JP2003089978A - Spray-type paste material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a paste composition imparting shape-retaining property and form-stabilizing effect to textiles. SOLUTION: This spray-type paste material is obtained by filling a paste composition in a spray can, wherein the paste composition comprises (a) a vinyl polymer containing specific monomer units (A), (B) and (C) in a specific ratio, (b) a silicone compound, (c) a specific compound such as polyethylene glycol and water.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a spray type paste.

[0002]

2. Description of the Related Art Conventionally, the problems to be solved by the invention
For the pasting of textile products, a method of treating at the rinsing stage of the washing process using a milky-type glue containing a high-molecular compound such as starch paste or polyvinyl acetate was used. Has developed a spray-type paste that can be used by directly spraying textile products during ironing.
Japanese Patent Laid-Open No. 58-18476 discloses a water-soluble silicone obtained by copolymerizing organopolysiloxane with polyoxyethylene or by anionization or cationization, and an ironing agent for clothes, which contains water. It is disclosed. Further, JP-A-5-239774 discloses a finishing agent for clothing containing a water-insoluble silicone having a particle diameter within a specific range. Further, JP-A-8-260356 discloses a spray type paste composition containing a water-soluble synthetic polymer, a water-soluble silicone, and water. On the other hand, in JP-A-9-241973, a water-soluble polymer having a carboxyl group is referred to as PH3.
Disclosed is a treatment agent for spraying which, when used in the range of 5 to 7.5, can obtain good iron slipperiness without using a silicone type iron slippery agent. JP-A-1
JP-A 0-110386 discloses a spray-type finishing composition for clothes, which contains a polyhydric alcohol having 13 to 200 carbon atoms and a water-soluble polymer and has good iron sliding property. JP-A-11-229266 discloses a water-soluble polymer paste, polyoxyethylene alkyl ether sulfate,
Disclosed is a spray type paste composition containing an anionic activator such as polyoxyethylene alkyl ether acetate and a water-soluble silicone, which does not adhere to the bottom surface of an iron and the cloth and is excellent in long-term stability. In addition, JP-A-11-
No. 189768 discloses an antistatic agent composition for chemical fibers containing a hydrophilic group-containing polymer and a polyhydric alcohol.

[0003] These techniques are to impart appropriate tension and shape by spraying textile products such as clothing and ironing (hereinafter referred to as shaping effect). However, when such a treated garment is worn, the folds of the slacks lose their shape over time, and the garment is deteriorated in shape such as wrinkles on the entire garment. Therefore, there is a demand for a spray-type paste that has an effect of suppressing wrinkles that occur when it is worn, and that can hold folds such as slacks for a long time (hereinafter referred to as a morphological stabilizing effect).

On the other hand, industrially, garments such as shirts are commercially available which have been subjected to a morphological stabilization treatment using formalin gas, formalin emitter, liquid ammonia or the like. Further, JP-A No. 11-158777 discloses a method of imparting a morphological stabilizing effect to a cellulose cloth by an aqueous liquid containing a specific water-soluble vinyl copolymer and an inorganic salt. However, the former has a problem in safety when it is used in general households, and the latter has a limited effect on cellulose cloth, so that it is not possible to impart a morphological stabilizing effect to clothing such as synthetic fibers and wool. Furthermore, these techniques cannot impart a shaping effect to clothing.

Therefore, the problem to be solved by the present invention is to provide a spray type paste which can impart a preferable shaping effect and an excellent shape stabilizing effect by spraying and ironing a textile product. It is in.

[0006]

The present invention is selected from the following (a) a monomer unit (A), a monomer unit (B) and a monomer unit (C) (in which case, the monomer unit (C) is selected). If not, the monomer unit (A)
And a monomer unit (B)], and the total proportion of the monomer units (A), (B) and (C) in all the constituent monomer units is 50 to 100. A vinyl-based polymer [hereinafter referred to as (a) component] that accounts for mol%, a (b) silicone compound [hereinafter referred to as (b) component], and (c) a compound represented by the following formula (1) [hereinafter (( c) component]], and a spray type paste prepared by filling a spray container with a paste composition containing water. Monomer unit (A): Vinyl-based monomer unit having a carboxyl group Monomer unit (B): Vinyl-based monomer unit having a hydroxyl group Monomer unit (C): Vinyl-based monomer unit having a carboxyl group and a hydroxyl group

[0007]

[Chemical 2]

[In the formula, R ¹ and R ³ are each independently
A hydrogen atom or an alkyl group having 1 to 12 carbon atoms, R ² is a hydrogen atom or CH ₃ , and n is an integer of 45 to 5000. ]

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION <Component (a)> In the present invention, (a)
The component is selected from the following monomer unit (A), monomer unit (B) and monomer unit (C) (in this case, when the monomer unit (C) is not selected, the monomer unit (A) and the monomer unit ( B) containing monomer units) (selected from both monomer units),
And the monomer unit (A) in all the constituent monomer units,
A vinyl polymer having a total ratio of (B) and (C) of 50 to 100 mol% is used. Monomer unit (A): Vinyl-based monomer unit having a carboxy group Monomer unit (B): Vinyl-based monomer unit having a hydroxyl group Monomer unit (C): Vinyl-based monomer unit having a carboxy group and a hydroxyl group Monomer unit having a carboxy group Examples of the vinyl-based monomer (A) for obtaining (A) include the following formula (A1)
To one or more kinds selected from the compounds represented by (A3).

[0010]

[Chemical 3]

[Wherein R ¹ and R ² are the same or different,
Hydrogen atom, alkyl group having 1 to 3 carbon atoms, CH ₂ COOM ⁵
(M ⁵ is a hydrogen atom, an alkali metal, an alkaline earth metal,
NH ₄ , organic amine). M ¹ , M ² , M ³ and M ⁴ are
The same or different, it shows a hydrogen atom, an alkali metal, an alkaline earth metal, NH ₄ , and an organic amine. Here, examples of the organic amine include monoethanolamine, diethanolamine, triethanolamine and the like. ].

Specific examples of the formulas (A1) to (A3) include:
Acrylic acid, methacrylic acid, itaconic acid, crotonic acid,
Examples thereof include maleic acid, fumaric acid, and the like, or salts thereof.
As the salt, sodium, potassium, lithium, ammonium, monoethanolamine, diethanolamine,
Examples include triethanolamine. The itaconic acid and maleic acid may be acid anhydrides represented by the following formulas (A4) and (A5). The acid anhydride is hydrolyzed to be a monomer unit constituting the polymer of the present invention.

[0013]

[Chemical 4]

Of the above, acrylic acid, methacrylic acid, maleic acid, itaconic acid or their sodium salts and potassium salts are preferred. In particular, a dicarboxylic acid such as maleic acid or its sodium salt, potassium salt, maleic anhydride, or itaconic anhydride is more preferable.

Examples of the vinyl-based monomer (B) used to obtain the monomer unit (B) having a hydroxyl group, which is used to obtain the vinyl-based polymer of the present invention, include the following formulas (B6) to (B11). 1) or more selected from the compounds represented by the formula (1).

[0016]

[Chemical 5]

[Wherein R ³ , R ⁵ , R ⁷ , R ⁹ , R ¹¹ and R ¹³
Are the same or different, and a hydrogen atom, an alkyl group having 1 to 100 carbon atoms, R ⁴ , R ⁶ , R ⁸ , R ¹⁰ , R ¹² and R ¹⁴ are the same or different and are alkylene having 2 to 6 carbon atoms. The group and m are the average number of moles added, and are numbers from 2 to 100. ].

A specific example of the formula (B6) is N- (2-
Hydroxyethyl) (meth) acrylamide, N- (3
-Hydroxypropyl) (meth) acrylamide, N-
(2-hydroxypropyl) (meth) acrylamide,
Hydroxyalkyl (meth) having 2 to 6 carbon atoms such as N- (4-hydroxybutyl) (meth) acrylamide and N- (6-hydroxyhexyl) (meth) acrylamide
Examples include acrylamide. Here, (meth) acryl means acryl or methacryl. Formula (B7)
Specific examples of hydroxyethyl vinyl ether,
Examples thereof include hydroxybutyl vinyl ether. Specific examples of the formula (B8) include oxyethylene (hereinafter referred to as EO) such as polyoxyethylene (meth) acrylamide and polyoxypropylene (meth) acrylamide.
Examples thereof include (meth) acrylamide polyoxyalkylene adducts obtained by using oxypropylene (hereinafter referred to as PO) and the like alone or in combination. Specific examples of the formula (B9) include EO such as polyoxyethylene (meth) allyl ether and polyoxypropylene (meth) allyl ether,
Examples thereof include polyoxyalkylene adducts of (meth) allyl ether obtained by using PO alone or in combination. Specific examples of the formula (B10) include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxyhexyl. Examples thereof include hydroxyalkyl (meth) acrylates having 2 to 6 carbon atoms such as (meth) acrylate. Specific examples of the formula (B11) include polyoxyalkylene adducts of (meth) acrylic acid obtained by using EO, PO and the like such as polyoxyethylene (meth) acrylate and polyoxypropylene (meth) acrylate alone or in combination. Is mentioned.

R ³ in the formulas (B6) to (B11),
When R ⁵ , R ⁷ , R ⁹ , R ¹¹ , and R ¹³ are alkyl groups, the number of carbon atoms is preferably 1 to 22, and particularly preferably 1 to
It is 5. The polyoxyalkylene average addition mole number m of the formulas (B8), (B9) and (B11) is preferably 2 to 5.
It is 0.

The monomer unit (C) having both a carboxy group and a hydroxyl group of the present invention may or may not coexist with the monomer unit (A) and the monomer unit (B). To calculate the equivalent ratio of a carboxy group and a hydroxyl group, in the case of a monomer unit (C) having both a carboxy group and a hydroxyl group, it is calculated assuming that each group has one equivalent. Specific examples of the vinyl-based monomer (C) used for obtaining such a monomer unit (C) include α-hydroxyacrylic acid.

The vinyl polymer of the present invention may have a monomer unit (D) other than the monomer units (A), (B) and (C). Specific examples of the vinyl-based monomer (D) for obtaining the monomer unit (D) include (meth) acrylic acid derivatives such as methyl (meth) acrylate and ethyl (meth) acrylate, N, N-dimethylacrylamide. , N, N-diethylacrylamide, isopropyl-acrylamide, tert-butylacrylamide, and other N-substituted (meth) acrylamide derivatives, monoalkyl ethers of polyoxyalkylene adducts of (meth) acrylic acid represented by formula (D12) , Formula (D1
3) a monoalkyl ether of a polyoxyalkylene adduct of (meth) acrylic acid amides, represented by the formula (D1
Examples thereof include monoalkyl ethers of polyoxyalkylene adducts of (meth) allyl alcohol represented by 4).

[0022]

[Chemical 6]

[In the formula, R ¹⁵ , R ¹⁸ , and R ²¹ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 100 carbon atoms, or R
¹⁷ , R ²⁰ and R ²³ are the same or different and have 1 to 10 carbon atoms.
An alkyl group of 0, R ¹⁶ , R ¹⁹ and R ²² are the same or different, and an alkylene group having 2 to 6 carbon atoms, m is an average number of moles added, and represents a number of 2 to 100].

In equations (D12), (D13) and (D14)
R in¹⁵, R¹⁷, R¹⁸, R²⁰, R ^{twenty one}, R^{twenty three}Is alkyl
The number of carbon atoms in the case of a group is preferably 1 to 22. Well
Further, the average number of moles of polyoxyalkylene added is preferably m.
Is 2 to 50 mol.

Other vinyl-based monomers (D) include vinyl ethers such as methyl vinyl ether and butyl vinyl ether, styrene derivatives such as styrene and styrene sulfonic acid or salts thereof, olefinic hydrocarbons such as ethylene and propylene, and vinyl sulfone. Examples thereof include sulfonic acid salt-containing vinyl monomers such as acids and allylsulfonic acids, and salts thereof. Preferred salts when these monomers are used as salts are the same as the salts used in formulas (A1) to (A3).

In the vinyl polymer used in the present invention, the total of the monomer units (A), the monomer units (B) and the monomer units (C) is 50 to 10 in all the constituent monomer units.
It is 0 mol%, preferably 60 to 100 mol%, particularly preferably 70 to 100 mol%. Particularly, from the viewpoint of morphological stabilization, the equivalent ratio of the carboxy group and the hydroxyl group in the vinyl polymer is preferably carboxy group: hydroxyl group = 9: 1 to 1:
9, more preferably 8: 2-1: 9, and particularly preferably 7: 3-2: 8. Here, equations (A4) and (A
The acid anhydride represented by 5) has 2 equivalents of carboxy group. In addition, this ratio may be a value (molar ratio of charged monomers) obtained by the ratio of the amount of vinyl-based monomers used during polymerization.

When at least one of vinyl monomers represented by the formulas (B10) to (B11) is a monomer unit constituting the polymer of the present invention, formulas (A1) to (A5).
The monomer unit (A) represented by
It is preferably mol%, and particularly preferably 5-45 mol%. Within this range, intramolecular or intermolecular crosslinking of the vinyl polymer is more efficiently formed, and higher morphological stability can be obtained regardless of the type of fiber.

As the method for synthesizing the vinyl polymer of the component (a) used in the present invention, the method described in, for example, JP-A-6-206750 can be applied. Specifically, it is obtained by radical-copolymerizing each of the above-mentioned monomers in a predetermined molar ratio in the presence of a radical initiator. The vinyl polymer thus obtained has a weight average molecular weight of 1,000 to 1,000,000 [gel permeation liquid chromatography (hereinafter referred to as GPC) method, polyethylene glycol (hereinafter referred to as PEG) conversion] Those in the range of are preferably used. Above all, 5,000-80
A range of 10,000 is more preferable, and 10,000 is more preferable.
To 500,000 is preferable, and particularly 10,000 to 10
A value of 000 is preferred.

Further, in the present invention, as the component (a), two or more kinds of the above vinyl polymers having different compositions or different weight average molecular weights may be used in combination.

<Component (b)> In the present invention, a silicone compound is used as the component (b). The silicone compound is preferably a non-modified silicone compound having at least one modified group selected from a polyether group, an amino group, an aminopolyether group, and an amide polyether group, and an unmodified silicone compound is particularly preferable. It is preferable from the viewpoints of stability, morphological stability and iron slipping property. Here, the unmodified silicone compound is an oil or gum of polydimethylsiloxane having a linear or crosslinked structure, or a mixture thereof. When these silicone compounds are used, they may be used as they are or in the form of an emulsion obtained by emulsifying / dispersing them in water or the like.

In the present invention, it is possible to use a commercially available silicone, and preferred ones are KT-97E and TEX10 of Toshiba GE Silicone Co., Ltd.
0, TEX101, TEX102, TEX103, TE
X104, TSF451, TSF4440, TSF44
41, TSF4445, TSF4446, XF42-B
5370, TSF4452, XF42-B5371, T
SF4460, XS65-822, L-720, L-7001, L-7002, L-700 of Nippon Unica Co., Ltd.
2, L-7604, L-7605, L-7607N, Y
-7006, FZ-2120, FZ-2161, FZ-
2162, FZ-2163, FZ-2164, FZ-2
165, FZ-2166, KF of Shin-Etsu Silicone Co., Ltd.
-351A, KF-352A, KF-353A, KF-
354A, KF-615A, KF-618, KF-94
5A, KF-6008, BY22-019, SH-3746, SH of Toray Dow Corning Silicone Co., Ltd.
-3771, SH-8400, SF-8410, SH-
8700 can be mentioned.

<Component (c)> In the present invention, a compound represented by the following formula is used as the component (c).

[0033]

[Chemical 7]

[In the formula, R and R ″ are each independently
A hydrogen atom or an alkyl group having 1 to 12 carbon atoms, R ′ is a hydrogen atom or CH ₃ , and n is a positive integer of 2 or more. ].

Specific examples of the above compounds include polyethylene glycol, polypropylene glycol, polypropylene glycol monobutyl ether, polypropylene glycol dibutyl ether, polypropylene glycol monododecyl ether, polyethylene glycol monobutyl ether and polyethylene glycol monododecyl ether.

As the component (c) of the present invention, polyethylene glycol having a weight average molecular weight of 2,000 to 200,000 is particularly preferable from the viewpoints of preventing iron sticking, shaping effect and shape stabilizing effect, and particularly, weight average. Molecular weight 1,0
Most preferred is a polyethylene glycol of from 00 to 20,000, more preferably from 2,000 to 10,000. The weight average molecular weight can be determined by the same method as for the vinyl polymer (a).

<Paste Composition> The paste composition used in the spray type paste of the present invention preferably contains the component (a) in an amount of 5 to 5.
30% by mass, more preferably 5 to 20% by mass, particularly preferably 5 to 15% by mass. Further, the component (b) is preferably 0.005 to 7.5 mass%, more preferably 0.01 to 5 mass%, and particularly preferably 0.05 to 2.5.
Contains by mass%. Further, the component (c) is preferably 0.0
The content is preferably 05 to 10% by mass, more preferably 0.01 to 7.5% by mass, and particularly preferably 0.05 to 5% by mass. Within this range, a preferable shaping effect and a high shape stabilizing effect can be obtained.

The paste composition of the present invention comprises the above component (a)
It is in the form of an aqueous solution in which the component (c) is dissolved or dispersed in water, and the pH at 20 ° C. is preferably 2.0 to 7.
0, more preferably 2.5 to 6.0, and particularly preferably 3.0 to 5.0. In this range, the strength of the fiber is not deteriorated and the shape stability is improved. pH is
It may be adjusted with an acid or an alkali agent which is publicly known as a fiber treating agent, or may be adjusted with a water-soluble inorganic salt described later.

It is preferable to add a water-soluble inorganic salt as the component (d) to the paste composition of the present invention for the purpose of further improving the morphological stabilization effect. Water-solubility in the present invention means that the solubility at 20 ° C. is 0.1 g / 100 water.
g or more. Specifically, phosphorous acid, hypophosphorous acid, phosphoric acid, metaphosphoric acid, pyrophosphoric acid, phosphoric acid such as polyphosphoric acid, boric acid such as boric acid, metaboric acid, silicic acid, silicic acid such as metasilicic acid. Alkali metal salts, alkaline earth metal salts or amine salts of acids selected from sulfuric acids such as sulfuric acid and sulfurous acid. In the present invention, particularly phosphorous acid,
Sodium and potassium salts of hypophosphorous acid, phosphoric acid, metaphosphoric acid and polyphosphoric acid are preferred from the viewpoint of improving morphological stability.
In the paste composition of the present invention, the component (d) is preferably 0.0
It is contained in an amount of 05 to 10% by mass, more preferably 0.05 to 7.5% by mass, and particularly preferably 0.1 to 5% by mass.

In the present invention, the mass ratio of the component (d) to the component (a) is, in terms of improving morphological stability,
Component (a): Component (d) is preferably 1: 0 to 1: 1,
It is more preferably 1: 0.05 to 1: 0.5, and particularly preferably 1: 0.1 to 1: 0.3.

The paste composition of the present invention preferably further contains a low molecular weight polyvalent carboxylic acid as the component (e) from the viewpoint of the shape stabilizing effect.

The component (e) is an organic acid having two or more carboxy groups in one molecule or a salt thereof, preferably an organic acid having at least two carboxy groups bonded to adjacent carbon atoms, or That salt. The acid has a molecular weight of 116 to 1,000, preferably 116.
To 800, and more preferably 116 to 500. Such compounds include succinic acid, maleic acid, citric acid, fumaric acid, tartaric acid, malic acid, citraconic acid, aconitic acid, itaconic acid, 1,2-cyclopentanedicarboxylic acid, phenylsuccinic acid, 1,2-cyclohexane. Dicarboxylic acid, 1,2-cyclopentanedicarboxylic acid,
1,2-cyclooctanedicarboxylic acid, 1,2-cycloheptanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 2,3-dimethylsuccinic acid, 2,3-diethylsuccinic acid, 2-ethyl-3-methylsuccinic acid , Tetramethylsuccinic acid, 3,3-dimethyl-cis-1,2-cyclopropanedicarboxylic acid, 2,3-di-tert-butylsuccinic acid, trimellitic acid, 1,2,4-cyclohexanetricarboxylic acid, butanetetra Examples thereof include carboxylic acid, cyclopentane tetracarboxylic acid, tetrahydrofuran tetracarboxylic acid and the like. Examples of the polyvalent carboxylic acid having surface activity include alkenylsuccinic acid having 8 to 18 carbon atoms. A part of these acids can be used as an alkali metal salt or an alkaline earth metal salt, or can be used as an acid anhydride such as maleic anhydride or succinic anhydride. Further, two or more kinds of acids and acid anhydrides may be used in combination.

Among these components (e), especially citric acid, maleic acid, tartaric acid, succinic acid, malic acid, 1, 2
-Cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, cyclopentanetetracarboxylic acid or salts thereof are preferable in terms of improving the morphological stabilization effect.

The paste composition of the present invention has the above-mentioned (e)
The component is preferably 0.01 to 20% by mass as an acid, more preferably 0.1 to 10% by mass, and particularly preferably 0.1.
1 to 5 mass% is contained.

If necessary, the paste composition of the present invention may contain a wax or an emulsion thereof for improving ironing slipperiness, an antibacterial / sterilizing / antifungal agent for improving storage stability and a feeling of use. Ingredients used in clothing spray pastes such as flavorings for improving the quality can be optionally blended. These components can be contained in the paste composition in an amount of 0 to 15% by mass.

The balance of the paste composition of the present invention is water, preferably 55 to 99.9% by mass, more preferably 65 to 9.
99.5% by mass, particularly preferably 75-99.5% by mass
Contained.

<Spray-type paste> The spray-type paste of the present invention is obtained by filling the above-mentioned paste composition in a spray container, and impregnating a textile product with the above-mentioned paste composition by spray treatment. By performing heat treatment such as ironing, a shaping effect and a shape stabilizing effect can be easily obtained.

Sprayers such as aerosol-type, manual-type trigger, and manual-type pumps can be used in the spraying process. Among them, a manual-type trigger or a manual-type pump is preferable, and a manual-type trigger is particularly preferable. In the present invention, it is most preferable to use the above composition as an article obtained by filling a container provided with these sprayers. The composition of these sprayers is preferably 0.1 per spray.
It is preferable that the size of the paste composition is about 1.5 g, preferably 0.2 to 1.0 g, particularly preferably 0.25 to 0.8 g. Further, when sprayed from a location 15 cm away from the textile product, the area where the paste composition adheres to the textile product by one spraying is 50 to 800 cm ² , and particularly 100 to 6
A container of 00 cm ² is preferred. Further, for example, the use of a pressure accumulating trigger as disclosed in Japanese Utility Model Laid-Open No. 4-37554 and Japanese Patent Application Laid-Open No. 9-122547 is favorable in terms of uniformity of spray mist and no dripping or dripping. .

In the present invention, the average amount of the vinyl polymer is 0.01 to 20 g, preferably 0.1 to 15 g, and particularly preferably 0.5 to 10 g based on 100 g of the fiber product by the above spray treatment. It is preferable to uniformly attach it because it does not adhere to the bottom surface of the iron when it is heated by the ironing process, there is no scorching on the bottom surface of the iron, and the iron has excellent slipperiness and a morphological stability effect.

In the present invention, after the paste composition is spray-treated on the textile product as described above, it is subjected to a heat treatment at 60 to 300 ° C. to obtain a preferable shaping effect, a high shape-stabilizing effect and an appropriate texture. A textile product having a soft touch is obtained. The heat treatment can be performed using a trouser press or a warm air dryer that is widely used in addition to the iron, but the iron and trouser press can simultaneously perform the heat treatment and shaping such as wrinkle removal and creasing. Is preferred, and ironing is particularly preferred because it is convenient. The iron is set at a temperature suitable for the fiber material, preferably 120 to 220 ° C., particularly preferably 140 to 200.
℃. The ironing time is preferably 1 to 90 seconds, particularly preferably 2 to 100 cm ² of the textile product.
60 seconds.

Natural drying may be optionally added between the spray treatment and the heat treatment, which does not hinder the purpose of the present invention.

The optimum formulation of the paste composition of the present invention and the spray paste are shown below. (I) As the component (a), a monomer unit (A) obtained from a vinyl monomer (A) having a carboxy group selected from (meth) acrylic acid, maleic acid, itaconic acid and maleic anhydride, and N- ( 2-hydroxyethyl)
(Meth) acrylamide, POA-added mono (meth) acrylamide and POA-added mono (meth) allyl ether, 2-hydroxyethyl (meth) acrylate, 3-
A vinyl-based copolymer having a monomer unit (B) obtained from a vinyl-based monomer (B) having a hydroxyl group selected from hydroxypropyl (meth) acrylate and POA-added mono (meth) acrylate, the polymer comprising: These monomers (A) and (B) occupy a total of 70 to 100 mol% in the constituent monomer units, and the equivalent ratio of the carboxy group and the hydroxyl group is carboxy group: hydroxyl group = 7: 3.
Vinyl copolymer such as 2: 8 0.5 to 10% by mass As the component (b), dimethylpolysiloxane, hydroxyl group-containing dimethylpolysiloxane, oil of dimethylpolysiloxane or hydroxyl group-containing dimethylpolysiloxane, or gum, And emulsions of these oils or gums 0.05 to 2.5% by mass (as silicone content) (c) component, polyethylene glycol (molecular weight 1,000 to 20,000) 0.05 to 5% by mass (II ) A water-soluble inorganic salt selected from sodium hypophosphite, sodium phosphite, sodium phosphate, disodium or potassium hydrogen phosphate, sodium or potassium dihydrogen phosphate, sodium sulfate, sodium sulfite and sodium thiosulfate. 1-5% by mass (III) Sodium hydroxide, hydroxy as required Potassium, phosphate, consists sulfate, and pH adjusting agent and the balance water selected from hydrochloric acid, pH at 20 ° C. is 4.0 to
A liquid paste composition having a size of 6.5 and a spray paste prepared by filling the composition in a container equipped with a trigger sprayer can be mentioned.

By impregnating the paste composition of the present invention into a fiber product and heat-treating it, intramolecular or intermolecular crosslinking of the vinyl polymer of component (a) is formed, and a polymer film is formed. A shaping effect and a shape-stabilizing effect can be imparted to a textile product. Therefore, the paste composition of the present invention can be used for any textiles as long as it can be heat-treated and is not substantially damaged by water.

[0054]

EFFECTS OF THE INVENTION According to the present invention, regardless of the type of fiber, excellent form stability at home, that is, wrinkle suppressing effect and crease holding effect, can be imparted to a textile product not only when worn but also after washing. In addition, it is possible to obtain a spray type sizing agent for textile products, which does not impair the morphological stability effect, has a favorable elasticity, and can impart appropriate texture and touch to the textile product.

[0055]

EXAMPLES Examples of synthesizing the component (a) will be given below.

Synthesis Example 1 (Synthesis of Vinyl Copolymer a-1) 1 equipped with a stirrer, nitrogen inlet tube, cooling device, and thermometer
In an L four-necked flask, 114.00 g of maleic anhydride,
After adding 130.00 g of water and 116.33 g of EO-added allyl ether [EO-added mole number 6], the temperature inside the tank was set to 7
The temperature was raised to 0 ° C., and a solution prepared by dissolving 48.47 g of 96% sodium hydroxide in 46.53 g of water was added. Furthermore, after replacing the inside of the tank with nitrogen, the temperature was raised to 98 ° C., and an aqueous initiator solution consisting of 65.92 g of 35% hydrogen peroxide solution and 6.93 g of sodium persulfate was dropped into the reaction tank over 6 hours, and further, The temperature in the bath was kept at 98 ° C. for 4 hours. The weight average molecular weight (PEG equivalent, hereinafter referred to as Mw) of the obtained maleic acid / EO addition type allyl ether (= 80/20 molar ratio) copolymer was 21,000 when measured by the following method. Met.

[Molecular Weight Measuring Method] Using GPC, the measurement was carried out under the following conditions. Column: Tosoh Corp. G4000PWXL + G25
00PWXL Eluent: 9: 1 volume ratio mixture of an aqueous solution containing 0.1 mol / L potassium dihydrogen phosphate and 1 mol / L disodium hydrogen phosphate and acetonitrile Detector: Differential refractometer Flow rate: 1.0 mL / Min Column (measurement) temperature: 40 ° C. Standard sample: PEG (9.20 × 10 ⁵ , 5.10 ×)
10 ⁵ , 2.50 x 10 ⁵ , 9.50 x 10 ⁴ , 4.60
× 10 ⁴ , 3.90 × 10 ⁴ ) Sample concentration: 5 mg / mL Eluent sample injection amount: 100 μL The molecular weight was calculated as a PEG-equivalent molecular weight using a calibration curve obtained from the above standard sample. For samples outside this molecular weight range, the reduced molecular weight was calculated by extrapolation of a calibration curve.

Synthesis Example 2 (Synthesis of Vinyl Copolymer a-2) 1 equipped with a stirrer, a nitrogen introducing pipe, a cooling device, and a thermometer
In an L four-necked flask, 78.40 g of maleic anhydride, 166.00 g of water, EOPO-added allyl ether [EO
After adding 87.60 g of addition mole number 6, PO addition mole number 2, triblock type: allyl ether (EO) ₂ (PO) ₂ (EO) ₄ ], the temperature inside the vessel was raised to 70 ° C., and 96 A solution of 28.33 g% sodium hydroxide in 66.34 g water was added. Further, after the inside of the tank was replaced with nitrogen, the temperature was raised to 98 ° C., and an initiator aqueous solution composed of 42.74 g of 35% hydrogen peroxide solution and 4.76 g of sodium persulfate was dropped into the reaction tank over 6 hours, and The temperature in the bath was kept at 98 ° C. for 4 hours. The obtained maleic acid / allyl ether (EO) ₂ (P
Mw of O) ₂ (EO) ₄ (= 80/20 molar ratio) copolymer
The (PEG conversion) was 20,000 when measured by the method described in Synthesis Example 1.

Synthesis Example 3 (Synthesis of Vinyl Copolymer a-3) 1 equipped with a stirrer, a nitrogen inlet tube, a cooling device, and a thermometer
In an L four-necked flask, maleic anhydride 156.80 g,
Water 308.80 g, EOPO addition type allyl ether [E
O addition mole number 6, PO addition mole number 1, triblock type:
Allyl ether (EO) ₂ (PO) ₁ (EO) ₄ ] 152.00
After adding g, the temperature in the tank was raised to 70 ° C., and 120.00 g of 48% sodium hydroxide aqueous solution was added. further,
After replacing the inside of the tank with nitrogen, the temperature was raised to 98 ° C., an initiator aqueous solution consisting of 85.49 g of 35% hydrogen peroxide solution and 9.53 g of sodium persulfate was dropped into the reaction tank over 6 hours, and further 4 hours. The temperature inside the tank was maintained at 98 ° C. The obtained maleic acid / allyl ether (EO) ₂ (PO) ₁ (EO) ₄ (= 80
The Mw (in terms of PEG) of the copolymer was 15,000 when measured by the method described in Synthesis Example 1.

Synthesis Example 4 (Synthesis of Vinyl Copolymer a-4) 1 equipped with a stirrer, a nitrogen introducing pipe, a cooling device, and a thermometer
In an L four-necked flask, maleic anhydride 156.80 g,
360.00 g of water, EOPO addition type allyl ether [E
O addition mole number 6, PO addition mole number 0.5, triblock type: allyl ether (EO) ₂ (PO) _0.5 (EO) ₄ ] 14
After adding 0.40 g, the temperature inside the tank was raised to 70 ° C.,
120.00 g of 8% sodium hydroxide aqueous solution was added.
Furthermore, after replacing the inside of the tank with nitrogen, the temperature was raised to 98 ° C.
Hydrogen peroxide water 85.49g, sodium persulfate 9.53
An initiator aqueous solution of g was added dropwise to the above reaction tank over 6 hours, and the temperature inside the tank was kept at 98 ° C. for 4 hours. Obtained maleic acid / allyl ether (EO) ₂ (PO) _0.5 (EO)
The Mw (in terms of PEG) of the ₄ (= 80/20 molar ratio) copolymer was 18,000 as measured by the method described in Synthesis Example 1.

Synthesis Example 5 (combined with vinyl copolymer a-5)
Formed) 1 equipped with a stirrer, nitrogen inlet tube, cooling device, thermometer
In an L four-necked flask, maleic anhydride 156.80 g,
Water 308.80 g, EOPO addition type allyl ether [E
O addition mole number 6, PO addition mole number 1, random type: ant
Ruether (EO / PO)₇] 152.20 g was added.
The temperature inside the tank is raised to 70 ° C, and a 48% aqueous sodium hydroxide solution is added.
120.00 g of solution was added. Furthermore, the tank is replaced with nitrogen.
After that, the temperature is further raised to 98 ° C. and 35% hydrogen peroxide solution 8
Start consisting of 5.49g, sodium persulfate 9.53g
The aqueous solution of the agent was added dropwise to the above reaction tank over 6 hours, and further 4
The temperature in the bath was kept at 98 ° C. for an hour. Maleic acid obtained /
Allyl ether (EO / PO) ₇(= 80/20 molar ratio)
The Mw (converted to PEG) of the copolymer is the method described in Synthesis Example 1.
It was 18,000 when measured by.

Synthesis Example 6 (Synthesis of Vinyl Copolymer a-6) 1 equipped with a stirrer, a nitrogen introducing pipe, a cooling device, and a thermometer
127.38 g of maleic anhydride in an L4 neck flask,
370.66 g of water, EOPO addition type allyl ether [E
O addition mole number 6, PO addition mole number 1, triblock type:
Allyl ether (EO) ₂ (PO) ₁ (EO) ₄ ] 243.28
After adding g, the temperature inside the tank was raised to 70 ° C., and 97.49 g of 48% sodium hydroxide aqueous solution was added. Furthermore, after replacing the inside of the tank with nitrogen, the temperature was raised to 98 ° C., and 12.44 g of 2-acrylamido-2-methylpropanesulfonic acid and 5 parts of water were added.
A monomer solution consisting of 0.00 g and an initiator aqueous solution consisting of 94.23 g of 35% hydrogen peroxide solution and 9.24 g of sodium persulfate were simultaneously dropped into the above reaction tank over 6 hours, and the temperature inside the tank was further 4 hours. Was maintained at 98 ° C. Obtained maleic acid / allyl ether (EO) ₂ (PO) ₁ (EO) ₄ /
The Mw (in terms of PEG) of the 2-acrylamido-2-methylpropanesulfonic acid (= 65/32/3 molar ratio) copolymer was 18,000 as measured by the method described in Synthesis Example 1. .

Synthesis Example 7 (Synthesis of Vinyl Copolymer a-7) 1 equipped with a stirrer, a nitrogen introducing pipe, a cooling device, and a thermometer
In an L four-necked flask, 88.20 g of maleic anhydride, 506.20 g of water, EOPO-added allyl ether [EO
Addition mole number 6, PO addition mole number 1, triblock type: allyl ether (EO) ₂ (PO) ₁ (EO) ₄ ] 418.00 g
After adding, the temperature in the tank was raised to 70 ° C., and 67.50 g of a 48% sodium hydroxide aqueous solution was added. After replacing the inside of the tank with nitrogen, the temperature was raised to 98 ° C., and 35% hydrogen peroxide water 116.
An initiator aqueous solution consisting of 57 g and sodium persulfate (9.53 g) was added dropwise to the reaction tank over 6 hours, and the temperature inside the tank was kept at 98 ° C. for 4 hours. The Mw (converted to PEG) of the obtained maleic acid / allyl ether (EO) ₂ (PO) ₁ (EO) ₄ (= 45/55 molar ratio) copolymer was measured by the method described in Synthesis Example 1. However, it was 15,000.

Synthesis Example 8 (Synthesis of Vinyl Copolymer a-8) 1 equipped with a stirrer, a nitrogen introducing pipe, a cooling device, and a thermometer
In an L four-necked flask, maleic anhydride 156.80 g,
Add 302.84 g of water and raise the temperature in the tank to 70 ° C.
120.00 g of 48% sodium hydroxide aqueous solution was added. Furthermore, after replacing the inside of the tank with nitrogen, the temperature is raised to 98 ° C.
-(2-hydroxyethyl) acrylamide 46.04
g of a monomer solution, 35% hydrogen peroxide water 116.
57 g and an aqueous initiator solution consisting of 9.53 g of sodium persulfate were simultaneously added dropwise to the above reaction tank over 6 hours, and the temperature inside the tank was kept at 98 ° C. for 4 hours. The obtained maleic acid / N- (2-hydroxyethyl) acrylamide (=
(80/20 molar ratio) Mw (converted to PEG) of the copolymer is
It was 35,000 as measured by the method described in Synthesis Example 1.

Synthesis Example 9 (Synthesis of Vinyl Copolymer a-9) 1 equipped with a stirrer, a nitrogen inlet tube, a cooling device, and a thermometer
To an L four-necked flask, 78.40 g of maleic anhydride and 216.52 g of water were added, and the temperature inside the tank was raised to 70 ° C.
66.67 g of 8% sodium hydroxide aqueous solution was added. Furthermore, after replacing the inside of the tank with nitrogen, the temperature was raised to 98 ° C.
-Hydroxyethyl) acrylamide monomer solution consisting of 138.12 g, 35% hydrogen peroxide water 116.57
g and an aqueous solution of an initiator consisting of 9.53 g of sodium persulfate were simultaneously added dropwise to the above reaction vessel over 6 hours, and further 4
The temperature in the bath was kept at 98 ° C. for an hour. Maleic acid obtained /
N- (2-hydroxyethyl) acrylamide (= 20
The Mw (converted to PEG) of the copolymer was 30,000 when measured by the method described in Synthesis Example 1.

Synthesis Example 10 (Synthesis of Vinyl Copolymer a-10) 1 equipped with a stirrer, a nitrogen inlet tube, a cooling device, and a thermometer
EO addition type allyl ether [EO
Addition number of moles 8] 384.00 g and water 441.67 g were added, the inside of the tank was replaced with nitrogen, and then the temperature inside the tank was raised to 90 ° C., from 57.67 g of acrylic acid and 53.33 g of 48% sodium hydroxide aqueous solution. Aqueous solution of monomer, 116.57 g of 35% hydrogen peroxide solution and an aqueous solution of initiator consisting of 9.53 g of sodium persulfate were simultaneously added dropwise to the above reaction tank over 6 hours, and the temperature inside the tank was kept at 98 ° C. for 4 hours. It was Obtained acrylic acid / EO addition type allyl ether (= 40 /
The Mw (in terms of PEG) of the copolymer (60 mol ratio) was 40,000 when measured by the method described in Synthesis Example 1.

Synthesis Example 11 (Synthesis of Vinyl Copolymer a-11) 1 equipped with a stirrer, a nitrogen introducing pipe, a cooling device, and a thermometer.
L4 four-necked flask, EOPO addition type allyl ether [EO addition mole number 6, PO addition mole number 1, triblock type: allyl ether (EO) ₂ (PO) ₁ (EO) ₄ ] 418.
00 g and 475.67 g of water were added, the temperature in the tank was raised to 70 ° C. under a nitrogen atmosphere, and 57.67 g of acrylic acid,
48% sodium hydroxide aqueous solution 53.33 g, N, N-
A monomer solution consisting of 9.91 g of dimethylacrylamide and an initiator aqueous solution consisting of 116.57 g of 35% hydrogen peroxide solution and 9.53 g of sodium persulfate were simultaneously added dropwise to the above reaction tank over 6 hours, and the tank was further stored for 4 hours. The internal temperature was maintained at 98 ° C. Obtained acrylic acid / EOPO addition type allyl ether / N, N-dimethylacrylamide (=
40/55/5 molar ratio) Mw of copolymer (PEG conversion)
Was measured by the method described in Synthesis Example 1.
It was 0,000.

Synthesis Example 12 (Synthesis of Vinyl Copolymer a-12) 1 equipped with a stirrer, nitrogen inlet tube, cooling device, thermometer
To an L four-necked flask, 475.00 g of water and 25.00 g of isopropyl alcohol (hereinafter referred to as IPA) were added, and the temperature inside the tank was raised to 75 ° C. under a nitrogen atmosphere to obtain 64.88 g of acrylic acid and N-. A monomer solution consisting of 143.00 g of (3-hydroxypropyl) acrylamide and an aqueous solution of an initiator consisting of 0.95 g of sodium persulfate and 50.00 g of water were simultaneously added dropwise over 2 hours, and the temperature inside the tank was 75 ° C. for 4 hours. Further polymerization was carried out while keeping the above.
From the obtained reaction solution at 75 ° C. under reduced pressure (10,600-1
It was concentrated under 3300 Pa) until IPA was not distilled off, and a transparent aqueous solution of an acrylic acid / N- (3-hydroxypropyl) acrylamide (= 55/45 molar ratio) copolymer was obtained. Mw (PE of the obtained copolymer
The G conversion) was 120000 when measured by the method described in Synthesis Example 1.

Synthesis Example 13 (Synthesis of Vinyl Copolymer a-13) 1 equipped with a stirrer, nitrogen introducing tube, cooling device, and thermometer
L4 neck flask, water 475.00g, IPA25.
00 g was added, and the temperature inside the tank was raised to 75 ° C. under a nitrogen atmosphere, and 57.67 g of acrylic acid, 143.00 g of N- (3-hydroxypropyl) acrylamide, N, N-
A monomer solution composed of 9.91 g of dimethylacrylamide and an aqueous initiator solution composed of 0.95 g of sodium persulfate and 50.00 g of water were added dropwise over 2 hours, respectively, and 4
Further polymerization was carried out while the temperature inside the tank was kept at 75 ° C. From the resulting reaction solution at 75 ° C. under reduced pressure (10,600
˜13,300 Pa), IPA is concentrated until it is not distilled off, and acrylic acid / N- (3-hydroxypropyl) acrylamide / N, N-dimethylacrylamide (= 40/55/5 molar ratio) A combined clear aqueous solution was obtained. Mw of the obtained copolymer (converted to PEG)
Is 1 when measured by the method described in Synthesis Example 1.
It was 0.0 million.

Synthesis Example 14 (Synthesis of vinyl polymer aa-1) 1 equipped with a stirrer, a nitrogen introducing pipe, a cooling device, and a thermometer
After replacing the inside of the tank of the L4 neck flask with nitrogen, 156.80 g of maleic anhydride and 202.08 g of ion-exchanged water were added,
The temperature inside the tank was raised to 70 ° C., and 133.33 g of a 48% sodium hydroxide aqueous solution was added. Furthermore, the temperature inside the tank is set to 9
The temperature is raised to 8 ° C., and 2-hydroxyethyl acrylate 4
Monomer consisting of 5.28 g and 35% hydrogen peroxide water 8
An initiator aqueous solution composed of 5.49 g and sodium persulfate (9.53 g) was added dropwise to the above reaction tank over 6 hours, and the inside of the tank was kept at 98 ° C. or higher for 4 hours. The obtained maleic acid / 2-hydroxyethyl acrylate (= 8
The Mw (in terms of PEG) of the copolymer (0/20 molar ratio) was 35,000 as measured by the method described below.

Synthesis Example 15 (Synthesis of Vinyl Polymer aa-2) 1 equipped with a stirrer, a nitrogen introducing pipe, a cooling device and a thermometer
After the inside of the tank of the L 4-necked flask was replaced with nitrogen, 58.80 g of maleic anhydride and 217.28 g of ion-exchanged water were added, the temperature in the tank was raised to 70 ° C., and 50.00 g of a 48% aqueous sodium hydroxide solution was added. . Furthermore, the temperature in the tank is raised to 98 ° C., and 2-hydroxyethyl acrylate 158.
Monomer consisting of 48 g and 35% hydrogen peroxide water 85.
An aqueous initiator solution consisting of 49 g and sodium persulfate (9.53 g) was added dropwise to the above reaction tank over 6 hours, and the inside of the tank was kept at the reflux temperature for 4 hours. The Mw (in terms of PEG) of the obtained maleic acid / 2-hydroxyethyl acrylate (= 30/70 molar ratio) copolymer was 41,000 as measured by the method described in Synthesis Example 1.

Synthesis Example 16 (Synthesis of Vinyl Polymer aa-3) 1 equipped with a stirrer, a nitrogen introducing pipe, a cooling device, and a thermometer
After replacing the inside of the tank of the L four-necked flask with nitrogen, 148.96 g of maleic anhydride and 192.00 g of ion-exchanged water were added, the temperature inside the tank was raised to 70 ° C., and 126.67 g of 48% aqueous sodium hydroxide solution was added. . Furthermore, the temperature inside the tank is set to 98
2-hydroxyethyl acrylate 4
3.02 g, N, N-dimethylacrylamide 9.91
35% hydrogen peroxide water 97.14
g, and an aqueous solution of an initiator consisting of 9.53 g of sodium persulfate were added dropwise to the above reaction tank over 6 hours, and the inside of the tank was kept at the reflux temperature for 4 hours. Maleic acid obtained /
The Mw (in terms of PEG) of the 2-hydroxyethyl acrylate / N, N-dimethylacrylamide (= 76/19/5 molar ratio) copolymer was 48,000 when measured by the method described in Synthesis Example 1. there were.

Synthesis Example 17 (Synthesis of Vinyl Polymer aa-4) 1 equipped with a stirrer, a nitrogen introducing pipe, a cooling device and a thermometer
After replacing the inside of the tank of the L 4 neck flask with nitrogen, 98.00 g of maleic anhydride and 435.00 g of ion-exchanged water were added, the temperature in the tank was raised to 70 ° C., and 48% sodium hydroxide 8
3.33 g was added. Furthermore, the temperature inside the tank was raised to 98 ° C., and a monomer consisting of 336.09 g of polyoxyethylene addition type acrylate (EO addition mole number about 6) and 3
85.49 g of 5% hydrogen peroxide solution, sodium persulfate 9.
An initiator aqueous solution consisting of 53 g was added dropwise to the above reaction tank over 6 hours, and the inside of the tank was kept at the reflux temperature for 4 hours. Mw of the obtained maleic acid / polyoxyethylene addition type acrylate (= 50/50 molar ratio) copolymer
The (PEG conversion) was 58,000 as measured by the method described in Synthesis Example 1.

Synthesis Example 18 (Synthesis of Vinyl Polymer aa-5) 1 equipped with a stirrer, a nitrogen introducing pipe, a cooling device and a thermometer
In an L four-necked flask, ion-exchanged water 100.00 g, isopropyl alcohol (hereinafter referred to as IPA) 400.0
0 g was added, the temperature in the tank was raised to 75 ° C. under a nitrogen atmosphere, and a monomer consisting of 115.34 g of acrylic acid and 46.44 g of 2-hydroxyethyl acrylate, 0.95 g of sodium persulfate, and 40 ion-exchanged water. An initiator aqueous solution of 0.000 g was added dropwise to the above reaction tank over 2 hours, and the temperature inside the tank was kept at 75 ° C. for 4 hours.
The reaction solution obtained was depressurized at 75 ° C (10,600 to 1).
Under 3,300 Pa), IPA was concentrated until no more distilling out, to obtain a transparent aqueous solution of acrylic acid / 2-hydroxyethyl acrylate (= 80/20 molar ratio) copolymer. The Mw (in terms of PEG) of the obtained copolymer was 53,000 as measured by the method described in Synthesis Example 1.

Synthesis Example 19 (Synthesis of Vinyl Polymer aa-6) 1 equipped with a stirrer, a nitrogen inlet tube, a cooling device, and a thermometer
After replacing the inside of the tank of the L 4-necked flask with nitrogen, 58.80 g of maleic anhydride and 236.88 g of ion-exchanged water were added, the temperature inside the tank was raised to 70 ° C., and 48% sodium hydroxide 8
3.33 g was added. Furthermore, the temperature inside the tank was raised to 98 ° C., and 3-hydroxypropyl acrylate 178.0
8 g of monomer and 35% hydrogen peroxide water 85.4
A 9 g aqueous initiator solution was added dropwise to the above reaction tank over 6 hours, and the inside of the tank was kept at the reflux temperature for 4 hours. Mw (PE of the obtained maleic acid / 3-hydroxypropyl acrylate (= 30/70 molar ratio) copolymer
The G conversion) was 52,000 as measured by the method described in Synthesis Example 1.

Synthesis Example 20 (Synthesis of vinyl polymer aa-7) 1 equipped with a stirrer, a nitrogen introducing pipe, a cooling device, and a thermometer
To an L four-necked flask, 475.00 g of ion-exchanged water, I
PA25.00g was added, the temperature in the tank was raised to 75 ° C. under a nitrogen atmosphere, and a monomer composed of 7.20 g of acrylic acid and 215.10 g of 2-hydroxyethyl acrylate and 4.76 g of sodium persulfate were ion-exchanged. Water 50.
An initiator aqueous solution consisting of 00 g was dropped into the above reaction tank over 2 hours, and the temperature inside the tank was kept at 75 ° C. for 4 hours. From the obtained reaction solution, decompression at 75 ° C (10,600 ~
Under 13,300 Pa), the IPA was concentrated until it did not distill out to obtain a transparent aqueous solution of an acrylic acid / 2-hydroxyethyl acrylate (= 5/95 molar ratio) copolymer. The Mw (in terms of PEG) of the obtained copolymer was 175,000 when measured by the method described in Synthesis Example 1.

Synthesis Example 21 (Synthesis of vinyl polymer aa-8) 1 equipped with a stirrer, a nitrogen introducing pipe, a cooling device and a thermometer
To an L four-necked flask, 475.00 g of ion-exchanged water, I
PA25.00g was added, the temperature in the tank was raised to 75 ° C under a nitrogen atmosphere, and a monomer composed of acrylic acid 136.97g and 2-hydroxyethyl acrylate 11.32g was ion-exchanged with sodium persulfate 4.76g. Water 5
An aqueous initiator solution consisting of 0.00 g was dropped into the above reaction tank over 2 hours, and the temperature inside the tank was adjusted to 75 for 4 hours.
It was kept at ℃. The reaction solution obtained was depressurized at 75 ° C. (10,
The mixture was concentrated under 600 to 13,300 Pa) until IPA was no longer distilled out to obtain a transparent aqueous solution of acrylic acid / 2-hydroxyethyl acrylate (= 95/5 molar ratio) copolymer. Mw of the obtained copolymer (converted to PEG)
Is 1 when measured by the method described in Synthesis Example 1.
It was 50,000.

Synthesis Example 22 (Synthesis of Vinyl Polymer aa-9) 1 equipped with a stirrer, a nitrogen inlet tube, a cooling device, and a thermometer
L-four-necked flask, α-hydroxyacrylic acid 11
0.00g, sodium persulfate 6.60g, water 40
0.00g was added, and the temperature inside the tank was 70 ° C under nitrogen atmosphere.
The temperature was raised to 70 ° C., and polymerization was carried out for 6 hours while maintaining the temperature inside the bath at 70 ° C. to obtain a transparent aqueous solution of sodium poly-α-hydroxyacrylate. The Mw (converted to PEG) of the obtained polymer was 150000 when measured by the method described in Synthesis Example 1.

Synthesis Example 23 (Synthesis of Vinyl Copolymer a'-1) 1 equipped with a stirrer, nitrogen introducing pipe, cooling device, thermometer
L4 neck flask, water 475.00g, IPA25.
00 g was added, the temperature in the tank was raised to 75 ° C. under a nitrogen atmosphere, and a monomer solution consisting of methacrylic acid 86.09 g and N, N-dimethylacrylamide 99.13 g was added,
An aqueous solution of an initiator consisting of 0.95 g of sodium persulfate and 50.00 g of water was simultaneously added dropwise over 2 hours, and further polymerization was carried out while keeping the temperature inside the tank at 75 ° C. for 4 hours. 75 ° C. from the obtained reaction solution at reduced pressure (10,600 to 13,
At 300 Pa), the solution was concentrated until IPA was not distilled off, and a transparent aqueous solution of a methacrylic acid / N, N-dimethylacrylamide (= 50/50 molar ratio) copolymer was obtained. The Mw (converted to PEG) of the obtained copolymer was 175,000 when measured by the method described in Synthesis Example 1.

Synthesis Example 24 (Synthesis of Vinyl Copolymer a'-2) 1 equipped with a stirrer, a nitrogen introducing pipe, a cooling device, and a thermometer
To an L4 four-necked flask, 500.00 g of IPA was added, and the temperature in the tank was raised to 75 ° C. under a nitrogen atmosphere to obtain N- (2
-Hydroxyethyl) acrylamide 184.16 g,
Monomer solution consisting of 44.00 g of methyl methacrylate, V-65 [Wako Pure Chemicals Reagent] 0.99 g and IPA
An aqueous solution of an initiator consisting of 50.00 g was simultaneously added dropwise over 2 hours, and further polymerization was carried out for 4 hours while keeping the temperature inside the tank at 75 ° C. IP at 75 ° C. under reduced pressure (10,600 to 13,300 Pa) from the obtained reaction solution.
The mixture was concentrated until A was not distilled off, and a solid of a methyl methacrylate / N- (2-hydroxyethyl) acrylamide (= 20/80 molar ratio) copolymer was obtained. The Mw (in terms of PEG) of the obtained copolymer was 50,000 as measured by the method described in Synthesis Example 1.

Synthesis Example 25 (Synthesis of Vinyl Copolymer a'-3) 1 equipped with a stirrer, nitrogen introducing pipe, cooling device, thermometer
Sodium styrenesulfonate (Spinomer NaSS manufactured by Tosoh Corporation, purity 88%) 11 in a L4 neck flask
0.00g, sodium persulfate 6.60g, water 40
0.00g was added, and the temperature inside the tank was 70 ° C under nitrogen atmosphere.
The temperature was raised to 70 ° C., and polymerization was performed for 6 hours while maintaining the temperature inside the bath at 70 ° C. to obtain a transparent aqueous solution of sodium polystyrene sulfonate. The Mw (converted to PEG) of the obtained polymer is
When measured by the method described in Synthesis Example 1, it was 20.0.
It was good.

Table 1 shows the component (a) composed of the vinyl polymer obtained in the above synthesis example.

[0083]

[Table 1]

The component (b) is shown below. b-1: BY22-019 (dimethylpolysiloxane oil emulsion, manufactured by Toray Dow Corning Silicone Co., Ltd.) b-2: XS65-822 (dimethylpolysiloxane gum emulsion, manufactured by GE Toshiba Silicones Co., Ltd.) b-3 : KT-97E (dimethylpolysiloxane gum emulsion, manufactured by GE Toshiba Silicone Co., Ltd.).

Table 2 shows formulation examples x-1 to x-3 in which the components (a) and (b) are blended.

[0086]

[Table 2]

* 1: Weight average molecular weight of 3,000, manufactured by Katayama Chemical Co., Ltd. * 2: 1,2-benzisothiazolin-3-one solution, manufactured by Avicia Co., Ltd.

The components (a) and (b) were blended with the formulation examples of Table 2 as shown in Tables 3 and 4 to obtain paste compositions of Tables 3 and 4. Using the obtained paste composition, the morphological stability was evaluated by the method described below. The results are shown in Tables 3 and 4.

(Preparation of test cloth) 100% cotton broad #
60 (white plain, with fluorescent exposure) (obtained from Dyeing Test Material Tanigami Shoten Co., Ltd.), detergent attack for clothing (Kao Corporation)
Using a fully automatic washing machine, wash for 12 minutes-to rinse 1
After repeating the process of 5 times for spin-drying for 3 minutes for 5 cycles, rinse with running water for 15 minutes in a domestic two-tub type washing machine for 5 minutes for spin-drying, and naturally dry, then 15 cm × 25 cm (longitudinal yarn The test cloth is cut in the parallel direction.

100% of the paste compositions of Tables 3 and 4 were added. w.
f. After spraying uniformly on the entire test cloth using a spray vial (No. 6 manufactured by Maru-M) so that (on the weight of fabrics, the amount of the compositional material relative to the mass of the cloth), approximately at the center of the long side. Fold it in half and quickly iron it with a household iron (NI-A55 automatic iron manufactured by Matsushita Electric) for 60 seconds. Fold it in half again, turn it over, and continue ironing for 60 seconds.

Five treatments are similarly carried out for one paste composition. One of them is used for evaluation of firmness, and one is used for evaluation of texture. Spread the remaining three treated cloths and use a fully automatic washing machine (NA-F50K1 manufactured by Matsushita Electric Industrial Co., Ltd.) to wash for 12 minutes-12 times for rinsing-40 seconds for dehydration, high water level, standard amount of detergent attack for clothing. Washing is performed with, and the product that is naturally dried by flat-drying in the spread state is used for evaluation of morphological stability.

(Evaluation of elasticity) With respect to the above treated test cloth, the evaluation of elasticity was carried out by 5 panelists at 20 ° C /
Under the condition of 60% RH, relative evaluation with a control (one in which only water was sprayed and ironing was performed at the same temperature and time) was performed based on the following criteria. The average of five panelists was calculated, and 1 or more and less than 1.5 was evaluated as ⊚, 1.5 or more and less than 2 was evaluated as ○, and 2 or more and 3 or less was evaluated as x. The results are shown in Tables 3 and 4.
Shown in. Sufficient firmness compared to the control 1 It was comparable to the control 2 which was slightly firmer than the control 3.

(Evaluation of texture) The texture of the above treated test cloth was evaluated by 5 panelists at 20 ° C. /
Under the condition of 60% RH, relative evaluation with a control (one in which only water was sprayed and ironing was performed at the same temperature and time) was performed based on the following criteria. The average of 5 panelists was calculated, and 1 or more and less than 1.5 was evaluated as ⊚, 1.5 or more and less than 2 was evaluated as ○, 2 or more and less than 3 was evaluated as Δ, and 3 or more was evaluated as x. The results are shown in Tables 3 and 4. Significantly favorable texture compared to control 1 Slightly favorable texture to control 2 Equal to control 3 Poor texture to control 4

(Evaluation of Morphological Stability) With respect to the test cloth after drying, the wrinkle suppressing effect and the crease holding effect were visually evaluated by five panelists under natural light. That is, the relative evaluation with the control (those sprayed with water, ironed at the same temperature and time, washed and dried in the same manner),
Each of the wrinkle suppressing effect and the crease holding effect was evaluated according to the following criteria. The average of 5 panelists was calculated, and 1 or more and less than 1.5 was evaluated as ⊚, 1.5 or more and less than 2 was evaluated as ○, 2 or more and less than 3 was evaluated as Δ, and 3 or more was evaluated as x. The results are shown in Tables 3 and 4.

(Wrinkle suppression effect) Less wrinkles compared to the control 1 Less wrinkles than the control 2 Equal wrinkles compared to the control 3 There are more wrinkles than the control 4.

(Fold hold effect) Clear creases remain compared to the control 1 There are folds remaining compared to the control 2 It is the same crease remaining as compared to the control 3 No more folds left than the control 4

[0097]

[Table 3]

[0098]

[Table 4]

Claims (4)

[Claims] 1. (a) It is selected from the following monomer unit (A), monomer unit (B) and monomer unit (C) [in this case, when the monomer unit (C) is not selected, the monomer unit (A ) And a monomer unit (B)
Selected from both monomer units of], and the ratio of the monomer units (A), (B) and (C) in all the constituent monomer units is 50 to 100 in total.
A spray type paste prepared by filling a spray container with a paste composition containing a vinyl polymer accounting for mol%, (b) a silicone compound, (c) a compound represented by the following formula (1), and water. Fee. Monomer unit (A): Vinyl monomer unit having a carboxyl group Monomer unit (B): Vinyl monomer unit having a hydroxyl group Monomer unit (C): Vinyl monomer unit having a carboxyl group and a hydroxyl group [In the formula, R and R ″ are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and R ′ is a hydrogen atom or CH.
₃ and n are integers of 45 to 5000. ] 2. The paste composition comprises (a) 5 to 30% by mass, (b) 0.005 to 7.5% by mass, and (c) 0.
The spray-type paste according to claim 1, which contains 005 to 10 mass% and has a PH at 20 ° C of 3.0 to 7.5. 3. The spray type paste according to claim 1, wherein the equivalent ratio of the carboxyl group to the hydroxyl group of (a) is carboxyl group: hydroxyl group = 9: 1 to 1: 9. 4. (a) is a weight average molecular weight of 1,000 to
It is a high molecular weight polymer of 1,000,000.
Spray-type paste according to any one of the above.