JPH0931126A - Scourability improver - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain scourability improver which can give a scoured fiber excel lent in wettability and water absorptivity and is effective even when used in a small amount. SOLUTION: This scourability improver comprises a (co) polymer obtained by polymerizing an α, β-unsaturated carboxylic acid (salt) in the presence of a radical polymerization initiator and a chain transfer agent for radical polymerization represented by the formula (Q is a polyvalent organic group; X<1> is carbonyl or -CONH-; A<1> and A<2> are each a 1-8 C alkylene; X<2> is oxygen, sulfur or an NH group; Z is a chain transfer group, p, q, r and x are each 0 or 1; m is an integer of 1-50; n is an integer of 2-100; and the units within Δ} and the units with Δ} may be the same or different from each other).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a scouring agent for fibers.

[0002]

2. Description of the Related Art Heretofore, scouring of fibers has been widely carried out by a method in which an alkali agent and a surfactant are used in combination. The refining removes water-repellent substances such as fats, waxes, spinning oils, spinning oils, sizing agents, or machine oils that the fibers have to give the fibers wettability and water absorption, and bleaching which is a subsequent step, This is a pre-process that enables efficient dyeing and finishing. However, in the refining method using a combination of an alkaline agent and a surfactant, when the hardness of the water used during refining is high, the fat and oil component is hydrolyzed by the alkaline agent, and the produced fatty acid binds to the hardness component of water, Metal soap forms and deposits on the fibers. Since the metal soap cannot be easily emulsified and dispersed with a usual surfactant used for scouring, water repellency remains after the scouring step and sufficient wettability and water absorption cannot be obtained, and bleaching and dyeing which are post-steps. However, there is a problem that finishing processing cannot be performed efficiently. The same problem also occurs in the bleaching and dyeing processes. A salt of a (meth) acrylic acid polymer is known as a refining property improving agent for solving this problem (for example, JP-A-59-187669). This is a bleaching improver in the bleaching and dyeing process,
It is also used as a dyeability improver.

[0003]

However, the molecular weight distribution of the above-mentioned polymers obtained by ordinary radical polymerization is relatively wide, and these scouring agents improve the wettability and water absorption of fibers after scouring. It is not yet satisfactory, and there is a problem that the amount used is large.

[0004]

Means for Solving the Problems The present inventors have found that a specific polymer having a narrow molecular weight distribution obtained by radical polymerization using a specific chain transfer agent solves the above-mentioned problems and has reached the present invention. did. That is, the present invention is obtained by polymerizing an α, β-unsaturated carboxylic acid (salt) as a constitutional unit using a radical polymerization initiator and a chain transfer agent for radical polymerization represented by the following general formula (1). It is a scouring property improver comprising a (co) polymer. General formula In the formula, Q is a polyvalent organic group, X ¹ is a carbonyl group or -C
ONH-, A ¹ and A ² are alkylene groups having 1 to 8 carbon atoms, X
² is an oxygen atom, a sulfur atom or an NH group, Z is a chain transfer group, p, q, r and x are 0 or 1 respectively, and m is 1 to 5
An integer of 0 and n are integers of 2 to 100, and may be the same or different in [] and in {} when m is 2 to 50.

In the present invention, examples of the α, β-unsaturated carboxylic acid (salt) include (meth) acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, and anhydrous. Α, β-unsaturated carboxylic acids such as citraconic acid or their anhydrides; and alkali metal (lithium, sodium, potassium, etc.) salts of these α, β-unsaturated carboxylic acids, alkaline earth metals (calcium, magnesium, etc.) Examples thereof include salts, ammonium salts, organic amine (alkanolamine, lower alkylamine, etc.) salts, and combinations of two or more of these. Among these, preferred are (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, alkali metal salts or ammonium salts thereof, and combinations of two or more thereof.

A copolymer with another copolymerizable monomer may be used as long as the effect of the present invention is not impaired. Examples of other copolymerizable monomers include (a) aromatic ethylenically unsaturated monomers: styrenes such as styrene, α-methylstyrene, vinyltoluene, vinylnaphthalene, styrenes such as dichlorostyrene. (B) Aliphatic ethylenically unsaturated monomers: ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, butadiene, isoprene, etc .; Cyclic ethylenically unsaturated monomers: cyclopentadiene, pinene,
Limonene, indene, bicyclopentadiene, ethylidene norbornene, etc .; (d) alkyl (meth) acrylate having an alkyl group having 1 to 50 carbon atoms: methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl ( (Meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, eicosyl (meth) acrylate and the like; (e) hydroxyl group-containing (meth) acrylate: hydroxyethyl Examples thereof include (meth) acrylate and hydroxypropyl (meth) acrylate.

In the copolymer, the content of the monomer other than the α, β-unsaturated carboxylic acid (salt) is usually 0 to 60% by weight, preferably 0 to 30%.

In the general formula (1), Q is a residue obtained by removing OH from polyhydric alcohol or polyhydric phenol,
Examples thereof include a residue obtained by removing COOH from a polycarboxylic acid. As the polyhydric alcohol, alkylene glycol having 2 to 8 carbon atoms (ethylene glycol, propylene glycol, 1,3- and 1,4-butanediol, 1,6
-Hexanediol, neopentyl glycol, etc.),
Dihydric alcohols such as diols having a cyclic group and having 5 to 10 carbon atoms; 3 carbon atoms such as glycerin, trimethylolpropane, trimethylolethane and hexanetriol
~ 12 trihydric alcohol; 4 to 20 carbon atoms such as pentaerythritol, methylglycoside, diglycerin, etc.
Alcohols having a higher number of functional groups, such as pentitols (adnitol, arabitol, xylitol, etc.), hexitols (sorbitol, mannitol, iditol, taritol, dulcitol, etc.), sugars [sucrose, monosaccharides (glucose, mannose, etc.). , Fructose, sorbose, etc.), oligosaccharides (crehalose, lactose, raffinose, etc.)]; glucosides [eg polyols (glycol,
Glucosides of glycerin, trimethylolpropane, alkanepolyols such as hexanetriol); polyalkanepolyols [eg polyglycerin such as triglycerin, tetraglycerin]; polypentaerythritol (dipentaerythritol, tripentaerythritol, etc.); cycloalkanepolyols [Tetrakis (hydroxymethyl) cyclohexanol etc.] and the like can be mentioned. Further, polyvinyl alcohol having a degree of polymerization of up to 100 can be used.

Further, di- and triethanolamine; alkylamines having 2 to 20 carbon atoms, 2 to 6 carbon atoms
Alkylenediamines such as ethylenediamine, propylenediamine, hexamethylenediamine, polyalkylenepolyamines such as aliphatic amines such as diethylenetriamine, triethylenetetramine, aniline, phenylenediamine, diaminotoluene, xylylenediamine, methylenedianiline, diphenyletherdiamine, etc. Examples thereof include alicyclic amines such as group amines, isophoronediamine, cyclohexylenediamine, and dicyclohexylmethanediamine, and alkylene oxide adducts such as aminoethylpiperazine.

Examples of polyphenols include monocyclic polyphenols such as pyrogallol, hydroquinone and phloroglucin; bisphenols such as bisphenol A and bisphenol sulfone; condensation products of phenol and formaldehyde (novolak) and polyphenols.

As the polyvalent carboxylic acid, divalent carboxylic acid [(1) aliphatic dicarboxylic acid having 2 to 20 carbon atoms (maleic acid, fumaric acid, succinic acid, adipic acid, sebacic acid, malonic acid, azelaic acid, Mesaconic acid, citraconic acid, glutaconic acid, etc.); (2) Alicyclic dicarboxylic acid having 8 to 20 carbon atoms (cyclohexanedicarboxylic acid, methylmedic acid, etc.); (3) Aromatic dicarboxylic acid having 8 to 20 carbon atoms (phthalate) Acid, isophthalic acid, terephthalic acid, toluenedicarboxylic acid, naphthalenedicarboxylic acid, etc.);
(4) Alkyl or alkenyl succinic acid having a hydrocarbon group having 4 to 35 carbon atoms in the side chain (isododecenyl succinic acid, n-dodecenyl succinic acid, etc.), trivalent or higher carboxylic acids [(1) carbon number 7 to 20 aliphatic polycarboxylic acids (1,2,4-butanetricarboxylic acid, 1,2,5
-Hexanetricarboxylic acid, 1,3-dicarboxylic acid-
2-methyl-2-methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, etc.); (2) carbon number 9-20
Alicyclic polycarboxylic acids (e.g., 1,2,4-cyclohexanetricarboxylic acid); (3) aromatic polycarboxylic acids having 9 to 20 carbon atoms (1,2,4-benzenetricarboxylic acid, 1,2,5 -Benzenetricarboxylic acid, 2,5,7
-Naphthalene tricarboxylic acid and 1,2,4-naphthalene tricarboxylic acid, pyromellitic acid, benzophenone tetracarboxylic acid, etc.)] and the like. Further, an unsaturated polycarboxylic acid polymer having a degree of polymerization of up to 100 can be mentioned.

In the general formula (1), Z is SH,
SR, SSR, CX ₃ (R is an alkyl, aryl, aralkyl, alkoxy, aryloxy or cycloalkyl group having 1 to 20 carbon atoms, which may be substituted with a halogen atom, an alkyl group, a cyano group or a nitro group. Is a chlorine atom, a bromine atom.) And the like. Of these, SH is preferred.

In the general formula (1), p is 0 when Q is a polyhydric alcohol or polyhydric phenol residue, and p is 1 when Q is a polyhydric carboxylic acid residue. If p is 0,
x and q are 0 or 1, and r is 0. When p is 1, x is 0 and q and r are 0 or 1, respectively.

In the general formula (1), n is preferably 2 to 8 and m is preferably 1 to 30.

The chain transfer agent represented by the general formula (1) is Z
When is SH, it can be manufactured by the following method, for example. Chain Transfer Agent 1 (when p is 0, x is 0, q is 0 and r is 0) After the cyclic ether is added to the ω-mercapto-alkyl alcohol, it is etherified with the polyhydric alcohol. Alternatively, a cyclic ether is added to a polyhydric alcohol, the terminal is chlorinated with thionyl chloride or the like, and then reacted with an alkali hydrosulfide. Specific examples of chain transfer agents include polyoxyethylene glycol-di-2-mercaptoethyl ether.

Chain transfer agent 2 (p is 1, x is 0, q is 0,
When r is 0) A cyclic ether (cyclic sulfide, cyclic imine) is added to ω-mercapto-alkyl alcohol, and then esterified with a polyvalent carboxylic acid.

Chain transfer agent 3 (p is 0, x is 1, q is 1,
When r is 0) A cyclic lactone (cyclic lactam) is added to the polyhydric alcohol, and then esterified (amidated) with ω-mercapto-carboxylic acid. Specific examples of chain transfer agents include triethanolamine-ε-caprolactone adduct-tri-3-mercaptopropionic acid ester.

Chain transfer agent 4 (p is 0, x is 1, q is 0,
When r is 0) After adding a cyclic lactone (cyclic lactam) to the polyhydric alcohol, etherification (amination) is carried out with ω-mercapto-halogenide. Specific chain transfer agents include triethanolamine-ε-caprolactone adduct-tri-2
-Mercaptoethyl ether and the like.

Chain transfer agent 5 (p is 0, x is 0, q is 1,
When r is 0) After adding a cyclic ether (cyclic sulfide, cyclic imine) to the polyhydric alcohol, esterification (thioesterification, amidation) is carried out with ω-mercapto-carboxylic acid. Specific examples of chain transfer agents that can be produced by this method include the following. (1) 1-10 alkylene oxides (ethylene glycol, propylene glycol, etc.) in alkylene glycols (ethylene glycol, propylene glycol, etc.)
A product obtained by adding 0 mol and forming a diester with 3-mercaptopropionic acid at the end. Polyoxyethylene glycol (number average molecular weight 630) di-3-mercaptopropionic acid ester, polyoxypropylene glycol (number average molecular weight 600) di-3-mercaptopropionic acid ester and the like. (2) A compound in which 1 to 150 mol of alkylene oxide is added to a trihydric or higher polyhydric alcohol (glycerin, pentaerythritol, sho, etc.), and the end is formed into a diester with 3-mercaptopropionic acid. Tetra-3-mercaptopropionic acid ester of pentaerythritol ethylene oxide 20 mol adduct and the like. (3) Polyvinyl acetate (weight average molecular weight 50,000,
Esterified with 2-mercaptoacetic acid (saponification degree 10%).

Chain transfer agent 6 (p is 1, x is 0, q is 1,
When r is 0) After adding a cyclic ether (cyclic sulfide, cyclic imine) to the polycarboxylic acid, esterification (thioesterification, amidation) is carried out with ω-mercapto-carboxylic acid. Specific examples of the chain transfer agent include propylene oxide adipate 4 mol adduct-di-2-mercaptoacetic acid ester.

Chain transfer agent 7 (p is 1, x is 0, q is 0,
When r is 1) A cyclic lactone (cyclic lactam) is added to the polycarboxylic acid, and then esterified with ω-mercapto-alcohol.

Of these chain transfer agents, preferred are chain transfer agents 1 to 4, more preferred are chain transfer agents 1 and 2, and particularly preferred is chain transfer agent 1.

In the production of the above compound, it is also possible to co-add a cyclic ether and a cyclic lactone,
When co-adding, either random co-adding or block co-adding may be used. In the above compounds, examples of the cyclic ether include ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, and styrene oxide, examples of the cyclic thioether include episulfide, and examples of the cyclic imine include ethyleneimine. These may be co-added, and when co-added, either random co-addition or block co-addition may be performed. Of these, preferred are cyclic ethers, and more preferred are ethylene oxide, propylene oxide and mixtures thereof.

In the above compounds, the cyclic lactone includes ε-caprolactone, δ-valerolactone and the like, and the cyclic lactam includes ε-caprolactam and the like. These may be co-added, and when co-added, either random co-addition or block co-addition may be performed.

The main purpose of the chain transfer agent is that a plurality of chain transfer groups are present with at least four functional groups (ether, ester, amide, etc.) separated from each other. It allows the production of narrow polymers.

As long as the above conditions are satisfied, the structure can be arbitrarily selected depending on the properties of the polymer to be obtained. For example, in terms of the compound 1, the cyclic ether to be added is preferably ethylene oxide in order to obtain a (meth) acrylic acid (salt) polymer, and is preferable in order to obtain a (meth) acrylic acid ester polymer or a styrene polymer. Propylene oxide is preferred.

The amount of the chain transfer agent used in the production method of the present invention is usually 0.001 to 50% by weight based on the monomer.
It is preferably 0.01 to 30% by weight, particularly preferably 0.1.
1 to 15% by weight.

The radical polymerization initiator is of a type that produces free radicals to initiate polymerization, for example, 2,2 '.
-Azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1- Arbonitrile), 2,2 '
-Azobis (2,4,4-trimethylpentane), dimethyl 2,2'-azobis (2-methylpropionate), 2,2'-azobis [2- (hydroxymethyl)
Propionitrile], azo compounds such as 1,1′-azobis (1-acetoxy-1-phenylethane); dibenzoyl peroxide, dicumyl peroxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, Organic peroxides such as benzoyl peroxide, lauroyl peroxide, persuccinic acid; persulfates,
Inorganic peroxides such as perborate can be used. Hydrogen peroxide, a redox type initiator or the like can be used.
These may be used in combination of two or more. The amount of the radical polymerization initiator is usually 0.01 to 10% by weight with respect to the monomer,
Preferably it is 0.05 to 5% by weight.

As the polymerization method, solution polymerization, emulsion polymerization,
Either suspension or bulk polymerization may be used, but solution polymerization is preferable in order to obtain a polymer having a narrow molecular weight distribution. Solvents for solution polymerization include water, alcohols (methanol, ethanol, isopropanol, etc.), ketones (acetone, methyl isobutyl ketone, etc.), ethers (tetrahydrofuran, etc.), aliphatic hydrocarbons (hexane,
Heptane, etc.), aromatic hydrocarbons (toluene, xylene, etc.), halogenated solvents (ethylene dichloride, etc.), and mixtures thereof.

The polymerization temperature is usually 50 to 200 ° C.,
Preferably it is 60-150 degreeC. Examples of the temperature include a temperature lower than the boiling point of the polymerization solution under normal pressure, a boiling point of the polymerization solution under normal pressure, and a temperature higher than the boiling point of the polymerization solution under pressure. In order to further narrow the molecular weight distribution, it is preferable to carry out the polymerization at a boiling point or higher of the polymerization solution under pressure. Further, when a dispersion medium, an emulsifier, a dispersant, etc. are used, there is no particular limitation and known ones can be used.

The weight average molecular weight of the (co) polymer is usually 1,
000 to 20,000, preferably 3,000 to 15,
000. When the weight average molecular weight is less than 1,000, the effect of improving the scouring property is not obtained, and when it exceeds 20,000, the effect of improving the scouring property is lowered. The molecular weight distribution (weight average molecular weight / number average molecular weight) of the (co) polymer is usually 1.
2 to 2.0, preferably 1.2 to 1.8. When the molecular weight distribution exceeds 2.0, a large amount of the improver is required and the effect of improving the scouring property is deteriorated.

The scouring agent of the present invention comprises a scouring agent comprising a nonionic surfactant or an anionic surfactant and a builder (caustic soda, soda ash, ammonia, alkali builder such as sodium tripolyphosphate, EDTA, NTA). Usually used together. Further, hydrophilic solvents (methanol, ethanol, isopropyl alcohol, ethylene glycol, etc.), antifoaming agents (silicone antifoaming agents, prolonic antifoaming agents, mineral oil antifoaming agents, etc.) may be mixed or used in combination. .

In the present invention, the fibers can be applied to natural fibers, synthetic fiber and mixed spun and knitted fibers thereof. Natural fibers include cotton, hemp, and wool. Synthetic fiber fibers include rayon and regenerated cellulose fibers such as acetate.
Synthetic fibers such as polyester, polyamide fiber, acrylic and spandex are listed. These blended and interwoven fibers include cotton and hemp and other fibers (such as wool, polyester, polyamide, and acrylic), wool and other fibers (such as polyester, polyamide, and acrylic), and polyester fiber and other fibers (such as rayon, Acetate, polyamide, acrylic, spandex, etc.), polyamide fibers and other fibers (rayon, acetate, acrylic, spandex, etc.).

The amount of the scouring agent of the present invention used is usually
0.02-5 g / l, preferably 0.05 per solid
~ 2 g / l. If it is less than 0.02 g / l, the scouring effect is insufficient, and if it exceeds 5 g / l, the effect does not change.
The scouring agent is usually used in an amount of 0.05 to 10 g / l, and if necessary, an alkali builder is usually used in an amount of 0.2 to 5 g / l. The fiber form is usually a yarn or a knitted fabric.

When the scouring agent of the present invention is used for scouring, the scouring method is not particularly limited, and a conventional method (batch treatment with a wince or jet dyeing machine, continuous treatment with a continuous scouring device, etc.) can be used. . In the case of batch processing, the bath ratio is not particularly limited, but is usually 1: 4 to 1:40, preferably 1: 6 to 1:30.

The refining temperature can be arbitrarily selected depending on the type of fiber to be applied, but it is usually 5 to 140 ° C., preferably 30 to 130 ° C. The scouring property improver of the present invention can be used in a desizing process, a bleaching process and a dyeing process other than the scouring process.

[0037]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. In Examples and Comparative Examples,% and parts represent% by weight and parts by weight. The method for measuring the weight average molecular weight and the molecular weight distribution by GPC is as follows. Machine type: Waters600 (manufactured by Japan Waters Limited) Column: TSK gel G5000pwXL (manufactured by Tosoh) TSK gel G3000pwXL (manufactured by Tosoh) Column temperature: 40 ° C. Detector: RI Solvent: 0.5% sodium acetate water / methanol ( Volume ratio 70/30) Sample concentration: 0.25% by weight Injection volume: 200 μl Standard: Polyoxyethylene glycol

[0038]

【Example】

(Production of Chain Transfer Agent) Production Example 1 A pressure resistant reactor was charged with 620 parts of ethylene glycol and 3 parts of potassium hydroxide, and the temperature was raised to 130 ° C. after purging with nitrogen.
5,740 parts of ethylene oxide was charged and reacted at 130 to 160 ° C. for 5 hours. After aging at the same temperature for 1 hour, the mixture was cooled to 50 to 70 ° C., 160 parts of water and 60 parts of synthetic magnesium silicate were added, and the mixture was stirred for 2 hours and then filtered. Then, it was dehydrated to obtain 6,000 parts of polyoxyethylene glycol having a number average molecular weight of 630. Then, 630 parts of this polyoxyethylene glycol was charged into a reaction vessel, and 260 parts of thionyl chloride was added dropwise at 80 ° C. over 2 hours while stirring. After maintaining the same temperature for 1 hour, 500 parts of a 30% sodium hydrosulfide aqueous solution was added dropwise over 3 hours. After being kept at the same temperature for 1 hour, the temperature was returned to room temperature, liquid separation was performed, and polyoxyethylene glycol-di-
600 parts of 2-mercaptoethyl ether were obtained. This is designated as chain transfer agent A.

Production Example 2 680 parts of pentaerythritol and 60 parts of potassium hydroxide were charged into a pressure resistant reactor, and the temperature was raised to 130 ° C. after purging with nitrogen. Ethylene oxide 4,450 at 130-160 ° C
The parts were charged and reacted for 5 hours. After aging at the same temperature for 1 hour, the mixture was cooled to 50 to 70 ° C., 160 parts of water and 60 parts of synthetic magnesium silicate were added, and the mixture was stirred for 2 hours and then filtered. After that, dehydration was performed to obtain 5,000 parts of an ethylene oxide 20 mol adduct of pentaerythritol. Then, 510 parts of this adduct was charged into a reaction vessel and stirred at 80 ° C.
Then, 260 parts of thionyl chloride was added dropwise over 2 hours. After maintaining the same temperature for 1 hour, 500 parts of a 30% sodium hydrosulfide aqueous solution was added dropwise over 3 hours. After maintaining at the same temperature for 1 hour, the temperature was returned to room temperature and liquid separation was performed to obtain 580 parts of tetra-2-mercaptoethyl ether of 20 mol of ethylene oxide adduct of pentaerythritol which is the chain transfer agent of the present invention. This is designated as chain transfer agent B.

Example 1 260 parts of isopropyl alcohol and 8 parts of water were placed in a pressure resistant reactor.
5 parts were charged, the atmosphere was replaced with nitrogen, the vessel was sealed, and the temperature was raised to 100 ° C. With stirring, a uniform mixture of 380 parts of 80% aqueous solution of acrylic acid and 18 parts of chain transfer agent A and 80 parts of 4% aqueous solution of sodium persulfate were simultaneously added dropwise from separate containers over 4 hours. After holding at the same temperature for 2 hours, it was neutralized with 350 parts of a 48% aqueous solution of sodium hydroxide to obtain a sodium polyacrylate solution. The weight average molecular weight of sodium polyacrylate was 8,000, and the molecular weight distribution was 1.6.

Comparative Example 1 A sodium polyacrylate solution was obtained in the same manner as in Example 1 except that the chain transfer agent A was not used. The weight average molecular weight of sodium polyacrylate was 9,000, and the molecular weight distribution was 2.2.

Example 2 100 parts of isopropyl alcohol and 3 parts of water were placed in a pressure resistant reactor.
3 parts, 20 parts of chain transfer agent B, 38 parts of 80% aqueous solution of acrylic acid, and 10 parts of 10% aqueous solution of sodium persulfate were charged, and the atmosphere was replaced with nitrogen and sealed. Then, the temperature was raised to 105 ° C. with stirring, the reaction was carried out at the same temperature for 2 hours, and then sodium hydroxide 48
% Aqueous solution to neutralize to obtain a sodium polyacrylate solution. The weight average molecular weight of sodium polyacrylate was 9,000 and the molecular weight distribution was 1.7.

Comparative Example 2 A sodium polyacrylate solution was obtained in the same manner as in Example 2 except that the chain transfer agent B was not used. The weight average molecular weight of sodium polyacrylate was 10,000 and the molecular weight distribution was 2.3.

Example 3 260 parts of isopropyl alcohol and 8 parts of water were placed in a pressure resistant reactor.
5 parts were charged, the atmosphere was replaced with nitrogen, the vessel was sealed, and the temperature was raised to 100 ° C. 300 parts of methacrylic acid and a chain transfer agent A20 under stirring
Part of the homogeneous mixture and 80 parts of 4% aqueous sodium persulfate solution were simultaneously added dropwise from separate containers over 4 hours. After holding at the same temperature for 1 hour, it was neutralized with 350 parts of a 48% aqueous sodium hydroxide solution to obtain a sodium polymethacrylate solution. The weight average molecular weight of sodium polymethacrylate was 11,000 and the molecular weight distribution was 1.6.

Comparative Example 3 A sodium polymethacrylate solution was obtained in the same manner as in Example 3 except that the chain transfer agent A was not used. Weight average molecular weight of sodium polymethacrylate 11,000,
The molecular weight distribution was 2.3.

Test Example 1 A cotton knitted fabric was scoured under the following conditions, and its wettability after scouring was examined. The results are shown in Table 1. Scouring conditions: caustic soda flakes 10 g / l, Granup CS-500 (Sanyo Kasei Kogyo scouring agent) 2 g / l,
Scouring property improver (Examples 1 to 3, Comparative Examples 1 to 3) 2 g / l
Into the scouring bath, a cotton knitted fabric was put and scoured in a stainless beaker at a bath ratio of 1:15 at 95 ° C for 20 minutes. Washing with hot water (60 ° C., 2 minutes) was carried out twice, washing with running water for 2 minutes, dehydration and drying. Evaluation: 30 by the Pyreck method for the sample subjected to scouring treatment
The water absorption height per second was measured and used as a measure of wettability.

[0047]

[Table 1]

[0048]

The scouring property improver of the present invention exhibits good scouring properties and has an excellent effect on the wettability of fibers after scouring.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Seiji Yamashita 1 1-11, Hitotsubashi-honmachi, Higashiyama-ku, Kyoto Sanyo Chemical Industry Co., Ltd. Within the corporation

Claims (5)

[Claims] 1. A radical polymerization initiator and a compound represented by the following general formula (1) using an α, β-unsaturated carboxylic acid (salt) as a constituent unit.
A scouring property improver comprising a (co) polymer obtained by polymerization using a chain transfer agent for radical polymerization represented by General formula In the formula, Q is a polyvalent organic group, X ¹ is a carbonyl group or -C
ONH-, A ¹ and A ² are alkylene groups having 1 to 8 carbon atoms, X
² is an oxygen atom, a sulfur atom or an NH group, Z is a chain transfer group, p, q, r and x are 0 or 1 respectively, and m is 1 to 5
An integer of 0 and n are integers of 2 to 100, and may be the same or different in [] and in {} when m is 2 to 50. 2. The α, β-unsaturated carboxylic acid (salt) is at least one selected from the group consisting of (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid and alkali metal salts or ammonium salts thereof. The improver according to claim 1, which is a compound. 3. The improver according to claim 1, wherein Z in the general formula (1) is SH. 4. In the general formula (1), p, q, r, x
Are 0 and X ² is an oxygen atom, respectively. 5. The improver according to claim 1, wherein the polymerization is carried out by solution polymerization.