JPS6328979A - Finish composition for clothes - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a finish for clothing that can be easily used at home, improves the color development of dyed clothing, and improves the depth and clarity of color. The present invention relates to a drug composition.

[Conventional technology]

BACKGROUND ART Fabric softeners, starch agents, antistatic agents, water and oil repellents, and the like are used as finishing agents for clothing in the home in order to maintain and restore the functionality or texture of textile products.

At present, the functions and effects of these finishing agents have become established in daily life, and the treatment of clothing with finishing agents has become a part of washing habits. This is simply because the above-mentioned finishing agents are designed so that anyone can easily use them at home. However, in recent years, the diversification of clothing, especially the diversification of designs including the colors and patterns of outerwear, has been remarkable, and has become the main factor determining the preferences of the wearer. Finishes used in traditional homes are used to adjust the color of clothing,
It does not show an equally positive effect on the handle.

On the other hand, in the textile processing industry, a wide variety of textile treatments are performed compared to the finishing agent treatments performed at home. One of these is a type of resin processing using a so-called darkening agent, which has been proposed in order to improve the color development of dyed products and increase the depth of hue.

For example, in JP-A-53-111192, the refractive index is 1.
．． Discloses a fiber structure having a thin film formed from a polymer with a refractive index of 50 or less, and as a manufacturing method thereof, a monomer having a refractive index of 1.5 or less as a polymer is placed together with fibers in a closed container, and plasma polymerization or electric discharge is performed. We are proposing a method of forming thin films through graft polymerization. Also, special public service 58-5155
Publication No. 7 discloses a method in which a compound having a low refractive index of 1.45 or less is adsorbed on the surface of a fiber structure in the form of a thin film of 0.3% to 10% and then subjected to dry heat or hot heat treatment,
Fluororesins, acrylic acid ester resins, vinyl polymers whose polymer refractive index is 1.45 or less are used as raw materials for thin film formation.
We will describe scales using silicone resin, and give specific examples of scales using emulsions and solvent solutions of fluorine-containing compounds and acrylic esters, by immersion adsorption at high temperatures, or by spray coating and then dry heat or heat treatment. Discloses a method for forming thin films on fibers.

However, these methods require special processing equipment, the processing bath temperature must be kept at a high temperature, or post-processing such as heat cent, which requires washing-finishing-drying-wearing at home. It is almost impossible to incorporate this cycle into a habit.

Furthermore, Japanese Patent Publication No. 60-30796 discloses an aqueous resin composition obtained by polymerizing a monomer having a polymerizable unsaturated bond in the presence of polyurethane emulcidin having thermosetting reactivity. A color deepening agent characterized in that a dry film of an aqueous resin composition has a refractive index of 1.50 or less is disclosed.

Unlike the above two examples, this treatment agent has a deep coloring effect even in home treatment cycles, but it cannot be said to be sufficient, and furthermore, it is necessary to devise ways to avoid damaging the texture of treated clothing. However, they do not have the same texture retention or texture properties as traditional household finishes. Furthermore, when these color deepening agents for fiber processing are used in home processing cycles, there is a problem that the resin is fixed and dries, causing a so-called whitening phenomenon.

This is because the conditions for resin processing as illustrated do not originally match the processing conditions at home. Therefore, even if these resin processing techniques are simply used, it is impossible to expect sufficient effects as a finishing agent for household clothing.

The object of the present invention is to improve the above-mentioned drawbacks, and to relate to a finishing agent that can easily increase the depth of the hue of dyed clothing at home, and that can also impart softness with rich elasticity to clothing.

[Means for solving problems]

As a result of intensive research, the present inventors succeeded in organically and synergistically combining conventional finishing technology and resin processing technology, and invented a finishing composition with completely new functions and effects. I came to the conclusion.

That is, the present invention provides (A) a monomer selected from the group consisting of a monomer having an unsaturated bond that is polymerizable in the presence of a cationic emulsifying dispersant, and a monomer having a polymerizable unsaturated bond and a crosslinking reactive group; species or two
An aqueous resin composition obtained by polymerizing more than one type of monomer, wherein the glass transition temperature (Tg) of the polymer constituting the aqueous resin composition is in the range of 20 to 150°C, and the drying A substantially water-based emulsion containing an aqueous resin composition whose film has a refractive index of 1.50 or less and (B) an aqueous polyurethane, comprising 1 to 40% by weight of component (A) as a solid content and component ( B) to component (A) at a solid content weight ratio of 1/200 to 4/1
The present invention provides a clothing finishing composition comprising:

When colored clothing is treated with the finishing composition, due to the organic and synergistic effect of the two components, the hue becomes deeper and the pattern becomes more vivid than would be possible with the prior art. Furthermore, the treatment does not impair the texture of any type of clothing, and more actively imparts softness and elasticity, while also eliminating unevenness, whitening, and other problems that have been a problem with conventional technology. No untoward phenomenon will occur.

These effects are based on the film properties of the aqueous resin composition and aqueous polyurethane, particularly the refractive index and Tg of the former, and the adhesion or affinity with fibers and the film properties of the latter, but according to the present invention, It is important to demonstrate these abilities in the cycle of washing, finishing, drying, and wearing at home.

Desirably, the garment finish composition of the present invention is a substantially aqueous emulsion.

The method for obtaining the finishing composition of the present invention is as follows: (1) Separately prepare and mix an aqueous dispersion of an aqueous resin composition and an aqueous dispersion or an aqueous solubilized aqueous polyurethane.

(2) An aqueous polyurethane or its aqueous dispersion or aqueous solubilizer is preliminarily coexisted with or added to the water used when producing an aqueous dispersion of an aqueous resin composition.

(2) A dispersion of an aqueous resin composition in water is preliminarily added to the water used when dispersing or solubilizing an aqueous polyurethane in water.

This method is preferable.

The content of the aqueous resin composition (A) in the finishing composition is 1 to 40% by weight as a solid content, and the aqueous polyurethane (
B) is desirably prepared so that the solid content is in the range of 1/200 to 4/1 by weight relative to the solid content of the aqueous resin composition (A). If the concentration is below this concentration, the desired performance may not be given to clothing, or the amount required for one treatment of the finishing agent is too large and the treatment is not convenient, and above this concentration, the performance of the product of the present invention or have poor mechanical or thermal stability as a finish composition.

The product of the present invention not only does not impair the essential feel of treated clothing, but also can impart elasticity and softness to the clothing. Although this function is due to the essential effect of the water-based polyurethane, it is not impaired in any way by the coexistence of the water-based resin composition. Therefore, if you want to achieve this effect depending on the purpose, it is better to adjust the ratio of water-based polyurethane to a high level within the above-mentioned allowable range.

The aqueous resin composition in the present invention is a group consisting of a monomer having an unsaturated bond that can be polymerized in the presence of a cationic emulsifying dispersant, and a monomer having a polymerizable unsaturated bond and a crosslinking reactive group. It is obtained by polymerizing one or more monomers selected from the following.

The cationic emulsifying dispersant used in the present invention is selected from the group consisting of cationic surfactants or cationic polymeric emulsifying dispersants.

Desirable examples of cationic surfactants include the compound (
One or more long chain aliphatic groups as shown in 11 to (4),
Examples include, but are not limited to, those having one or more quaternary nitrogen atoms. Of course, the main component is a cationic surfactant such as the one illustrated, and generally “
A chemical substance known as "knitted fabric softener" may be used. When using this knitted fabric softener, 50% by weight of a cationic surfactant as exemplified may be used.
It is desirable that the content is above.

Quaternary ammonium compound R+: cs to Cz2 saturated or unsaturated linear or branched alkyl group or C8 to C2□ secondary alkanol group R1R4: C, to C3 alkyl group or hydroxyalkyl group or -+CHz C1120 >-T-H n-1
~R, :R, or R,, same as R4 x :C1hSOn, c mountain soP.

C mountain-+C00e n-0~17°C, L--tOPOP n=8~18°HOCHzC
Ooo.

Halogen Ra, Rt: C+ to C8 alkylene group or fC
HZ CHZ n-1 to 10 at 0 loaf It is essential that the cationic polymer emulsifying dispersant used in the present invention contains a basic nitrogen atom or a cationic nitrogen atom, but it also contains carbon atoms in the molecule. It may contain groups such as acid salts, sulfonate salts, amides, esters, etc., including the following.

(a) Homopolymers of salts or quaternary ammonium salts of nitrogen-containing monomers represented by the following general (1) to (V), or copolymers of two or more thereof.

R■ [In the formula, A represents 10- or -NH-, n represents an integer of 1 to 3, R represents H or CH3, R2 and R3 represent H,
Indicates CO, or C18. ] R+ [In the formula, R1* R2, R31n, I are the same as in formula (I)] In the C formula, R1 is the same as in formula (1), the substitution position of pyridine is the 2 or 4 position] [In the formula, R, , R, are the same as in formula (1), and the substituent position of piperidine is the 2 or 4 position] [In the formula, R1, RZ, and R3 are the same as in formula (I)] Specific examples of these monomers include (1) ) Formula 0 % Methacrylamide, etc.: (■) Dimethylaminomethylethylene, diethylaminomethylethylene, dimethylaminomethylpropene, diethylaminomethylproben, etc. of formula (■): Vinylpyridine, etc. of formula (■): Vinylpiperidine of formula (■) , vinyl-N-methylpiperidine, etc.: (V
) vinylbenzylamine, vinyl-N, N-dimethylbenzylamine, and the like.

Among the copolymers, those having an average molecular weight of 1,000 to 10,000,000 are used as homopolymers of these monomers.

(middle) one or two of the nitrogen-containing monomers represented by the above general formulas (I) to (V) or their salts or quaternary ammonium salts;
and α, β-unsaturated carboxylic acids or salts thereof or derivatives thereof, vinyl compounds containing sulfonic acid groups or salts thereof, acrylonitrile, vinylpyrrolidone, and carbon atoms having 2 to 2 carbon atoms.
A copolymer with one or more vinyl monomers selected from the group consisting of 20 aliphatic olefins.

Examples of the vinyl monomer include vinylpyrrolidone, acrylonitrile: acrylic acid, methacrylic acid, maleic acid, or alkali metal salts, ammonium salts, amide compounds or esters of these acids: vinylsulfonic acid, methallylsulfonic acid. , 2-acrylamino-
Examples include 2-methylpropanesulfonic acid, p-styrenesulfonic acid, and alkali metal salts or ammonium salts of these acids. Of the copolymer of the nitrogen-containing monomer and vinyl monomer, the average molecular weight is 1,000.
0~to, ooo, oooO are used.

(C) Salt or quaternary ammonium salt of ring-opening polymer of ethyleneimine.

Specifically, this repeating unit has the following general formula (VI
), and the average molecular weight is i, oo.

~10,000,000.

CH*CHJ)It [In the formula, n2 is an integer of 1 to 5, and n3 is an integer of O to 5] (d) Condensation product of aliphatic dicarboxylic acid and polyethylene polyamine or dipolyoxyethylene alkylamine salt or quaternary ammonium salt.

Specifically, these repeating units are a condensation product with polyethylene polyamine represented by the general formula (■) and a condensation product with dipolyoxyethylene alkylamine represented by the general formula (■), and the molecular weight is 1.000~10.000.0
00 is mentioned.

11l-QC-Re-CONH1R'-NH廿Rゝ-N
)l→-(■) [In the formula, R# is a dimer acid residue or an alkylene group having 1 to 10 carbon atoms, R'' is -CH2CH2-1
n represents an integer of 2 to 7] [In the formula, R# is the same as the formula (■), R5 is an alkyl group having 1 to 8 carbon atoms, R8 is 11 or C) 13, r1% and n
6 represents an integer of 1 to 10] Examples of the aliphatic dicarboxylic acids include dimer acid and adipic acid, and examples of polyethylene polyamines include:
Diethylenetriamine, triethylenetetramine, etc. can be used.

(e) Dihaloalkane-polyalkylenepolyamine condensation product.

Specifically, dihaloalkanes such as 1,2-dichloroethane, 1,2-dibromoethane, and 1,3-dichloropropane, and polyalkylene polyamines having two or more tertiary amino groups in the molecule are used. It is a condensation product that is a quaternary ammonium salt, and its average molecular weight is 1.00.
0 to 10,000,000.

Examples of the polyalkylene polyamines mentioned above include the following.

(f) Shrimp halohydrin-amine condensation product.

Specifically, the repeating unit is represented by the following general formula (X),
The average molecular weight is 1.000 to io, ooo, oo.

The following is mentioned.

-E-0-CH2C)I←R6 [In the formula, R? ~R1 is an alkyl group having 1 to 4 carbon atoms, Xo
indicates a halogen ion] The polymers of t8) to (f) above have an average molecular weight of 10
．． 000 to 1,000,000 is more preferable.

(g) Salts of chitosan or cationically modified products of starch or cellulose.

(h) Cationically modified polyvinyl alcohol.

As mentioned above, as a cationic polymer emulsifying dispersant (al
Although the polymers of type (h) are shown, the present invention is not limited thereto.

As the monomer having a polymerizable unsaturated bond used in the present invention, a radically polymerizable compound is used, such as pentadecafluorooctyl acrylate (no =
1.339), tetrafluoro-3-(pentafluoroethoxy)propyl acrylate (no”1.35)
, hebutafluoroptyl acrylate (no ” 1.
367), 2-(heptafluorobutoxy)ethyl acrylate (no-1,39), trifluoroisopropyl methacrylate (no”1.42), 2,2.2-
Trifluoro-1-methylethyl methacrylate (n
o = 1.42), etc., fluorinated acrylic esters or methacrylic esters, vinyl isobutyl ether (no
= 1.45), vinyl ethyl ether (no=1
．． 454), vinyl butyl ether (rlo ” 1
．． 456), butyl acrylate (no-1, 46), ethyl acrylate (no-
1,47), 2-ethoxyethyl acrylate (no-
1,471), isopropyl methacrylate (n, depth 1.473), n-butyl methacrylate (no=1.473),
483), isobutyl methacrylate (no=1.47)
7), n-hexyl methacrylate (no = 1,
4313), methyl methacrylate (no -1,49
), α,β-unsaturated compounds such as esters of α,β-unsaturated carboxylic acids, and vinyl ester compounds such as vinyl propionate (no ” 1.4665) are mainly used.

In addition, monomers having polymerizable unsaturated bonds and crosslinking reactive groups for imparting further reactivity include α,β-unsaturated carboxylic acids such as itaconic acid, acrylic acid, methacrylic acid, fumaric acid, and maleic acid. , acrylamide, methacrylamide, maleic acid amide, maleic acid amide, α, β-unsaturated carboxylic acid amide such as maleic acid imide, unsaturated carboxylic acid substituted amide such as methylol acrylamide, methylol methacrylamide, methoxymethyl acrylamide, N-isobutoxymethyl acrylamide, etc. Heterocyclic vinyl compounds, such as vinylpyridine, vinylpyrrolidone,
Examples include polyvinyl compounds represented by divinylbenzene, allyl compounds such as allyl alcohol and allyl acetate, and glycidyl methacrylate, which can be used as subcomponents for modification to impart reactivity. One or more monomers are used.

Preferably, among all the monomers used, selected from methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, 3111C-butyl methacrylate, 2-hydroxyethyl methacrylate, phenyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate It is desirable that the weight fraction of the monomer is 50% by weight or more.

Among the polymers obtained by polymerizing these monomers, those whose T is in the range of +20 to 150°C and whose dry film has a refractive index of 1.50 or less are the aqueous resins of the present invention. constitute a compound. These Tg and refractive index can be known from the Polymer Handbook. Further, the Tg and refractive index of the copolymer of two or more monomers are determined according to the following formula.

For example, in the case of a copolymer of monomers ^, B and C, (Tg)
A, (Tg)s, (Tg)c: Tg of each homopolymer of A, B, C WA, WII, Wc: A, B, C in copolymer
Each composition ratio (ii) refractive index of copolymer n=Lni +L+ns +
Wcnc” A+ no + n C' A IB
Refractive index Wa, we, wc of each homopolymer of HC: A, B, in the copolymer
C Each composition ratio The polymerization catalyst used in the radical emulsion polymerization of the above-mentioned monomer having a polymerizable unsaturated bond in the presence of a cationic emulsifying dispersant includes potassium persulfate, ammonium persulfate, and persulfate. Hydrogen oxide, benzoyl peroxide, t-butyl hydroperoxide, succinic acid hydroperoxide, cumene hydroperoxide, p-
Peroxides such as menthane hydroperoxide, di-tert-butyl peroxide, and tert-butylperbenzoic acid, or azobis-based initiators such as 2.2′-azobis(2-amidinopropane) hydrochloride, azobiscyclohexanecarbonitrile, etc. Preferred representative examples include ethylene diamine, diethylene triamine, triethylene chloride, etc., as necessary. Water-soluble amines such as tolamin, tetraethylenepentamine, pentaethylenehexamine, monoethanolamine, jetanolamine, triethanolamine, propylene diamine, diethylamine, monoethylamine, pyrosulfite, sodium bisulfite, sodium formaldehyde sulfoxylate, etc. can be used as an activator in combination with a polymerization catalyst, and organic halogen compounds, nitro compounds, alkyl mercaptans, diisopropyl xanthate, etc. can also be used as polymerization degree regulators.

The emulsion polymerization reaction according to the present invention is carried out by a known method by appropriately combining the above polymerizable monomer, catalyst, catalyst activator, polymerization degree regulator, etc. in the presence of a cationic emulsifying dispersant. It will be implemented without making any efforts.

Further, the mixing ratio of the cationic emulsifying dispersant and the polymerizable monomer may be any ratio, but it is 0.5 to 50% by weight to 99.5 to 50% by weight of the polymerizable monomer. It is preferable to use a cationic emulsifying dispersant of 2 to 98 to 70% by weight of the polymerizable monomer.
It is preferable to use a strong organic emulsifying dispersant of 30 to 30 wt.

The aqueous resin composition obtained in this way generally exhibits a positive charge in water, but preferably the ζ-potential (measurement conditions: ionic strength 10-3.p) l=7) is +5 to +5. The one with +80mv is good.

The aqueous resin composition used in the present invention may be used alone or in combinations of two or more in any proportion, but preferably the aqueous resin composition made of the above polymer accounts for the total weight of the aqueous resin composition. It is desirable that the content be 50% by weight or more.

The water-based polyurethane used in the present invention can be made water-based by introducing a group capable of forming a salt into the polyurethane or by imparting strong hydrophilicity to the hydroxy compound forming the polyurethane structure. When introducing a group capable of forming a salt, it may be introduced during the production of polyurethane or by grafting after production. . These methods are detailed below.

(1) When obtaining a polyurethane block from a compound having a hydroxyl group, a compound having an isocyanate group, and optionally a chain extender having an active hydrogen atom, at least one hydrogen atom reactive with an isocyanate group or an isocyanate group is added. and a compound having at least one salt-type or salt-forming group, in which case the compound has at least two hydrogen atoms capable of reacting with an isocyanate group, or has at least two isocyanate groups. (in the case of a compound containing hydroxyl groups, a compound containing isocyanate groups, and a chain extender, this compound can completely replace the compound containing hydroxyl groups, the compound containing isocyanate groups, and the chain extender constituting the polyurethane mass), the resulting polyurethane mass is then converted into salt form. and finally convert the polyurethane mass (which may dissolve in the organic layer depending on the physical properties of the mass) into an aqueous solution.

(2) When obtaining a polyurethane lump from a compound having a hydroxyl group, a compound having an isocyanate group, and optionally a chain extender having an active hydrogen atom, a diol having an unsaturated bond is used in combination, and the resulting polyurethane lump ( The polyurethane obtained is converted into an aqueous polyurethane by graft polymerization of a compound having an unsaturated bond and a salt-forming group (which may dissolve in the organic layer depending on the physical properties of the lump).

(3) After obtaining a polyurethane block from a polyhydroxyl compound such as polyethylene glycol in which the hydroxyl compound forming the polyurethane structure is aqueous, optionally a chain extender having an active hydrogen atom, and a compound having an isocyanate group. The resulting polyurethane mass (which may dissolve in the organic layer depending on the physical properties of the mass) is converted into an aqueous solution.

In methods (1) to (3) above, to convert the polyurethane mass into water-based one, the polyurethane lumps are dispersed in water, an aqueous solution containing an emulsifier, an acid aqueous solution, or an alkaline aqueous solution, or these water or aqueous solutions are It may be dispersed in a solution partially or entirely replaced with a water-soluble solvent.

Preferred compounds used in the above production methods (1) to (3) are illustrated below.

(I) Compound having a hydroxyl group Preferred compounds having a hydroxyl group are:
Mention may be made of polyethers, polyesters and polyesteramides, polyacetals and polythioethers.

(2) Examples of polyethers include polymerization products of tetrahydrofuran, propylene oxide and ethylene oxide, and copolymers or graft polymers of these compounds, such as addition products of alkylene oxide and polystyrene. For example, hexanediol,
By condensation of methylhexanediol, heptanediol, and octanediol, lower glycols 1 may be produced.
It is also possible to start from homogeneous or mixed polyethers, such as those obtained by adding 0 to 30%. Furthermore, propoxylated and ethoxylated (or mixed-alkoxylated) glycols and amines also come into consideration.

(2) Examples of polyesters and polyesteramides include those obtained by a known method from polyhydric alcohols and polycarboxylic acids, and optionally in combination with diamines and amino alcohols.

(2) As polyacecules, water-insoluble types, such as those of hexanediol and formaldehyde or of 4,4'-dioxyethoxy-diphenyl-dimethyl-methane and formaldehyde, are particularly suitable.

■ Examples of polythioethers include thiodiglycol alone or condensation products of thiodiglycol with other glycols, and the glycols must have a tertiary amino group (for example, dioxyethylaniline). Can be done.

(2) As other preferred hydroxyl compounds, it is also possible to start from polyhydroxyl compounds which already contain urethane or urea groups. Of course, mixtures of various polyhydroxyl compounds can also be used, for example hydrophilic polyethers (polyethylene glycols), polyesters and polyacetals mixed in certain proportions with hydrophobic polyhydroxyl compounds. Natural polyols such as castor oil, tar oil, and carbohydrates can also be used in combination. In addition, if necessary, glycols commonly used together with the above polyols, such as ethylene glycol, di- or triethylene glycol, butanediol, propanediol, 1
．． 6-hexanediol, neopentyl glycol, bisphenol A1 and bisphenol A ethylene oxide adducts, propylene oxide adducts, etc. are used in combination.

(II) Compounds having isocyanate groups As diisocyanates, all aliphatic and aromatic diisocyanates R1 such as 1°5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate,
, 4'-Schiff, enyl-dimethylmethane-diisocyanate, di- and tetraalkyl-diphenylmethane-diisocyanate, 4.4'-dibenzyl-diisocyanate, 1.3-dimethylmethane-diisocyanate, 1.4
-phenylene diisocyanate, xylylene diisocyanate, toluylene diisocyanate, chlorinated and brominated isocyanates, phosphorus-containing isocyanates,
Butane-1,4-diisocyanate, hexane-1,6
-diisocyanate, dicyclohexylmethane-diisocyanate, cyclohexane-1,4-diisocyanate. Partially or fully reacted with partially masked isocyanates, such as dimeric toluylene diisocyanate, and also with e.g. phenol, tertiary butanol, phthalimide, caprolactam, in particular with the possibility of forming self-reticulating polyurethanes. Polyisocyanates (which, if completely masked, do not initially take part in the reaction and are simply mixed) can be mentioned.

(III) As the chain extender having a reactive hydrogen atom, which is optionally used in combination, examples include commonly used glycols, such as ethylene glycol, di-, tri- and tetra-ethylene glycol, butanediol, propanediol-1, 2, propanediol-1,3, neopentyl glycol, dioxyethoxyhydroquinone,
Dioxyethyl diamine, further diamines such as ethylene diamine, hexamethylene diamine, hydrazine,
ammonia, benzidine, diaminodiphenylmethane,
These are amino alcohols and water.

polyethylene polyamine, polypropylene polyamine,
Various polyalkylene polyamines are also used, including polybutylene polyamines and the like. More specifically, nitrogen is
Polyamines which are linked by groups of the formula -CfiHz- which are larger integers, and where there are from 2 to about 8 such groups in the molecule. The nitrogen atom is a group -
C, H! , - are bonded to adjacent carbon atoms in, but not to the same carbon atom. Specifically, the use of polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine and dipropylenetriamine, as well as mixtures and various crude polyamine materials, is contemplated. Additionally, hydroxylalkyl-substituted polyamines may also be used in combination. Furthermore, when these polyamines are used, epichlorohydrin may be used in combination.

(IV) Compounds containing at least one hydrogen atom capable of reacting with an isocyanate group or at least one isocyanate group and at least one salt-forming group include the following compounds alone or in combination. Mixtures are considered (with the exception that in the case of compounds with few (both 2) hydrogen atoms capable of reacting with isocyanate groups or with at least 2 isocyanate groups, the hydroxy compounds constituting the polyurethane mass, isocyanate and chain extenders).

■ Compounds with basic tertiary amino groups that can be neutralized with aqueous acids or quaternized (a) Alcohols, especially alkoxylated aliphatic, cycloaliphatic, aromatic and heterocyclic groups; amines such as N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-dibutylethanolamine, 1-dimethylaminepropanol(2), N,N
-Methyl-β-hydroxyethyl-aniline, N,N-
Methyl-β-hydroxypropyl-aniline, N,N-
Ethyl-β-hydroxyethyl-aniline, N,N-butyl-β-hydroxyethylaniline, N-oxyethylpiperidine, N-oxyethylmorpholine, α-hydroxyethylpyridine, γ-hydroxyethylxyline (b) Diol and triols, especially alkoxylated aliphatic, cycloaliphatic, aromatic and heterocyclic primary amines, such as N
-Methyl-jetanolamine, N-butyl-jetanolamine, N-oleyl-jetanolamine, N-
Cyclohexyl-jetanolamine, N-methyl-diisopropanolamine, N-cyclohexyl-diisopropanolamine, N,N-dioxyethylaniline, N,N-dioxyethyl-m-toluidine, N,N
-dioxyethyl-p-toluidine, N,N-dioxypropyl-naphthylamine, N,N-tetraoxyethyl-α-aminopyridine, dioxyethylpiperazine,
Polyethoxylated butyl-jetanolamine, polypropoxylated methyljetanolamine (molecules 11100
0), polypropoxylated methyljetanolamine (molecule 12000), polyester with tertiary amino group, tri(2-hydroxypropyl-(1)-)
-amine, N-N-di-n-(2,3-dihydroxypropyl)-aniline, N, N'-dimethyl-N, N
'-bis-oxyethylhydrazine, N, N'-dimethyl-N, N'-bis-oxypropyl-ethylenediamine (C) Amino alcohols, e.g. obtained by hydrogenation, alkylene oxides and acrylonitrile and primary amines. addition products with N-methyl-N-(3-aminopropyl)-ethanolamine, N-cyclohexyl-N
-(3-aminopropyl)-propanol-(2)-amine, N,N-bis-(3-aminopropyl)-ethanolamine, N-3-aminopropyl-jetanolaminetd) Amines such as N, N-dimethylhydrazine, N.

N-dimethyl-ethylenediamine, 1-cynythylamino-4-amino-pentane, α-aminopyridine, 3-
Amino-N-ethylcarbazole, N,N-dimethyl-
Propylene-diamine, N-aminopropyl-piperidine, N-aminopropyl-morpholine, N-aminopropyl-ethyleneimine, 1,3-bis-piperidino-
2-amino-propane) diamines, triamines, amides, especially compounds obtained by hydrogenation of addition products of acrylonitrile with primary and di-secondary amines, such as bis-(3-aminopropyl) -Methylamine, bis-(3-
aminopropyl)-cyclohexylamine, bis-(3
-aminopropyl)-aniline, bis-3-aminopropyl)-toluidine, diaminocarbazole, bis-
(Aminopropooxyethyl)-butylamine, tris-(aminopropyl)-amine, N,N'-bis-carbonamidopropyl-hexamethylenediamine, and compounds obtained by addition of acrylamide with diamines and diols■ Compounds containing halogen atoms or corresponding esters of strong acids capable of quaternization reaction; 2-chloroethanol, 2-7'rommethanol, 4-
Chlorobutanol, 3-bromopropatol, β-chloroethylamine, 6-chlorohexylamine, ethanolamine-sulfuric ester, N,N-bis-hydroxyethyl-N”-m-chloromethylphenyl-urine, N-hydroxy Ethyl-N l-chlorohexyl-urea, glycerin-amino-chloroethyl-urethane, chloroacetyl-ethylenediamine, bromo-acetyl-dipropylene triamine, trichloroacetyl-triethylenetetramine, glycerin-α-bromohydrin, polypropoxyl chlorinated glycerol-α-chlorohydrin, polyester with aliphatically bonded halogen, ll3
-dichloropropanol-2 Isocyanates i include the following; chlorohexyl isocyanate, m-chlorophenyl-
Isocyanate, p-chlorophenyl-isocyanate, bis-chloromethyl-diphenylmethane-diisocyanate, 2,4-diisocyanate-benzyl chloride, 2,6-dicyanatepenzyl chloride,
N-(4-methyl-3-isocyanatophenyl)-β
- Bromoethyl urethane■ Compounds having a carboxylic acid group or hydroxyl group capable of forming salts; (a) Hydroxy- and mercapto-carboxylate salts; Glycols, triglycols, lactic acid, trichlorolactic acid, malic acid, dioxymalein acid,
Dioxymaleic acid, tartaric acid, dioxytartaric acid, mucilage acid, sugar acid, citric acid, glycerin-boric acid, pentaerythritol-boric acid, mannitoboric acid, salicylic acid, 2,6-dioxybenzoic acid, protocatechuic acid, α-resorcylic acid, β -Resorcilic acid, hydroquinone-2,5-dicarboxylic acid, 4-hydroxynaphthoic acid, 4.6-hydroxyisofucuric acid, oxyterefucuric acid, 5,6.7.8-tetrahydro-naphthol-(2)- Carboxylic acid-(3), 1-hydroxynaphthoic acid-(2), 2,8-dihydroxynaphthoic acid-(3), β-oxypropionic acid, m-oxybenzoic acid, pyrazoline-carboxylic acid, uric acid, barbituric acid ,
Resole and other formaldehyde-phenol condensation products (bl polycarboxylic acids; sulfonodiacetic acid, nitrile-triacetic acid, ethylenediamine-tetraacetic acid, diglycolic acid, thiodiglycolic acid, methylene-bis-thioglycolic acid, malonic acid, oxal Acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, gallic acid, phthalic acid, tetrachlorofucuric acid, isophthalic acid, terephthalic acid, naphthalenetetracarboxylic acid (1,4゜5.8), 〇 -Tolylimidodiacetic acid, β-naphthylimidodiacetic acid, pyridine-carboxylic acid, dithiodipropionic acid (C) Aminocarboxylic acids; oxaluric acid, anilideacetic acid, 2-hydroxy-carbazole-carboxylic acid-(3), glycine, sarcosine, Methionine, α-alanine, β-alanine, 6-aminocarboxylic acid, 6-penzoylamino-2-chloro-carboxylic acid, 4-amino-butyric acid, aspartic acid, glutamic acid, histidine, anthranilic acid,
2-ethylaminobenzoic acid, N-(2-carboxyphenyl)-aminoacetic acid, 2-(3'-amino-benzenesulfonyl-amino)-benzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, N-
Phenylamino-acetic acid, 3,4-diaminobenzoic acid, 5
-Aminobenzene-dicarboxylic acid, 5-(4'-aminobenzoyl-amino)-2-aminobenzoic acid (d) Hydroxy- and carboxy-sulfonic acids; 2-hydroxyethanesulfonic acid, phenolsulfonic acid- (2) , phenol sulfone! −
(3), phenolsulfonic acid-(4), phenoldisulfonic acid-(2゜4), sulfoacetic acid, m-sulfobenzoic acid, p-sulfobenzoic acid, benzoic acid-(1)-disulfonic acid-(3, 5)-2-chloro-benzoic acid-(1)-
Sulfonic acid (1), 2-hydroxybenzoic acid (1)
)-sulfonic acid-(5), naphthol-(1)-sulfonic acid, naphthol-(1)-disulfonic acid, 8-chloronaphthol-(1)-disulfonic acid, naphthol-(1)-disulfonic acid
)-)disulfonic acid, naphthol-(2)-sulfonic acid-(1), naphthol-(2)-)disulfonic acid, l.

7-hydroxynaphthalene sulfonic acid (3),
1.5-dihydroxynaphthalene disulfonic acid-(2,
4), chromotocopic acid, 2-hydroxynaphthoic acid-(3)-sulfonic acid-(6), 2-hydroxycarbazole-sulfonic acid-(7) (el aminosulfonic acids; amidosulfonic acid, hydroxyamine-monosulfonic acid, Hydrazine-disulfonic acid, sulfanilic acid, N-phenylamino-methanesulfonic acid, 4
．． 6-dichloroaniline-sulfonic acid-(2), -y
Enylenediamine-(1,3)-disulfonic acid-(
4,6), N-acetylnaphthylamine=(1)-sulfonic acid-(3), naphthylamine-(1)-sulfonic acid, naphthylamine-(2)-sulfonic acid, naphthylamine-disulfonic acid, naphthylamine-trisulfonic acid, 4,4'-di(p-aminobenzoyl-amino)-
Diphenylurea-disulfonic acid-(,3,3'), phenylhydrazine-disulfonic acid-(2,5), 2.3
-dimethyl-4-aminoazobenzene-disulfonic acid-
(4”, 5), 4”-aminostilbendisulfonic acid-
(2,2'')-4-azo-4>-anizole, carbazole-disulfonic acid-(2,7), taurine, methyltaurine, butyltaurine, 3-amino-benzoic acid-
(1)-Sulfonic acid-(5), 3-amizutornine-N-methane-sulfonic acid, 6-nitrilo-1,3-dimethylbenzene-4-sulfamic acid, 4,6-diatubenzene-disulfonic acid -(1,3), 2,4-diamino-toluene-sulfonic acid-(5), 4,4'-diamino-diphenyl-disulfonic acid-(2,2''), 2-
Aminephenol-sulfonic acid-(4), 4.4'-
Diamino-diphenyl ether sulfonic acid (2),
2-Amino-Ayuzole-N-methanesulfonic acid, 2-
Amino-diphenylamine-sulfonic acid (V) Main chain of diols having unsaturated bonds such as 1,2-polybutadiene diol, 1,4-polybutadiene diol, copolymer diol of propylene oxide and butadiene monoxide, etc. and carbon in the side chain
Diol with carbon unsaturated bonds.

(V[) Compounds with unsaturated bonds and groups capable of forming salts ■ Vinyl monomers used in the unsaturated carboxylic acid grafting reaction are α, β-unsaturated, such as acrylic acid, methacrylic acid, and maleic acid. It may be carboxylic acids, itaconic acid, sorbic acid, cinnamic acid, or a mixture of these unsaturated carboxylic acids and a vinyl monomer such as acrylic acid ester, methacrylic acid ester, or vinyl acetate.

Examples of vinyl monomers used for mixing include α- and β-monomers such as acrylic esters and methacrylic esters.
Unsaturated carboxylic acid esters are used. Particularly hydrophilic vinyl monomers include ethylene glycol monomethacrylate, ethylene glycol monoacrylate, diethylene glycol monomethacrylate, diethylene glycol monoacrylate, 2-hydroxypropyl monomethacrylate, 2-hydroxybrobyl monoacrylate, dipropylene glycol monomethacrylate, and diethylene glycol monomethacrylate. Also included are polyhydric alcohol monoesters of α,β-unsaturated carboxylic acids, such as propylene glycol monoacrylate, and monovinyl or monoallyl esters of organic oxycarboxylic acids, such as tartaric acid, pyruvic acid, malic acid, and other acids. Furthermore, unsaturated sulfuric acids, unsaturated phosphoric acids, unsaturated sulfonic acids are also considered.

■ Compounds 2-vinylpyridine, 4-vinylpyridine that have an unsaturated bond and at least one nitrogen atom; ■ Any halogen atom or corresponding strong acid ester group that also has an unsaturated bond and has a quaternization reaction. Compounds having one etc. are also considered.

(■) Aqueous polyhydroxy compounds■ Polyethylene glycol, ethylene oxide-propylene oxide block copolymer, diols such as ethylene glycol, polyethylene glycol, butanediol, propanediol, 1,6-hexanediol, neopentyl glycol, bisphenol Ethylene oxide adducts such as A, glycerin,
Ethylene oxide adducts of pentaerythritol, sorbitol, ethylene oxide adducts of mannitol, ethylene oxide adducts of dicarboxylic acids or tri- or tetra-carboxylic acids, ethylene oxide adducts of polyesters with terminal hydroxyl groups or carboxylic acid groups, etc. Compounds with hydrophilicity imparted by ethyl ether groups Compounds in which the polyhydroxyl compound itself contains a salt-forming group through copolymerization For example, terminal hydroxyl polyester compounds polymerized so that carboxyl groups remain, etc. I) When producing polyhydroxyl compounds of each group of -■, ■, ■, ■, unsaturated diols of group (V) are allowed to coexist, and later compounds of groups (VI)-■, ■, and 0 are grafted. Also included are polyhydroxyl compounds obtained by polymerization.

(■) Salt-forming agent ■ A salt-forming agent corresponding to the compounds of ■-■ group among the compounds containing a group having salt-forming ability used in production method (1),
Among the compounds containing an unsaturated bond and a group having salt-forming ability used in production method (2), the salt-forming agent corresponding to the compounds of the ■-■ group contains organic and inorganic acids and reactive halogen atoms. Compounds with and corresponding esters of strong acids are considered. Some examples include hydrochloric acid, nitric acid, hypophosphorous acid, amidosulfonic acid, hydroxylamine-monosulfonic acid, formic acid, acetic acid, glycolic acid, lactic acid, chloroacetic acid, bromoacetic acid ethyl ester, sorbitol-? 1ll
(1; Methyl chloride, butyl bromide, dimethyl sulfate, diethyl sulfate, benzyl chloride, p-toluenesulfonic acid methyl ester, methyl bromide, ethylene chlorohydrin, ethylene bromohydrin, glycerin-α-bromohydrin, chloroacetic ester , chloracetamide, bromoacetamide, dibromoethane, chlorobromobutane, sifurombutane, ethylene oxide, propylene oxide, 2.3
- Epoxypropanol.

■ For compounds of the ■ ■-■ group, the ■-■ group, organic and inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium bicarbonate,
Ammonia, primary, secondary and tertiary amines are suitable. Inorganic phosphorus compounds are also considered as salt-forming compounds, and basic phosphines which can be incorporated (e.g. diethyl-β-hydroxyethylphosphine, methyl-bis-β-hydroxyethylphosphine, methyl-bis-β-hydroxyethylphosphine,
tris-β-hydroxymethyl-phosphine) and e.g. phosphinic acid, phosphinic acid, derivatives of phosphinic acid and esters of phosphorous acid and phosphoric acid and thio homologues,
For example, bis-(α-hydroxy-isopropyl-β-phosphonic acid, hydroxyalkanephosphonic acid, phosphoric acid-bis-glycol esters are also considered.

2) The compounds of group 0 are quaternized or tertiaryized with tertiary amines and/or sulfides or phosphines. In this case, quaternary ammonium salts and phosphonium salts or tertiary sulfonium salts are formed.

For example, the following may be mentioned: trimethylamine, triethylamine, tributylamine, pyridine, triethanolamine and the compounds listed in group 1a and group 1b,
Furthermore, dimethyl sulfide, diethyl sulfide, thioglycol thiodiglycolic acid, trialkyl phosphine, alkylaryl phosphine, and triarylphosphine. Furthermore, when the polyhydroxyl compound used in the above production method (3) is selected from the group ■-■ Corresponding salt-forming agents of the above (■)-■, ■, and 0 groups can be used. When the polyhydroxyl compound (■)-0 group is used in production method (3), there is no need to use a salt forming agent.

The production of these polyurethane masses is carried out in a manner known per se in the presence or absence of solvents and does not cause any difficulties during the subsequent conversion in the aqueous phase. When choosing a solvent, it should be noted that the aqueous latex then formed should contain at most very small amounts of hydrophobic, especially flammable solvents, ie generally no more than 20% of the polyurethane mass. be. However, since the polyurethane latex is preferably completely free of solvents, the solvents added during the manufacturing process to facilitate processability should be easily removed from the water-containing layer by distillation. Benzene, acetate, acetone, methyl ethyl ketone are preferred solvents.However, also
Solvents that do not have a boiling point higher than water and do not have groups that react with isocyanates may also be used. however,
The latter limitation (no groups reacting with isocyanate) applies only if the solvent is added during the reaction, ie while free isocyanate groups are still present. For example, lower alcohols can be added to dilute the reaction mass after the reaction has been completed.

On the other hand, it is also possible to carry out the entire reaction in the molten state without solvent and to dissolve the rubbery mass obtained subsequently in a scratchy or non-polar and water-containing solvent.

The polyurethane mass obtained in this way is now not limited to being hydrophilic and can be simply dispersed in water using the usual methods in the chemistry of elastic and plastic polymers. Of course, it may be used for the purpose of producing the finishing composition of the present invention with or without a solvent.

However, if it is difficult to handle the polyurethane lump due to its physical properties, especially its viscosity properties, use water or a part or all of it in a water-soluble solvent so that the polyurethane lump becomes 20 to 50% by weight. It is preferable to use it by dispersing or dissolving it in the replaced aqueous solution.

At this time, in the case of a polyurethane block containing a group having salt-forming ability, it is preferable to simultaneously use a salt-forming agent as described above to convert it into a salt form.

These dispersion or dissolution is performed by a method known per se. For example, it is possible to simply dilute it in water, to use a strong stirring crab, to inject it into water through a nozzle, optionally using compressed air, or to apply ultrasonic waves.

In either case, it is possible to disperse or dissolve without adding an emulsifier; however, for example, oleyl alcohol polyglycol ether or oxyethylated phenols may be used to aid dispersion.

Of course, protective colloids such as casein decomposed with ammonia for anionic latexes and casein dispersed with acetic acid or lactic acid for cationic latexes,
Furthermore, it is possible to use gelatin, gum arabic, gum tragacanth, modified starch, fish glue, agar, rosin, polyvinyl alcohol.

Finally, it is also possible to add flocculants which act to chemically reticulate at room temperature or at relatively high temperatures after evaporation of the water.

Examples include sulfur-sols, formaldehyde and substances that give or react with formaldehyde, and masked isocyanates and peroxides. In this case, water-soluble reticulating agents such as formaldehyde, methylol compounds and their ethers are easily added to the latex, while hydrophobic masked isocyanates are dissolved in non-polar solvents that are immiscible with water. Preferably, it is emulsified in the form of a solution into a latex without the addition of emulsifiers. The hydrophobic latex particles then absorb the hydrophobic solvent together with the reticulating agent while expanding.

The aqueous polyurethane thus obtained is subjected to the preparation of the finishing composition of the present invention in the manner detailed above.

Among the above-mentioned water-based polyurethanes, particularly preferred are:
An aqueous polyurethane that does not contain a group having salt-forming ability and is itself aqueous, that is, the hydroxyl compound of manufacturing method (3) is (■)-■, or when it is in a salt form, its base It is an aqueous polyurethane containing a group having salt-forming ability such that it has the following structure.

Preferred base: In addition, when the finishing composition of the present invention is used for home use by housewives, it is preferable that the finishing composition adhered to clothing can be easily removed by normal washing, and as a water-based polyurethane. It is more preferable to have a molecular weight of 1,000 to 100,000, be mainly linear without branching, and not form a network later.

One type of aqueous polyurethane may be used in the present invention, but two or more types may be mixed in an appropriate ratio. The action of the aqueous polyurethane as described above not only improves phenomena such as unevenness and whitening of the aqueous resin composition, but also imparts elastic properties to the fibers, thereby imparting a desirable feel and shapeability to clothing.

The finishing composition of the present invention can be sufficiently effective with only the above-mentioned essential ingredients, but since the composition of the present invention is in the form of an aqueous emulsion, the purpose is to improve its mechanical or thermal stability. emulsifiers or dispersants such as polyoxyethylene alkyl ethers or polyoxyethylene sorbitan fatty acid esters, solvents such as ethylene glycol, propylene glycol, inorganic electrolytes such as sodium chloride, calcium chloride, ammonium chloride, and generally hydrotropic agents. A known wood structure destroying agent such as urea may also be added.

Of course, the positive charge of the aqueous resin also affects the final stability of the finishing composition, so a cationic surfactant or cationic polymer emulsifier such as those exemplified above may be added as a stability control agent. I don't mind.

Furthermore, silicone may be added to the finishing composition of the present invention for the purpose of improving iron slippage, and fragrances, dyes, pigments, and fluorescent brighteners may be added according to preference, and antibacterial Various preservatives, antibacterial agents, etc. may be added for the purpose of improving properties.

By using the finishing composition of the present invention, it has become possible for the first time to impart depth to the hue of dyed clothing without impairing its texture during washing machine processing or post-wash processing in general households.

The effect of the present invention is that it can add depth to the color of dyed fibers such as polyester fibers, cationically dyeable polyesters, polyamides, acrylics, triacetate, rayon, silk, and cotton, increase the clarity, and impair the texture. Therefore, it is not limited to the material, knitting method, or weaving method of clothing.

〔Example〕

EXAMPLES The present invention will be specifically described below with reference to Examples, but it goes without saying that the present invention is not limited to these Examples.

In addition, all parts and percentages in the examples are based on weight unless otherwise specified.

Example 1 of artificial synthesis of san 3.2 parts (solid content 2 5 parts of isobutyl methacrylate, 0.105 parts of menthane hydroperoxide, and radium formaldehyde sulfoxylate were added while stirring. Polymerization was initiated by adding 5 parts of an 81% aqueous solution in that order. Further, 15 parts of isobutyl methacrylate was added dropwise over 30 minutes, and after the monomer addition was completed, the mixture was aged at 50° C. for 2 hours to complete the polymerization.

Synthesis Example 2 8.6 parts (solid content: 3 parts) of nilauryltrimethylammonium chloride (manufactured by Kotamitsu 24 Kao ■) and 71.4 parts of water were placed in a 300-inch turning flask, and the mixture was heated without replacing the system with nitrogen. Polymerization was initiated by adding 5 parts of methyl methacrylate monomer at 60°C, followed by 0.15 parts of 2,2'-azobis(2-amidinopropane) hydrochloride, and then 30 parts of methyl methacrylate. After the monomer was added dropwise, the monomer was aged at 60° C. for 1 hour to complete the polymerization. A stable emulsion was obtained in which no polymer coagulation was observed during polymerization.

Synthesis Example 3 Cortamine D-86P (nidistearyldimethylammonium chloride manufactured by Kao) 6.7 parts (solid content: 5
500 Tn with a nitrogen introduction tube and a dropping funnel tube
! Add 233 parts of ion-exchanged water to a turning flask,
Next, the inside of the system was sufficiently purged with nitrogen, 10 parts of trifluoroisopropyl methacrylate was added, and the temperature was raised to 60°C. 2.2
0.105 parts of azobis(2-amidinopropane) hydrochloride was added, and after the start of polymerization, 90 parts of trifluoroisopropyl methacrylate was added dropwise over 1 hour. After the monomer addition was completed, the mixture was further aged at 60°C for 1 hour, and then cooled to room temperature. The coagulated material produced during the polymerization was filtered off through a 100-mesh wire gauze to obtain a stable emulsion completely free of unreacted monomer odor.

Synthesis Example 4 In the same manner as in Synthesis Example 1, Cortazine 86P Conc (Kao ■
Nistearyltrimethylammonium chloride) 1
1.9 parts (7.5 parts as solid content), 96 parts of isobutyl methacrylate, 3 parts of N-methylolacrylamide,
1 part of itaconic acid was added dropwise to 2,2゛-azobis(
0.15 part of 2-amidinopropane) hydrochloride,
Emulsion polymerization was carried out using 245.6 parts of ion-exchanged water to obtain a stable emulsion.

The following compounds were prepared as cationic polymer emulsifying dispersants and used in Synthesis Examples 5 to 7.

All were used as 20% aqueous solutions.

Polymerization of quaternary ammonium salt with methyl chloride of A dimethylaminopropyl methacrylamide (face=
800,000) B copolymer of glycolic acid neutralized product of dimethylamine ethyl methacrylate/sodium acrylate (6/1) (plate = 500,000) C = cationic modified cellulose - quaternary ammonium salt (flower - 1,000,000) Synthesis Example 5 10 parts (solid content: 2 parts) of polymer dispersant A were placed in a 300-inch turning flask equipped with a nitrogen introduction pipe, dropping funnel, etc.
Add 65 parts of ion-exchanged water and purify the system with nitrogen for 4 hours.
The temperature was raised to 5°C, and then 2 parts of isobutyl methacrylate and 0.10 parts of p-menthane hydroperoxide were added while stirring.
5 parts, radium formaldehyde sulfoxylate 81%
Polymerization was initiated by adding 5 parts of the aqueous solution in that order. Further, 15 parts of isobutyl methacrylate was added dropwise over 30 minutes, and after the monomer addition was completed, the mixture was aged at 50° C. for 2 hours to complete polymerization and obtain an emulsion.

Synthesis Example 6 In the same manner as in Synthesis Example 3, 30 parts of polymer dispersant C (6 parts as solid content) and 100 parts of trifluoroisopropyl methacrylate were added dropwise to 2゜2''-azobis(2-amidinopropane)hydro. Emulsion polymerization was performed using 0.105 parts of chloride and 233 parts of ion-exchanged water to obtain a stable emulsion.

Synthesis Example 7 In the same manner as in Synthesis Example 3, 850 parts of polymer dispersant (10 parts as solid content), 96 parts of isobutyl methacrylate, N-
2.2゛-azobis(2-amidinopropane) was obtained by sequentially adding 3 parts of methylol acrylamide and 1 part of itaconic acid.
0.15 parts of hydrochloride and 205 parts of ion-exchanged water
A stable emulsion was obtained by emulsion polymerization.

Synthesis example 8 of synthetic polyurethane Polytetramethylene ether glycol (hydroxyl value OH
V = 56, molecule 112000) After adding 27.7 parts of hexamethylene diisocyanate to 200 parts, 7
The mixture was stirred and reacted at 5° C. for 10 hours to obtain a urethane prepolymer block having isocyanate groups at the ends. Isocyanate M was analyzed and found to be 1.2%. Then N-
After adding 8.7 parts of methyljetanolamine, 75°C
The mixture was stirred for 5 hours to carry out a chain extension reaction, and a polyurethane block was obtained.

Next, 750 parts of a 0.74% hydroxyacetic acid aqueous solution is added with stirring, hydroxyacetic acid and water are added, and pH and concentration are adjusted. A homogeneous and stable aqueous polyurethane dispersion with a resin content of 25% is thus obtained.

Synthesis Example 9 Polybutylene adipate with terminal hydroxyl group (
molecular weight 2000) 200 parts methyl ethyl ketone 20
0 parts and then 31.0 parts of xylylene diisocyanate.
After adding 0 parts, the mixture was stirred and reacted at 75°C for 10 hours.
A urethane prepolymer solution having isocyanate groups at the ends is obtained. Next, 26.1 parts of N-stearyljetanolamine was added, and a chain extension reaction was carried out with stirring at 75° C. for 5 hours to obtain a polyurethane solution. Then 0.7
Add 750 parts of 4% hydroxyacetic acid with stirring, raise the temperature to 40-50°C, perform topping under reduced pressure, check the solvent in the system, then add a small amount of hydroxyacetic acid and water to reduce the resin content to 25%. % to obtain a homogeneous and stable aqueous polyurethane dispersion.

Synthesis Example 10 27.7 parts of hexamethylene diisocyanate is added to 200 parts of polytetramethylene ether glycol (OHV = 56, molecular weight 200) which can be dehydrated at 90°C and 50 mmHg for 1 hour, and the mixture is stirred and heated at 90°C for 2 hours. Then cool to room temperature and add tert-butanol 227.7
1 and diluted to obtain a urethane prepolymer solution having isocyanate groups at the ends.

The residual isocyanate groups in the obtained prepolymer solution were analyzed and found to be 1.2%.

Put 300 parts of tertiary-butanol and 3.46 parts of diethylenetriamine into another four-eye flask, and gradually add 200 parts of the above prepolymer solution while stirring while cooling from the outside and keeping the temperature below 25°C for 1 hour. and drop it, 5
The reaction was carried out at 0° C. for 30 minutes to obtain a polyurethaneurea polyamine solution. Next, add 4 parts of epichlorohydrin and heat at 50°C.
Heat and stir for 1 hour. Then after cooling to room temperature 0.68%
383 parts of acetic acid aqueous solution was added with stirring, and the temperature was increased to 40-5.
The temperature was raised to 0°C, topping was performed under reduced pressure, and after removing the solvent in the system, acetic acid and water were added to pHfiI! After cleaning and adjusting the concentration, an aqueous polyurethane with a solid content of 25% was obtained.

The compositions and physical property data of Synthesis Examples 1 to 7 are summarized in Table 1.

Table 1 Example 1 While stirring X part of ion-exchanged water at 25°C, add Y part of the aqueous resin composition shown in Synthesis Examples 1 and 5, and add 2 parts of the aqueous polyurethane shown in Synthesis Example 8 while continuing to stir. The aqueous dispersion was gradually added to obtain finishing compositions 1 to 7 having the compositions shown in Table 2.

Table 2 Clothing was treated using this finishing composition, and the deep color effect was measured, the texture was sensory tested, and the whitening was determined, and the results are shown in Table 3.

The processing method and evaluation method are shown below.

Evaluation> 1) Bathochromic effect The bathochromic effect was measured using a color machine (manufactured by Suga Test Instruments).
The L, a, and b values were determined. In the case of black and dark blue, the smaller the L value, the lower the brightness and the greater the depth. In the case of red, the MV mouth y, that is, the saturation is calculated from the a and b values, and the larger r is, the more vivid it is.

2) Texture Sensory Test The sensory test was conducted by a panel of 10 women, who judged the softness and squeaking when touched, and the feel of the product when worn, using the following criteria in a pairwise comparison.

3) Whitening The degree of whitening was evaluated with the naked eye on a three-level scale.

0 No whitening - 1 Slight whitening - 2 Whitening <Test clothing> 1. Polyester blouse (black) 10 pieces 1kg2,
Cotton blouses (navy blue) 4 pieces 1kg3, polyester polo shirts (red) 5 pieces 1kg 1 of these
~3 garment groups were subjected to treatment testing separately. Clothes were washed three times with a commercially available detergent before being tested.

Treatment test> A commercially available two-tank washing machine was heated with 3.5'DH water at 25°C for 30 minutes.
The finishing agent composition was added so that the solid content of the aqueous resin composition was 330 ppm, and after stirring for 1 minute, 1 kg of test clothing was added and stirred for 3 minutes, and then placed in a dehydration tank for 1 minute. After dehydration, air dry at 20℃, 65%RH
The samples were stored in a thermostatic chamber for 24 hours and subjected to evaluation.

All of the products of the present invention exhibit an excellent deep color effect, suppress staining and whitening phenomena, and can finish clothing with good texture.

Example 2 Finish compositions 8 to 1 shown in Table 4 were prepared in the same manner as in Example 1.
I got 8.

Using this finishing composition, polyester blouses (
The evaluation results are shown in Table 5. Processing method,
The evaluation method was the same as in Example 1. Further, Synthesis Example 11 of the aqueous resin composition used for Inventive Product 18 is shown below.

Synthesis Example 11 Add 8 parts of polyvinyl alcohol (completely saponified, degree of polymerization 1800) and 130 parts of ion-exchanged water to a 5-piece separable flask equipped with a thermometer, stirrer, reflux condenser, nitrogen introduction device, and quantitative dropping device. It was dissolved at 80°C. 40℃
Trimethylaminohydroxyethylated starch uII uJ Degree of cation substitution (average number of cationic groups introduced per unit of anhydroglucose) 0.5.1% aqueous solution viscosity 3
0.5 parts of distearyldimethylammonium chloride, 0.5 parts of distearyldimethylammonium chloride, and an aqueous sodium carbonate solution of 1 part of sodium carbonate and 10 parts of ion-exchanged water are added, and the air in the flask is replaced with nitrogen. Then acetic acid and nil monomer 1
0 part, 0.1 part of methacroxyethyltrimethylammonium chloride was added, 0.1 part of 2.2°-azobis(2-amidinobroban) hydrochloride and a polymerization initiator of 10 parts of ion-exchanged water were added, and the mixture was heated to 70°C. The temperature was raised to start polymerization.

90 parts of vinyl acetate monomer was continuously added over 100 minutes starting 10 minutes after the start of polymerization. After the continuous addition was completed, it was aged at 80°C for 1 hour to complete the emulsion polymerization reaction.
An aqueous resin composition containing a polymer having a temperature of g = 36°C and a refractive index of 1.4.67 was obtained.

Table 4 Table 5 All of the products of the present invention showed good effects.

Applicant's agent: Kaoru Furuya (Procedure signed by Kaoru Furuya) December 5, 1985 1. Indication of the case: Japanese Patent Application No. 167480/1983 2. Name of the invention: Finishing composition for clothing 3. Amended. Patent Applicant (091) Kao Co., Ltd. 4, Claims and Detailed Explanation of the Invention column 6 in the agent's specification, Contents of the amendment (1) Claims in the specification The range is shown in the attached sheet (for each correction)
Dispersion liquid" and correction (1) p. 2, line 1 to p. 7, line 3 "(A) Cationic...
・Corrected "Clothing Finish Composition" as follows: "(A) Polymerization of a monomer having a polymerizable unsaturated bond in the presence of a cationic polymer emulsifying dispersant and/or a cationic surfactant." An aqueous resin dispersion obtained by the above method, wherein the polymer constituting the aqueous resin dispersion has a glass transition temperature (Tg) in the range of 20 to 150°C, and the refractive index of the dry film is 1.50. A substantially aqueous emulsion comprising the following aqueous resin dispersion and (B) an aqueous polyurethane dispersion and/or a water-soluble polyurethane, the component (A) being 1 to 40% by weight as a solid content. , the solid weight ratio of component (B) to component (A) is 1/
200-4/1 "Poly" was corrected to "aqueous resin and poly" (1) "Composition in water" on page 8, lines 3, 6, and lines 11-12, respectively. delete.

(1) On page 8, lines 3 to 4, lines 7, and 10, and lines 6 to 5 from the bottom, “aqueous polyurethane” was corrected to “polyurethane”. (1) Line 7 from the bottom of page 8, and from the bottom 5th line “Composition”
(1) Delete "aqueous" in line 7 and line 9 from the bottom of page 9 (1) Delete "composition" in line 9 of page 9 (1) Delete "composition" in line 9 of page 9 Line 7 from the bottom to line 3 from the bottom "The composition means...two or more types of monomers" has been corrected as follows: "The dispersion means a cationic polymer emulsifying dispersant and/or a cationic polymer emulsifying dispersant and/or a cationic Monomer having an unsaturated bond that can be polymerized in the presence of a surfactant” (1) Delete “The present invention...selected” from the last line of page 9 to line 2 of page 10 (1) Same as above. Page 10, line 3, “Cationicity” is preceded by “Main development (
1) Corrected "compound" on page 22, line 6, to "dispersion.""Cationic emulsifying dispersant"
were respectively corrected to "cationic polymer emulsifier and/or cationic surfactant" (11 p. 25, line 1 "composition" deleted (1) p. 25 line 5 "composition" changed to "dispersion") Correction (1) "The fat composition is based on the weight of the total aqueous resin composition" on page 25, line 8 is corrected to "the fat is based on the weight of the total aqueous resin." (1) "Aqueous polyurethane" on page 25, line 10 was corrected to "polyurethane aqueous dispersion and/or water-soluble polyurethane." (1) Added "cationic" after "to urethane" on page 25, line 11. (1) "." on page 25, line 4 from the bottom. ``.'' (1)
Same page 55, line 7 “wo” corrected to “ga” full same 5
Page 6, line 4 “Aqueous polyurethane” was corrected to “Aqueous polyurethane dispersion and/or water-soluble polyurethane” (1) Page 56, lines 7, 11, 13 and the last line “Aqueous”
(1j Added "cationic" before "salt formation" on page 56, line 8 (11) Delete "aqueous" on page 57, lines 4 and 6, respectively (1) Delete "aqueous" on page 57, line 7 "composition" Corrected "composition" to "dispersion liquid" +11 Delete "composition" on page 59, line 10 (1) p. 6
"Composition" at the end of page 7 is corrected to "dispersion" (1) "Aqueous resin composition" in Table 2 on page 68 and Table 4 on page 75 is corrected to "aqueous resin dispersion" (page 11, page 68) "Aqueous polyurethane" in Table 2 and Table 4 on page 75 is corrected to "aqueous polyurethane dispersion or water-soluble polyurethane" (1) Line 6 from just below 71
Line 7 from the bottom, line 11 on page 73, and line 11 at the end of page 74, "composition" are respectively corrected to "dispersion" 2. Claim 1 (A) In the presence of cationic 1 hydrogen and/or cationic activity An aqueous resin composition obtained by polymerizing a monomer having an unsaturated bond that can be industrially polymerized, wherein the glass transition temperature (Tg) of the polymer constituting the aqueous resin composition is in the range of 20 to 150 ° C. and an aqueous resin composition whose dry film has a refractive index of 1.50 or less. %, a clothing finishing composition containing component (B) in a solid weight ratio of 1/200 to 4/1 to component (A).

The finishing composition according to claim 1, wherein the 2-eryurethane contains a group capable of forming a cationic salt.

The finishing composition according to claim 1, which is obtained from an aqueous polyhydroxy compound which does not contain any salt-forming groups.

1. The bottom of the 5th class of Emperor Hirohito.

Claims (1)

[Scope of Claims] 1(A) A monomer selected from the group consisting of a monomer having an unsaturated bond that can be polymerized in the presence of a cationic emulsifying dispersant, and a monomer having a polymerizable unsaturated bond and a crosslinking reactive group. An aqueous resin composition obtained by polymerizing one or more monomers, wherein the glass transition temperature (Tg) of the polymer constituting the aqueous resin composition is in the range of 20 to 150 ° C. A substantially aqueous emulsion containing an aqueous resin composition having a dry film having a refractive index of 1.50 or less and (B) an aqueous polyurethane, wherein the solid content of component (A) is 1 to 40. Weight %, solid content weight ratio of component (B) to component (A) 1/200 to 4/1
A clothing finishing composition containing: 2. The finishing composition according to claim 1, wherein the aqueous polyurethane contains a group capable of forming a cationic salt. 3. The aqueous polyurethane does not contain any salt-forming groups,
The finishing composition according to claim 1 or 2, which is obtained from a hydrophilic polyhydroxy compound exhibiting aqueous properties.