JPH09291486A - Darkening agent and darkening method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a color-deepening agent comprising the aqueous dispersion of a polymer obtained by copolymerizing an ethylenic unsaturated monomer mixture in the presence of a cationic surfactant and excellent in a color- deepening effect for fiber products and in abrasion resistance. SOLUTION: This color-deepening agent comprises an aqueous dispersion containing a polymer having a flexural index of <=1.5 and a silicone emulsion and/or an acidic phosphate ester. The polymer comprises a polymer obtained by copolymerizing an ethylenic unsaturated monomer mixture comprising methyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate, methylol acrylamide, etc., in the presence of a cationic surfactant such as cetyltrimethylammonium chloride in an amount of 0.1-0.5wt.% per that of the polymer, and has a glass transition point of 20-110 deg.C, the mixture of a polymer having a glass transition point of >110 deg.C with a polymer having a glass transition point of <20 deg.C in a weight ratio of 1/9 to 9/1, etc. A black-dyed polyester fabric is treated with the color-deepening agent and subsequently thermally treated to obtain the color-deepened fabric.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a darkening agent and a darkening method for a textile product. More specifically, it relates to a darkening agent which is excellent in scratch resistance and improves the depth of color of a dyed product.

[0002]

2. Description of the Related Art Conventionally, various proposals have been made as a coloring agent and a coloring method for a textile product. For example, a thin film layer of a fluorine-containing compound having a refractive index of 1.45 or less is formed on the surface of a fiber. (JP-A-55-26232), a glass transition point of 20 to 1 having a refractive index of 1.5 or less.
A method utilizing a cationic emulsion of a polymer at 10 ° C. (JP-A-62-289685) has been proposed.

[0003]

However, the former method of using a fluorine-containing compound has the drawback that the fluorine-containing compound is expensive and causes an increase in processing cost, and the cationic method having a specific glass transition point is used. The latter method using an emulsion has a limited darkening effect, and its use is limited.

An object of the present invention is to provide a darkening agent and a darkening method which are excellent in darkening effect for textile products.

[0005]

Means for Solving the Problems The inventors of the present invention have made extensive studies in view of the above-mentioned circumstances, and as a result, the above-mentioned problems are solved by an aqueous dispersion having a specific refractive index in which the ratio of the cationic surfactant to the polymer used is small. The inventors have found that they will be solved and have completed the present invention.

That is, the present invention provides a darkening of an aqueous dispersion of a polymer having a refractive index of 1.50 or less obtained by polymerizing an ethylenically unsaturated monomer mixture in the presence of a cationic surfactant. In the agent, the cationic surfactant is 0.1% by weight to 0.5% by weight based on the polymer, and relates to a darkening agent and a darkening method.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The cationic surfactant used in the present invention is not particularly limited, and any conventionally known one can be used. Examples of the cationic surfactant include alkyl quaternary ammonium salts.

[0008]

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The quaternary ammonium salt in which a part of the alkyl group is substituted with a monovalent organic group containing an ester bond or an amide bond.

[0010]

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Alkyl hydroxyethyl quaternary ammonium salt

[0012]

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Alkylbenzyl quaternary ammonium salt

[0014]

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An alkylpyridinium salt

[0016]

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An alkyl imidazolinium salt

[0018]

[Chemical 6]

Alkyl morpholinium salt

[0020]

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Primary amine salt

[0022]

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Secondary amine salt

[0024]

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Tertiary amine salt

[0026]

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And

[0028]

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[0029]

[0030]

[Chemical 12]

[0031]

[0032]

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Cationic group-containing ethylenic unsaturation such as
A monomer can be exemplified. In the above formula, R₁, R_Two,
R_Three, R_FourIs an alkyl group having 1 to 22 carbon atoms, R_FiveIs the carbon number
1 to 22 alkylene groups, X is Cl, Br, I, CH_Three
SO_Four, C_TwoH_FiveSO _Four, NO_Three, ClO_Four, HOCH_TwoCO
It represents a monovalent anionic group such as O.

Of course, a nonionic surfactant may be used in combination, if necessary, for the purpose of improving the stability of the aqueous dispersion. Examples of the nonionic surfactant include polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene polyoxypropylene block polymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene sorbitan fatty acid ester. Oxyethylene alkyl amine ether, fatty acid diethanol amide,
Examples thereof include sucrose ester, polyoxyethylene lanolin alcohol ether, polyoxyethylene lanolin fatty acid ester and the like.

The ratio of the cationic surfactant used in the present invention to the polymer is 0.
It is important to be 1% to 0.5% by weight. That is, when the ratio of the cationic surfactant to the polymer used is more than 0.5% by weight, the darkening effect is significantly reduced, and when it is less than 0.1% by weight, it is difficult to obtain a stable emulsion.

Specific examples of the ethylenically unsaturated monomer used in the present invention include the following formula CH ₂ = CHCOOCH ₂ CH ₂ C ₈ F ₁₇ CH ₂ = CHCOOCH ₂ C ₃ F ₇ CF ₃ (CF ₂ ) ₆ COOCH = CH ₂ CH ₂ = CHOCH ₂ C ₂ F ₅ fluorinated acrylic ester, fluorinated methacrylic ester, fluorinated vinyl ether or fluorinated vinyl ester, etc., methyl methacrylate, t-
Butyl methacrylate, i-butyl methacrylate, hexadecyl methacrylate, ethyl acrylate, i-
Butyl acrylate, α-β-unsaturated carboxylic acid ester such as 2-hydroxyethyl methacrylate, vinyl acetate, vinyl propionate, vinyl-2-ethylhexyl ether, vinyl hexyl ether, vinyl ester such as vinyl ethyl ether, vinyl ether compound Is mentioned. One or more monomers selected from these groups are used.

In addition to the above ethylenically unsaturated monomer, a crosslinkable ethylenically unsaturated monomer may be used. Examples of the crosslinkable ethylenically unsaturated monomer include N-methylol (meth) acrylamide, glycidyl (meth) acrylate, diacetone acrylamide, acetoacetoxyethyl acrylate, acetoacetoxyethyl methacrylate, acetoacetoxyethyl crotonate and acetoacetate. Acetoxypropyl acrylate, acetoacetoxypropyl methacrylate, acetoacetoxypropyl crotonate, 2-cyanoacetoacetoxyethyl methacrylate, N- (2-acetoacetoxyethyl) acrylamide, N- (2-acetoacetoxyethyl) methacrylamide, allyl acetoacetate,
Acetoacetyl group-containing ethylenically unsaturated monomer such as vinyl acetoacetate, blocked isocyanate group-containing ethylenically unsaturated monomer represented by the general formula (I)

[0038]

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[Wherein R ₃ is a hydrogen atom or a methyl group,
X is -OBO- (wherein B is an alkylene group having 2 to 10 carbon atoms which may be substituted with a halogen atom or an alkyl group) or -NH-, Y is an isocyanate residue of an aromatic diisocyanate, and Z is a ketoxime. Represents a hydrogen residue of] and the like.

The ratio (molar ratio) of the crosslinkable ethylenically unsaturated monomer and the ethylenically unsaturated monomer is 0.1 / 9.
9.9-10 / 90 is preferable. The polymer aqueous dispersion according to the present invention can be produced by a known and conventional method in the presence of a cationic surfactant. As a specific production method, for example, a method of dropping all or part of the ethylenically unsaturated monomer mixture into water containing a cationic surfactant and polymerizing the mixture with a polymerization initiation source, a cationic surfactant in advance. The method of dropping the monomer emulsion prepared by the method above into water and polymerizing the monomer emulsion with a polymerization initiation source can be used.

The polymerization initiation source is not particularly limited, but various polymerization initiators such as azo compounds and organic peroxides, and ionizing radiation such as ultraviolet rays or γ-rays may be used.

In order to obtain a stable aqueous dispersion free from flocs and precipitates, 2,2'-azobis (2-amidinopropane) dihydrochloride and 2,2'-azobis [2- () are used as polymerization initiation sources. It is preferable to use a water-soluble azo compound such as 2-imidazolin-2-yl) propane] dihydrochloride.

The aqueous dispersion of the polymer of the present invention must have a refractive index of 1.50 or less. The Tg of the polymer of the present invention is not particularly limited, but when it is alone, it is a polymer (A) having a Tg of 20 ° C to 110 ° C.
When two polymers are used together, Tg is 110 ° C.
A mixture of a polymer (B1) having a Tg of less than 20 ° C. and a polymer (B2) having a Tg of less than 20 ° C. is preferable.

It is important for darkening that the polymer has a specific refractive index and Tg. Particularly, by using two kinds of polymers having different Tg's, further abrasion resistance can be obtained for darkening. Therefore, the effect of increasing the sustainability of the dark color effect is achieved.

The refractive index of these polymers can be calculated and estimated by the following formula. <Refractive Index of Polymer> n = Σ [W (i) n (i)] In the formula, W (i) is the weight fraction of the monomer (i) of the polymer, and n
(I) shows the refractive index of the homopolymer of the monomer (i).

The glass transition point of the polymer can be measured by differential thermal analysis (DSC method). Polymer having a Tg of over 110 ° C (B1) and polymer having a Tg of less than 20 ° C (B2)
The use ratio of and is not particularly limited, but (B1) / (B2) = 1/9 to 9/1 is preferable in view of the darkening effect and scratch resistance.

The aqueous dispersion of the present invention preferably contains a silicone emulsion from the viewpoint of further improving scratch resistance. As the silicone emulsion, known and conventional ones can be used, for example, polydimethylsiloxane,

[0048]

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Amino-modified silicone,

[0050]

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[0051]

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Carboxy-modified silicone,

[0053]

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Carbinol-modified silicone,

[0055]

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Epoxy-modified silicone,

[0057]

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Polyether modified silicone

[0059]

[Chemical 21]

Emulsions such as can be used. Among these,
In particular, a silicone emulsion emulsified and dispersed with a nonionic surfactant is preferable in terms of enhancing scratch resistance without lowering the darkening effect. In this case, it is particularly preferable that the use ratio of the nonionic activator to the silicone resin is 15% by weight or less.

When a large amount of the silicone emulsion is used, the adhesion of dust becomes remarkable. Therefore, the ratio of the polymer (A) or the total amount of the polymer (B1) and the polymer (B2) to the total amount of the polymer (A A)] or [polymer (B
1) + polymer (B2)] / silicone (C) = 50/1
~ 1/1 is preferable.

From the viewpoint of further improving the degree of darkening level, it is preferable to further add an acidic phosphoric acid ester salt to the aqueous dispersion of the present invention. Examples of the acidic phosphoric acid ester salt include sodium salts and ammonium salts such as monomethyl phosphoric acid ester and monobutyl phosphoric acid ester. The amount of these acidic phosphoric acid ester salts to be used is [polymer (A) or the total amount of the polymer (A) or the polymer (B1) and the polymer (B2) in view of the stability of the aqueous dispersion. ] Or [polymer (B1) + polymer (B2)] / acidic phosphate ester salt (D) = 20/1 to 1/1 is preferable.

The darkening agent of the present invention obtained above can be applied to an object to be treated by any method depending on the type or adjusting form of the fiber structure to be treated. For example, a method may be employed in which dilution is carried out if necessary, and a heat treatment is carried out by attaching the material to the surface of the object to be processed by a known method of coating such as dip coating or spraying.

Examples of the fiber structure include not only polyester fibers, but also dyed fibers such as polyamide, acrylic, triacetate, rayon, silk, cotton and wool. By coating these fibers, it is possible to obtain an extremely deep dark color and a darkening effect having scratch resistance.

The conditions for the above-mentioned heat treatment are not particularly limited, and the usual heat treatment conditions, for example, after predrying in a heating oven at 80 to 120 ° C. for 30 seconds to 3 minutes, 13
Conditions for curing at 0 to 180 ° C. for 30 seconds to 3 minutes can be adopted.

[0066]

EXAMPLES Next, the present invention will be described in detail with reference to Examples and Comparative Examples. All parts and% are based on weight unless otherwise specified.

Example 1 Ion-exchanged water 220.0 was placed in a 500 ml four-necked flask equipped with a nitrogen introduction tube, a dropping funnel, a reflux condenser and a stirring device.
Part, cetyl trimethyl ammonium chloride 0.12
And 0.03 part of polyoxyethylene octyl phenyl ether (HLB = 12) were added, and the mixture was dissolved with stirring while substituting nitrogen in the system, then 16.5 parts of methyl methacrylate, 10.5 parts of i-butyl methacrylate, ethylene. 0.6 parts of dimethacrylate, 1.5 parts of 2-hydroxyethylmethacrylate and 0.9 parts of N-methylolacrylamide were added and the temperature was raised to 65 ° C. to obtain 2,2′-azobis (2-amidinopropane) dihydrochloride. Polymerization was initiated by the addition of 15 parts. Furthermore, methyl methacrylate 6
6.6 parts, i-butyl methacrylate 42.0 parts, ethylene dimethacrylate 2.4 parts, 2-hydroxyethyl methacrylate 6.0 parts, N-methylol acrylamide 3.6 parts, cetyl trimethyl ammonium chloride 0.48 parts, 0.12 parts of polyoxyethylene octyl phenyl ether (HLB = 12) and 1 ion-exchanged water
The monomer emulsion prepared from 30.0 parts was added dropwise over 2 hours. Upon completion of dropping the monomer emulsion, 0.15 parts of 2,2'-azobis (2-amidinopropane) dihydrochloride was added, and the mixture was aged for 2 hours to complete the polymerization, and a milky white stable solid content 30.0% emulsion (EM −
1) was obtained.

Next, 1000 parts of a treatment bath containing 4.0 parts of the polymer as a solid component was prepared. After padding this treatment bath with polyester satin black dyeing cloth, squeeze to 100%,
It was dried at 100 ° C. for 3 minutes and further cured at 170 ° C. for 1 minute. The obtained treated cloth was measured for lightness (hereinafter referred to as L value) with a dyeing fastness grade determination device [manufactured by Suga Test Instruments Co., Ltd.], and the degree of darkening was visually determined.

Copolymer composition, emulsifier used, Tg (DS
C method), the refractive index, the L value of the work cloth, and the visual evaluation results are summarized in Table 1. The smaller the L value, the lower the brightness and the darker the color.

[0070]

[Table 1]

Examples 2 to 5 and Comparative Examples 1 and 2 Emulsions (EM-2) to (EM-2) obtained by emulsion polymerization in the same manner as in Example 1 with the compounding compositions shown in Table 1.
The results of processing according to -7) are summarized in Table 1.

Example 6 In the same manner as in Example 1, the emulsion of Example 1 (E
M-1) was used to process a black polyester suede. Table 2 shows the results of measuring the L value of the treated cloth after processing and the L value after the treated cloths were rubbed 300 times under the condition of a load of 300 g using a Gakushin type friction fastness tester.

Examples 7 to 12 and Comparative Examples 3 and 4 In the same manner as in Example 6, the results obtained by using the polymer emulsion alone or in addition to the polymer emulsion and using the silicone emulsion and / or the acidic phosphate ester salt are summarized. It shows in Table 2.

[0074]

[Table 2]

[0075]

EFFECTS OF THE INVENTION According to the method of the present invention, it is possible to impart a deep coloration having scratch resistance to a textile product, and it is possible to improve the depth of color, which is effective for improving the texture of the textile product.

Claims (10)

[Claims] 1. A darkening agent comprising an aqueous dispersion of a polymer having a refractive index of 1.50 or less obtained by polymerizing an ethylenically unsaturated monomer mixture in the presence of a cationic surfactant. , The cationic surfactant is 0.
1% to 0.5% by weight of a darkening agent. 2. The polymer has a glass transition point (Tg) of 20 ° C.
The darkening agent according to claim 1, which is a polymer (A) at 110 ° C. 3. The polymer has a glass transition point (Tg) of 110.
The polymer (B1) having a temperature above 0 ° C and the glass transition point (Tg) are 2
The darkening agent according to claim 1, which is a mixture with the polymer (B2) having a temperature of less than 0 ° C. 4. The aqueous dispersion according to claim 1, further comprising a silicone emulsion (C) and / or an acidic phosphate ester salt (D).
The darkening agent according to the item. 5. The darkening agent according to claim 4, wherein the silicone emulsion (C) is water-dispersed with a nonionic surfactant in an amount of 1 to 15% by weight based on the silicone resin. 6. The weight ratio of the polymer (B1) to the polymer (B2) is 1/9 to 9/1.
The darkening agent described. 7. An aqueous dispersion of a polymer having a refractive index of 1.50 or less obtained by polymerizing an ethylenically unsaturated monomer mixture in the presence of a cationic surfactant is attached to a fiber structure. A method for darkening a fiber structure comprising heat treatment, wherein the ratio of the cationic surfactant to the polymer is 0.1% by weight to 0.5% by weight. . 8. The polymer has a glass transition point of 20 ° C. to 110 ° C.
Polymer (A) at ℃, glass transition point (Tg) is 11
The darkening method according to claim 7, which is a mixture of a polymer (B1) having a temperature of higher than 0 ° C and a polymer (B2) having a glass transition point (Tg) of lower than 20 ° C. 9. The method of darkening according to claim 7, wherein the aqueous dispersion further contains a silicone emulsion (C) and / or an acidic phosphoric acid ester salt (D). 10. The silicone emulsion (C) is water-dispersed with a nonionic surfactant in an amount of 1 to 15% by weight based on the silicone resin.
The darkening method described.