JP2003089977A - Paste composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a paste composition imparting shape-retaining property and form-stabilizing effect to textiles. SOLUTION: This paste composition comprises (a) a polymer forming intramolecular crosslink therein by heating, (b) a specific amount of another carboxy-containing polymer than (a) and water and has pH 2.0-7.0 at 20 deg.C.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a paste composition. The present invention also relates to a spray type paste in which a spray container is filled with the paste composition.

[0002]

2. Description of the Related Art A sizing agent is used to impart appropriate tension to a textile product such as clothing and adjust its shape (hereinafter referred to as a shaping effect). Also, in order to easily give a shaping effect to clothing,
BACKGROUND ART A spray-type paste that is used by directly spraying a textile product when ironing is known.

Recently, a manual spray paste which does not use high-pressure gas has been developed. Japanese Unexamined Patent Publication No. 9-2419
No. 73, there is disclosed a spray paste which uses a water-soluble polymer having a carboxy group in a pH range of 3.5 to 7.5 to obtain good iron sliding properties without using a silicone-based iron sliding agent. It is disclosed. Further, Japanese Patent Application Laid-Open No. 7-119042 discloses a treatment agent containing a water-soluble polymer and an inorganic salt, and one of the water-soluble polymers is a homo- or copolymer of acrylic acid and / or methacrylic acid. There is.

However, the conventional spray glue can give a sufficient shaping effect by ironing after washing and drying, but it cannot maintain the shaping effect under high humidity during wearing. Have difficulty. In addition, after washing again, the shaping effect is lost, and the ironing treatment must be performed again. Even if it is washed several times, the shaping effect does not have a shape stabilizing effect.

On the other hand, ironing a shirt or slacks is one of the laborious works, and a form stabilizing treatment using formalin gas or formalin emitter or liquid ammonia is applied to reduce the work. Clothing is on the market. Further, in Japanese Patent Publication No. 7-26321, a fibrous cellulose material is impregnated with a treatment solution containing a specific polycarboxylic acid and a specific curing catalyst, and heated to effect esterification and cross-linking of the polycarboxylic acid and cellulose. A method of doing so is disclosed. Further, JP-A-7-189131 discloses a method for strengthening a cellulose substrate containing a polycarboxylic acid having at least two carboxy groups, a phosphorus-containing accelerator and an active hydrogen compound, and JP-A-11-158733. The official gazette discloses a method for 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, all of these methods
It is an effect obtained by ester cross-linking of carboxylic acid and hydroxyl group of cellulose, and is a technique that is effective in imparting a shape-stabilizing effect only to cloth or clothing having a high cellulose content (hereinafter collectively referred to as clothing), and does not contain cellulose. There has been a problem that clothing made of synthetic fibers or wool has no morphological stabilizing effect, and clothing having a low cellulose content cannot have a sufficient morphological stabilizing effect. Furthermore, it is not possible to impart sufficient shaping properties to the dried textile product, and it is impossible to make the clothes crispy or dry. Further, there is a problem that it causes deterioration and coloring of fibers.

[0007] Therefore, the problem to be solved by the present invention is to provide a paste composition capable of imparting preferable shapeability after drying the treated fiber product and imparting an excellent shape-stabilizing effect to clothing. It is in. The present invention also provides a spray paste filled with the composition.

[0008]

Means for Solving the Problems The present invention relates to (a) 0.01 to 20% by mass of a polymer which forms an intramolecular crosslink upon heating, (b) a polymer other than (a) having a carboxy group. It relates to a paste composition containing 005 to 20% by mass and water and having a pH at 20 ° C. of 2.0 to 7.0.

The present invention also relates to a spray type paste prepared by filling the above paste composition of the present invention in a container equipped with a manual sprayer.

In the present invention, the term "intramolecular crosslinking" refers to a phenomenon in which a three-dimensional structure is formed between polymers of the same type without interposing a crosslinking agent. In the case of a high molecular weight polymer, "the same kind" means that the combination of the monomer units forming the polymer is the same.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to (a) a polymer which forms an intramolecular crosslink by heating [hereinafter referred to as (a) component], and (b) a polymer other than the (a) component having a carboxy group. A paste composition containing [hereinafter referred to as (b) component], wherein the (a) component includes the following monomer unit (A),
Selected from monomer units (B) and monomer units (C) [in this case, when monomer units (C) are not selected, both monomer units (A) and monomer units (B) are selected) ] The ratio of the monomer units (A), (B) and (C) in all constituent monomer units is 50 to 100 in total.
A mol% vinyl polymer is preferred.

As the component (b), among the monomer units constituting the polymer of the component (b), a vinyl-based monomer unit having a carboxy group, that is, the monomer unit (A) is contained in all the monomer units. 20-100 mol% of
A vinyl-based polymer is preferred. 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 (A) having a carboxy group
Examples of the vinyl-based monomer (A) for obtaining the compound include one or more selected from compounds represented by the following formulas (1) to (3).

[0014]

[Chemical 1]

[In the formula, 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 (1) to (3) include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid and the like or salts thereof. Examples of the salt include sodium, potassium, lithium, ammonium, monoethanolamine, diethanolamine, triethanolamine and the like. The itaconic acid and maleic acid may be acid anhydrides represented by the following formulas (4) and (5). The acid anhydride is hydrolyzed to be a monomer unit constituting the polymer of the present invention.

[0017]

[Chemical 2]

Among the above, acrylic acid, methacrylic acid, maleic acid, itaconic acid or their sodium salts and potassium salts are preferable. 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) for obtaining the monomer unit (B) having a hydroxyl group include at least one selected from compounds represented by the following formulas (6) to (11).

[0020]

[Chemical 3]

[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. ].

Specific examples of the formula (6) include N- (2-hydroxyethyl) (meth) acrylamide and 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. Specific examples of the formula (7) include hydroxyethyl vinyl ether and hydroxybutyl vinyl ether. Specific examples of the formula (8) include polyoxyethylene (meth).
Examples include polyoxyalkylene adducts of (meth) acrylamide obtained by using oxyethylene (hereinafter referred to as EO), oxypropylene (hereinafter referred to as PO), etc., such as acrylamide and polyoxypropylene (meth) acrylamide, alone or in combination. . As a specific example of formula (9),
Examples thereof include polyoxyalkylene adducts of (meth) allyl ether obtained by using EO, PO and the like such as polyoxyethylene (meth) allyl ether and polyoxypropylene (meth) allyl ether alone or in combination. Expression (1
Specific examples of 0) include 2-hydroxyethyl (meth)
Acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-
2 carbon atoms such as hydroxyhexyl (meth) acrylate
~ 6 hydroxyalkyl (meth) acrylate and the like. Specific examples of the formula (11) include polyoxyalkylene adducts of (meth) acrylic acid obtained by using EO such as polyoxyethylene (meth) acrylate and polyoxypropylene (meth) acrylate, PO, etc., alone or in combination. Is mentioned.

R ³ , R ⁵ and R in the formulas (6) to (11)
^{When 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 5. The polyoxyalkylene average addition mole number m of the formulas (8), (9) and (11) is preferably 2 to 50.

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 components (a) and (b) 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 such a monomer unit (D) include methyl (meth) acrylate and ethyl (meth).
(Meth) acrylic acid derivative such as acrylate, N, N-
N-substituted (meth) acrylamide derivatives such as dimethyl acrylamide, N, N-diethyl acrylamide, isopropyl-acrylamide, and tert-butyl acrylamide, and polyoxyalkylene adducts of (meth) acrylic acid represented by formula (12). Alkyl ether, monoalkyl ether of polyoxyalkylene adduct of (meth) acrylic acid amides represented by formula (13), Mono of polyoxyalkylene adduct of (meth) allyl alcohol represented by formula (14) Examples include alkyl ethers.

[0026]

[Chemical 4]

[Wherein 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 (12), (13) and (14)
R¹⁵, R¹⁷, R¹⁸, R²⁰, R^{twenty one}, R ^{twenty three}Is an alkyl group
The total carbon number is preferably 1 to 22. Also poly
The oxyalkylene average addition mole number m is preferably 2 to
50.

Other vinyl-based monomers (D) include vinyl ethers such as methyl vinyl ether and butyl vinyl ether, styrene, styrene derivatives such as styrene sulfonic acid or its salts, 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 the formulas (1) to (3).

The component (a) used in the present invention includes a monomer unit (A), a monomer unit (B) and a monomer unit (C).
Of 50 to 100 mol%, more preferably 60 to 100 mol%, especially 70 to 100 mol% in all the constituent monomer units.
Is preferred. When the component (a) contains the above-mentioned monomer units (A), (B) and (C), the equivalent ratio of the carboxy group and the hydroxyl group is preferably a carboxy group: Hydroxyl group = 9: 1
It is 1: 9, more preferably 8: 2 to 1: 9, and particularly preferably 7: 3 to 2: 8. Where equations (4) and (5)
The acid anhydride represented by the formula 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 (10) to (11) is a monomer unit constituting the polymer of the component (a) of the present invention, the formulas (1) to (1) to
The monomer unit (A) represented by (5) is 5 in the polymer.
It is preferably ˜50 mol%, particularly preferably 5 to 45 mol%. Within this range, intramolecular or intermolecular crosslinking of the vinyl polymer of the component (a) is formed more efficiently, and higher morphological stability can be obtained regardless of the type of fiber.

The component (b) used in the present invention contains the monomer unit (A) in an amount of 20 to 100 mol%, more preferably 50 to 100 mol%, and particularly 70 to 100 mol% in all the constituent monomer units.
Is preferred. Here, the acid anhydrides represented by the formulas (4) and (5) have 2 equivalents of carboxy groups. 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 the monomer unit constituting the polymer of the component (b) has the monomer units of (B) and / or (C), the molar ratio of carboxy group to hydroxyl group may exceed 9: 1. It is preferable in terms of shapeability and morphological stabilization effect.

Component (a) and (b) used in the present invention
The method for synthesizing the vinyl polymer as the component is described in, for example, JP-A-6-
The method as described in JP206750 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 component (a) of the present invention preferably has a weight average molecular weight in the range of 1,000 to 1,000,000. Among them, the range of 5,000 to 800,000 is more preferable, and the range of 10,000 to 500,0 is more preferable.
00 is particularly preferred.

The component (b) of the present invention preferably has a weight average molecular weight in the range of 1,000 to 1,000,000. Above all, 5,000 to 800,000
The range of 0 is more preferable, and 10,000 to 50 is more preferable.
10,000 is especially preferred.

In the present invention, the weight average molecular weight can be determined by gel permeation liquid chromatography (hereinafter referred to as GPC) method using polyethylene glycol (hereinafter referred to as PEG) as a standard substance.

In the present invention, it is also possible to use two or more kinds of the above vinyl-based polymers having different compositions or different weight average molecular weights in combination with each of the components (a) and (b).

The paste composition of the present invention comprises the component (a) of 0.
The content is 01 to 20% by mass, preferably 0.1 to 15% by mass, and particularly preferably 0.5 to 10% by mass. Also,
The component (b) is contained in an amount of 0.005 to 20% by mass, preferably 0.
005 to 15% by mass, particularly preferably 0.25 to 10% by mass. Furthermore, the mass ratio (% by mass:% by mass) of component (a): component (b) is preferably 10: 1 to 1: 1.
0, more preferably 5: 1 to 1: 5, and particularly preferably 3: 1 to 1: 3, and in such a range, excellent shapeability and high morphological stabilizing effect can be obtained.

The paste composition of the present invention has a pH at 20 ° C.
Is 2.0 to 7.0, preferably 2.5 to 6.0,
It is more preferably adjusted to 3.0 to 5.5. Within this range, the garment is given a favorable shaping property, the strength of the fiber is not deteriorated, and the shape stability is improved. pH
May be adjusted with an acid or alkaline agent used in a fiber treating agent or the like, or may be adjusted with a water-soluble inorganic salt described later.

By further adding a water-soluble inorganic salt to the paste composition of the present invention, the morphological stabilizing effect is improved. The term “water-soluble” as used in the present invention means that the solubility at 20 ° C. is 0.1 g / 100 g of water or more. In particular,
Phosphorous acid, hypophosphorous acid, phosphoric acid, metaphosphoric acid, pyrophosphoric acid, phosphoric acid such as polyphosphoric acid, boric acid, boric acid such as metaboric acid, silicic acid, silicic acid such as metasilicic acid, sulfuric acid,
It is an alkali metal salt, alkaline earth metal salt, or amine salt of an acid selected from sulfuric acids such as sulfurous acid. In the present invention, sodium salts and potassium salts of phosphorous acid, hypophosphorous acid, phosphoric acid and polyphosphoric acid are particularly preferable from the viewpoint of improving morphological stability.

The paste composition of the present invention preferably contains a water-soluble inorganic salt in an amount of 0.005 to 10% by mass, more preferably 0.
05-7.5% by mass, particularly preferably 0.1-5% by mass
contains.

In the present invention, the mass ratio of the water-soluble inorganic salt to the component (a) is preferably (component (a): water-soluble inorganic salt) from 1: 0 in order to improve morphological stability.
It is 1: 1, more preferably 1: 0.05 to 1: 0.5, particularly preferably 1: 0.1 to 1: 0.3.

It is preferable to further add a silicone compound to the paste composition of the present invention in order to improve the morphological stabilizing effect, appropriate texture and touch. Specific examples thereof include dimethylpolysiloxane oil, dimethylpolysiloxane oil having a hydroxyl group at a part or end of a side chain, dimethylpolysiloxane oil, or modified silicone oil obtained by introducing an organic group into hydroxyl group-containing dimethylpolysiloxane oil. Examples of the organic group introduced to obtain the modified silicone oil include an amino group, an amide group, a polyether group, an epoxy group, a carboxy group, an alkyl group, and a poly (N-acylalkyleneimine) chain.

The silicone compound can also be used by emulsifying it with an emulsifier. Emulsifiers include nonionic surfactants,
It is preferable to use any one or more of an anionic surfactant, a cationic surfactant and an amphoteric surfactant in arbitrary combination.

It is also possible to introduce a hydrophilic modifying group such as a polyether group into the silicone oil without using an emulsifying agent and self-emulsify the silicone oil before use.

The silicone compound as described above is available as the silicone compound itself or as an emulsified silicone preparation. For example, as the dimethylpolysiloxane emulsion, BY22-029 or the like is available from Toray Dow Corning Silicone Co., Ltd., and as the one having an amino group introduced into the hydroxyl group-containing dimethylpolysiloxane oil, Toray Dow Corning Silicone is available. SM8704C is available from
X-61-689 is available from Shin-Etsu Chemical Co., Ltd. as a dimethylpolysiloxane oil having an amino group and a polyether group introduced.

In any case, the paste composition of the present invention is
The silicone compound is preferably contained in an amount of 0.005 to 7.5% by mass, more preferably 0.01 to 5% by mass, still more preferably 0.05 to 2.5% by mass.

The paste composition of the present invention further contains a low molecular weight polyvalent carboxylic acid and a nonionic surfactant to further improve the shape stabilizing effect.

The low molecular weight polyvalent carboxylic acid is an organic acid having two or more carboxy groups in one molecule or a salt thereof, preferably having at least two carboxy groups respectively bonded to adjacent carbon atoms. It is an organic acid or a salt thereof. The molecular weight as an acid is 116 to 1,000, preferably 116 to 800, more preferably 116 to 500.
Is. 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, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid, tetrahydrofuran tetracarboxylic acid, etc. . 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.

Of these low molecular weight polycarboxylic acids,
Particularly in that citric acid, maleic acid, tartaric acid, succinic acid, malic acid, 1,2-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, cyclopentanetetracarboxylic acid or salts thereof improve the morphological stability effect. preferable.

The paste composition of the present invention contains such a low molecular weight polyvalent carboxylic acid as an acid, preferably 0.01 to 2
0% by mass, more preferably 0.1 to 10% by mass, particularly preferably 0.1 to 5% by mass.

The nonionic surfactant is selected from those which improve the wettability or penetrability of the paste composition of the present invention into a textile product. Preferred examples thereof include polyoxyalkylene (hereinafter referred to as POA) adduct of alcohol having 6 to 18 carbon atoms, POA adduct of alkylphenol having an alkyl group having 6 to 18 carbon atoms, and 6 carbon atoms.
-18 fatty acid POA adduct, polyhydric alcohol C6-18 fatty acid ester POA adduct, carbon 6-
18-alkylamine POA adduct having 6 to 18 carbon atoms
POA adduct of fatty acid amide, POA adduct of fat and oil,
Examples include POA-type nonionic surfactants such as POA adducts of polypropylene glycol. Where POA is
Polyoxyethylene or polyoxypropylene is preferred, and the average number of added moles is 2 to 100 moles, preferably 5 to 80 moles.

Further, fatty acid ester of glycerol having 6 to 18 carbon atoms and pentaerythritol having 6 to 18 carbon atoms.
Fatty acid esters of sorbitol and sorbitan having 6 to 18 carbon atoms, sucrose fatty acid esters having 6 to 18 carbon atoms, polyhydric alcohols having 6 to 18 carbon atoms, alkanolamines having 6 to 1 carbon atoms
Examples thereof include polyhydric alcohol type nonionic surfactants such as fatty acid amide of 8.

In both cases of POA type and polyhydric alcohol type, the alcohol, alkyl group and fatty acid may be linear or branched. Moreover, those carbon numbers may be a mixture.

The paste composition of the present invention preferably contains a nonionic surfactant in an amount of 0.001 to 5% by mass, particularly 0.01 to 2.5% by mass. The content of all the surfactants in the paste composition of the present invention is preferably 5% by mass or less.

If necessary, the paste composition of the present invention comprises a wax or an emulsion thereof for improving iron slipperiness, an antibacterial / sterilizing / antifungal agent for improving storage stability, alcohol, and polyol. Etc. and components used in clothing spray pastes such as fragrances for improving the feeling of use can be optionally blended.

The balance of the paste composition of the present invention is water, preferably 37.5 to 99.9% by mass.

In the usage form of the paste composition of the present invention, the textile product is impregnated with the paste composition and then subjected to heat treatment to impart shapeability and shape stability to the textile product. The method of impregnation treatment and heat treatment is not particularly limited, but the impregnation treatment includes spray treatment, coating treatment, dipping treatment and the like.
An iron, a trouser press, a press, or the like can be used for the heat treatment. Among them, it is convenient and preferable to spray the fiber composition with the paste composition to impregnate it and heat it by ironing.

For spray processing, an aerosol type or a manual type is used.
It is possible to use sprayers such as riggers and manual pumps.
Yes, with a manual trigger or manual pump being preferred.
However, a manual trigger is particularly preferable. In the present invention, the glue
Fill the container with these sprayers
Most preferably, it is used as an article. these
The structure of the sprayer is not particularly limited, but one spray
0.1 to 1.5 g, preferably 0.2 to 1.0 g,
Preferably, 0.25 to 0.8 g of the paste composition is ejected.
Things are good. 15 cm away from textiles
When sprayed from a separate place
The area where the product adheres is 50 to 800 cm ², 100 more
~ 600 cm²Is preferred. Moreover, for example,
Kaifaira 4-37554 and JP-A 9-122547
When using the accumulator trigger as disclosed in the publication
Uniformity of spray mist and no dripping or dripping
Is good at.

In the present invention, the vinyl-based polymer of the component (a) is on average 0.01 to 20 g, and further 0.1 to 15 per 100 g of the fiber product by the above spray treatment.
It is preferable to uniformly attach g, particularly 0.5 to 10 g, from the viewpoint of shapeability and shape stabilizing effect.

In the present invention, after the fiber composition is impregnated with the paste composition as described above, a heat treatment at 60 to 300 ° C. is performed to obtain a fiber product having shapeability and morphological stabilizing effect. . The heat treatment can be performed by using an iron, a trouser press, a warm air dryer, etc. which are generally popular, but an iron and a trouser press that can simultaneously perform heat treatment and shaping such as wrinkle removal and creasing are preferable. It is simple and preferable. The iron is set at a temperature suitable for the fiber material, but preferably 1
20-220 degreeC, Especially preferably, it is 140-200 degreeC. The ironing time is preferably 10 for textile products.
^{1 to} 90 seconds per 0 cm ² , particularly preferably 2 to 60 seconds
Seconds.

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

The product form of the paste composition of the present invention may be used as it is for the above-mentioned impregnation treatment, but it is diluted with water to prepare the paste composition of the present invention. It may be a concentrate. As an example of a method for preparing the paste composition of the present invention from a specific concentrate, for example, a container in which a textile product such as a washing tub or a washbasin can be immersed is filled with water, and the concentrate is contained in the container. There is a method in which the paste composition of the present invention is prepared by measuring and adding using a lid of a container or the like and mixing, and immersing the textile product in the composition. In addition, there is a method in which an appropriate amount of the concentrate and water are added to and mixed with a container equipped with the sprayer as described above, and the mixture is sprayed.

The most preferred method of use is to impregnate the textile composition with the paste composition of the present invention by spraying and subsequently heat-shape by ironing.

The optimum composition 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-based copolymer such as 2: 8 0.5 to 10% by mass As a component (b), a vinyl-based monomer having a carboxy group selected from (meth) acrylic acid, maleic acid, itaconic acid and maleic anhydride. A vinyl-based polymer comprising one or more kinds of monomer units (A) obtained from (A), wherein these monomers (A) account for 100 mol% in the constituent monomer units of the polymer. 0.25-10% by mass (II) selected from sodium hypophosphite, sodium phosphite, trisodium phosphate, disodium or potassium hydrogen phosphate, sodium or potassium dihydrogen phosphate, sodium sulfate and sodium sulfite. Water-soluble inorganic salt
0.1-5% by mass (III) Dimethyl polysiloxane oil, hydroxyl group-containing dimethyl polysiloxane oil, dimethyl polysiloxane oil or modified silicone oil obtained by introducing at least one of amino group and amide group into hydroxyl group-containing dimethyl polysiloxane oil, and Emulsions of these oils
0.05 to 2.5% by mass (as silicone oil content) (IV) A pH adjusting agent selected from sodium hydroxide, potassium hydroxide, phosphoric acid, sulfuric acid and hydrochloric acid as necessary, and the balance of water, PH at 20 ° C is 4.0-
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.

[0067]

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 paste composition for a textile product, which does not impair the shape-stabilizing effect, has a desirable firmness, and can impart an appropriate texture and feel to the textile product.

[0068]

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, 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] GPC was measured 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 inlet tube, 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 (combining 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 inlet tube, 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 inlet tube, 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 inlet tube, 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 introducing 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 inlet tube, 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 introducing tube, cooling device, and 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, a nitrogen inlet tube, a cooling device, and a 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, nitrogen introducing pipe, cooling device and 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 introducing pipe, 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, a nitrogen inlet tube, a cooling device, and a 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 inlet tube, 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, a nitrogen inlet tube, a cooling device, and a 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.

[0096]

[Table 1]

The component (b) is shown below. b-1: sodium polyacrylate (Wako Pure Chemical Industries, Mw
= 70,000) b-2: Sodium polymethacrylate (Japan NSC,
ALCOSPERSE-124, Mw = 9,500) b-3: Polyacryl malein (Kao Corporation, POIZE-52)
0, Mw = 20,000) In Table 2, prescription example x in which the above components (a) and (b) are blended
-1 to x-4 are shown.

[0098]

[Table 2]

* 1: Amodimethicone emulsion, manufactured by Toray Dow Corning Silicone Co., Ltd. * 2: Aminopolyether-modified silicone, manufactured by Shin-Etsu Chemical Co., Ltd. * 3: 1,2-benzisothiazolin-3-one Liquid, manufactured by Avicia Co., Ltd.

The components (a) and (b) were blended in 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.

The paste compositions shown in Tables 3 and 4 were treated with 100% o. 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

[0109]

[Table 3]

[0110]

[Table 4]

Continued front page    F-term (reference) 4L031 AA02 AB32 AB33 BA33                 4L033 AA02 AB05 AB06 AC12 CA20                       CA24 CA48 CA59

Claims (7)

[Claims] 1. (a) 0.01 to 20% by mass of a polymer that forms intramolecular crosslinks by heating, (b) 0.005 to 20% by mass of a polymer other than (a) having a carboxy group, and water. And a pH of the paste composition at 20 ° C. is 2.0 to 7.0. 2. (a) is the following monomer unit (A),
Selected from monomer units (B) and monomer units (C) [in this case, when monomer units (C) are not selected, both monomer units (A) and monomer units (B) are selected) ] The ratio of the monomer units (A), (B) and (C) in all constituent monomer units is 50 to 100 in total.
The paste composition according to claim 1, which is a vinyl-based polymer in a mol%. 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 3. The paste composition according to claim 2, wherein the equivalent ratio of the carboxy group to the hydroxyl group in (a) is carboxy group: hydroxyl group = 9: 1 to 1: 9. 4. Among the monomer units constituting (b),
20 to 1 vinyl monomer unit having a carboxy group
The paste composition according to any one of claims 1 to 3, occupying 00 mol%. 5. A water-soluble inorganic salt in an amount of 0.005 to 10% by mass.
The paste composition according to any one of claims 1 to 4, which comprises. 6. A silicone compound is added in an amount of 0.005 to 7.5.
The paste composition according to any one of claims 1 to 5, which comprises mass%. 7. A spray type paste prepared by filling the paste composition according to claim 1 in a container equipped with a manual sprayer.