DDC (trade name, didecyldimethylammonium chloride, trade name, manufactured by Sanyo Chemical Co., Ltd.) at a solid content of 100/1, and ethanol as emulsion P1 In a stirring vessel equipped with a stirrer equipped with a propeller so that the total solid content of the paste composition becomes 0.5%, 1%, and 3%, respectively. The mixture was stirred and mixed for minutes, to prepare an aqueous paste composition solution. 100 parts of the obtained aqueous solution of the paste composition for each concentration and a cotton white cloth (cotton No. 3) 20
The part was placed in a rounder-o-meter, stirred at 20 ° C. for 5 minutes, and then dewatered for 10 seconds. After the dehydration, the treated cloth was air-dried and subjected to an iron press treatment at 150 ° C. for 30 seconds to obtain a test sample. Using the obtained sample, the gluing effect and the desizing property were measured by the following methods. Table 3 shows the results.

1. Gluing effect A test piece of 10 cm in length and 10 cm in width was prepared from the sample, and the bending resistance was measured by the 45 ° cantilever method of JIS L1096A. Bending degree <2.0: too soft, indicating no gluing effect. 2.0 to 4.0: good texture> 4.0: too hard and rough texture

2. Paste-falling property A washing machine having a capacity of 12 kg is charged with 10 L of tap water, 1 kg of a sample treated with an aqueous solution of the paste composition, and 20 g of a neutral detergent (Attack, manufactured by Kao Corporation), washed at 35 ° C. for 5 minutes, and rinsed 2 times.
Dehydration was performed for 3 minutes (35 ° C. × 5 minutes). After the dehydration treatment, the sample was air-dried and subjected to an iron press treatment at 150 ° C. for 30 seconds to obtain a sample.
Was prepared. Using this, JIS L1096
The bending resistance was measured by the 45 ° cantilever method of A, and the adhesive removal property was calculated from the following equation. 80% or more: Good degreasing property Less than 80%: Poor degreasing property

[Examples 2 to 6, Comparative Examples 1 to 6] Tables 3 and 4
A paste composition aqueous solution was prepared in the same manner as in Example 1 except that the type and amount of the copolymer emulsion, the amount of the antibacterial agent, and the amount of ethanol were changed as shown in Example 1, and the evaluation was performed in the same manner. went. The results are shown in Tables 3 and 4.

From the results shown in Tables 3 and 4, the sizing composition of the present invention is excellent in sizing properties, gives a good texture to the garment after the sizing treatment, and is excellent in sizing property during washing, and It was confirmed that the texture could be maintained well.

[0040]

[Table 3]

[0041]

[Table 4]

[0042]

Industrial Applicability The paste composition of the present invention imparts a good texture to clothing after the sizing treatment, and is excellent in the ability to remove glue during washing and can maintain the texture of clothing. It is very useful practically for gluing.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shuichiro Shinohara 2-17-33 Kitafu, Takefu City, Fukui Prefecture Inside Nissin Kagaku Kogyo Co., Ltd. (72) Yuhei Mizuno 4-23-1, Bunkyo, Fukui City, Fukui Prefecture No. Within Nikka Kagaku Co., Ltd. (72) Inventor Kazufumi Okumura 4-231-1, Bunkyo, Fukui City, Fukui Prefecture Inside Nikka Kagaku Co., Ltd. (72) Megumi Sakai 4-23, Bunkyo Fukui City, Fukui Prefecture No. 1 F-term in Nikka Chemical Co., Ltd. (reference) 4J011 KA08 KA15 KA16 KA18 KA24 KA25 KB02 KB05 KB29 QA02 QA03 4L033 AC12

Claims (3)

[Claims] 1. A monomer mixture containing a monomer selected from (meth) acrylic acid esters, having a saponification degree of 70 to
An emulsion of an acrylic copolymer having a glass transition temperature of -40 to 80 ° C, which is obtained by polymerizing 98 mol% of polyvinyl alcohol having an average degree of polymerization of 300 to 3,000 or a modified product thereof as a protective colloid. A paste composition comprising: 2. The amount of polyvinyl alcohol or a modified product thereof is 5 to 50% by weight based on the total amount of the monomer mixture.
The paste composition according to claim 1, which is: 3. The paste composition according to claim 1, wherein a cationic and / or nonionic emulsifier is used in combination with polyvinyl alcohol or a modified product thereof.