JP2000290884A - Hyperchromic agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a hyperchromic agent capable of obtaining a high hyperchromic effect, excellent color fastness to rubbing and whitening preventive property, comprising an aqueous dispersion containing a specific fine particle, a specific acrylic resin and a silicone compound. SOLUTION: This hyperchromic agent is composed of an aqueous dispersion containing (A) preferably 5-55 wt.% of positively charged metal oxide-type fine particles (preferably produced by covering a silica fine particle with alumina, especially an alumina-covered silica-based compound obtained by treating the silica fine uartiele with basic aluminum chloride), (B) preferably 5-80 wt.% or a cationic acrylic resin having <=1.50, preferably <=1.48 refractive index and <=110 deg.C, preferably <=50 deg.C, more preferably <=20 deg.C glass transition point and (C) preferably 15-85 wt.% of a silicone compound (e.g. dimethylpolysiloxane). Preferably, the hyperchromic agent is attached on a fiber structural material and heat-treated.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for darkening solid surfaces such as colored fibers.

[0002]

2. Description of the Related Art One of the major drawbacks of synthetic fibers, especially polyester fibers, is that the color of dyed articles is inferior in depth and sharpness as compared with natural fibers such as wool and silk. I have. For this reason, research has been continued to improve the sharpness and color depth of dyed products, and several reports have been made. For example, a method using a cationic emulsion having a specific zeta potential of a polymer having a refractive index of 1.5 or less and a glass transition point of 20 to 110 ° C. (JP-A-62-2)
No. 89685), a method of treating fibers with a coloring agent containing metal oxide type fine particles having a specific particle size (JP-A-9-256280).
No.), refractive index obtained by polymerizing an ethylenically unsaturated monomer mixture in the presence of a specific ratio of a cationic surfactant
A method using an aqueous dispersion of a polymer of 1.5 or less (see
No. 9-291486) has been proposed.

[0003] However, a deepening agent excellent in darkening effect and excellent in fastness to friction and anti-whitening property has not yet been found.

[0004]

SUMMARY OF THE INVENTION The present invention relates to a positively charged metal oxide type fine particle (component A), a cationic acrylic resin having a refractive index of 1.50 or lower and a glass transition point of 110 ° C. or lower (component B), and a silicone compound (component B). The present invention relates to a deepening agent comprising an aqueous dispersion containing the (C component), and a deepening method comprising applying the deepening agent to a fiber structure and heat-treating the fibrous structure.

[0005]

DETAILED DESCRIPTION OF THE INVENTION (Component A) The positively charged metal oxide type fine particles of the present invention include compounds such as alumina compounds, zirconia compounds, and silica compounds. Compounds are preferred. The presence of positively charged metal oxide fine particles can be easily confirmed by using electrophoresis using laser light. The particle size of the fine particles is 20 to
120 nm is preferred. This particle size is converted from the specific surface area by the BET method.

[0006] The silica fine particles which are silicon oxide are negatively charged, but the positively charged fine particles of the present invention can be obtained by treating the silica fine particles with basic aluminum chloride and / or zirconium oxychloride. Can,
In the present invention, an alumina coating treated with basic aluminum chloride is particularly preferred. A production method relating to alumina coating of silica fine particles is described in U.S. Pat. No. 3,0078,783.
Reference can be made to JP-A-26959. Further, aminated silica fine particles obtained by treating silica fine particles with an amino compound-based silane coupling agent such as γ-2-aminoethyl-propyltrimethoxysilane can also be used.

(B component) The cationic acrylic resin used in the present invention is prepared by mixing an acrylic acid monomer and, if necessary, a monomer copolymerizable therewith in the presence of a cationic surfactant. When it is composed of a polymer obtained by polymerization by a known method and is obtained as an aqueous dispersion after the reaction, it can be used as it is.

Examples of the cationic surfactant include quaternary ammonium salts, alkylpyridium salts, alkylimidazolinium salts, amine salts and the like. In particular, a quaternary ammonium salt of a mono-long chain alkyl type, a quaternary ammonium salt in which an ester bond or an amide bond is inserted into an alkyl group, and a quaternary ammonium salt such as an alkylhydroxyethyl quaternary ammonium salt are preferable. The ratio of the cationic surfactant to the polymerizable monomer is preferably 0.5 to 50 based on 100 parts by weight of the polymerizable monomer.
It is used in an amount of 5 parts by weight, more preferably 5 to 25 parts by weight.

The acrylic acid monomers include acrylic acid, methacrylic acid and derivatives thereof, such as acrylic acid ester, fluorinated acrylic acid ester, acrylamide, N-methylolacrylamide, N-methylolmethacrylamide and the like. . In particular, esters of acrylic acid or methacrylic acid such as butyl acrylate, methyl methacrylate and butyl methacrylate with an alcohol having 1 to 4 carbon atoms, N-methylol acrylamide and N
-Methylol methacrylamide is preferred.

[0010] The refractive index of the dried film of component B is 1.50 or less, preferably 1.48 or less, and the glass transition point (hereinafter referred to as Tg) is 110 ° C or less, preferably 50 ° C or less, more preferably 20 ° C or less. It is.

(Component C) Examples of the silicone compound include dimethylpolysiloxane, amino-modified silicone, carboxy-modified silicone, carbinol-modified silicone, epoxy-modified silicone, and polyether-modified silicone. Silicones are preferred and they are usually used in the form of an emulsion.

The amino-modified silicone has an amino group such as -R-NH ₂ or -RNHR'NH ₂ (where R and R 'represent a hydrocarbon group) at a part of the methyl group of dimethylpolysiloxane. It has been introduced and can be used as an oily substance or an emulsion. The emulsion may be prepared using a surfactant or may be self-emulsified. Examples of the surfactant used in the preparation of the emulsion include ethylene oxide condensates of higher alcohols, nonionic surfactants such as fatty acid monoglycerides, cationic surfactants such as alkylamine salts and quaternary ammonium salts, Anionic surfactants such as higher alcohol sulfates and alkylbenzene sulfonates are exemplified. Considering the surface potential of a colored solid such as a colored fiber structure, it is desirable to use an amino-modified silicone emulsified with a nonionic surfactant or a cationic surfactant. In particular, when a nonionic surfactant is used, a remarkably excellent effect can be obtained.

(Darkening agent)
5 to 55% by weight, especially 10 to 50% by weight,
80% by weight, especially 15-70% by weight, C component 15-85% by weight,
In particular, it is preferable to contain 20 to 70% by weight.

The deepening agent of the present invention is usually used as a diluted processing solution. In that case, the total solid content concentration in the processing solution (the sum of the A component, the B component, and the C component) is
It is preferably used in an amount of 0.01 to 5.0% by weight, particularly 0.1 to 2.0% by weight.

In addition to the above-mentioned components A to C, other water-soluble or emulsion-type resins can be added to the deepening agent of the present invention. The resin component of the water-soluble or emulsion-type resin used in the present invention includes vinyl acetate resin, melamine resin, glyoxal resin, epoxy resin, acrylic resin and the like. The water-soluble or emulsion type resin is incorporated in the deepening agent in an amount of 0.01 to 5.0% by weight (as a solid content), preferably 0.05 to 2.0% by weight.

Further, a hydroxycarboxylic acid and / or a salt thereof can be blended with the deep-coloring agent of the present invention, and excellent antistatic properties can be obtained in addition to the deep-color effect. Hydroxycarboxylic acids used in the present invention include gluconic acid, glycolic acid, lactic acid, butyric acid, malic acid, and the like, and counter ions include sodium, potassium, ethanolamines, and the like. The hydroxycarboxylic acid (salt) is present in the deepening agent in an amount of 0 to 2.0% by weight, preferably 0.1% by weight.
02 to 1.0% by weight.

The darkening method of the present invention uses the above-described deepening agent of the present invention, and is excellent in control of the amount of adsorption, in terms of equipment and workability, by the pad-dry-cure method or the immersion method. Preferably, the darkening agent is applied to the fibrous structure, followed by heat treatment. The temperature of the heat treatment is preferably from 110 to 200 ° C, particularly preferably from 130 to 170 ° C, from the viewpoint of the deep color effect. Further, the heat treatment time is preferably from 10 seconds to 5 minutes, particularly preferably from 0.5 to 2 minutes, from the viewpoint of the deep color effect. Thereby, a film having a high darkening effect is formed. The fiber structure in the present invention refers to dyed fibers such as polyester, nylon, acrylic, polyamide, diacetate, triacetate, wool, silk, cotton, and the like, which are woven, knitted, and thread-like.

The present invention can be applied not only to the treatment of the fiber surface, but also to the surface of the printed matter, the printed matter of the ink jet type ink,
It can be used for surface treatment of plastics, surface treatment of rubber molded products such as tires, hair coloring agents and the like. In particular, in the ink jet type color print, the ink penetrates into the paper surface, and the amount of ink on the surface is reduced, so that there is a problem that it is difficult to obtain a vivid color. However, the present invention solves this problem.

[0019]

In the examples, "%" and "parts" are% by weight and parts by weight unless otherwise specified.

<Component A> Aluminum-based fine particles I: Alumina sol aqueous solution prepared by using nitric acid as a stabilizer with alumina having a particle diameter of 30 nm. Solid content concentration is 20% in terms of Al ₂ O ₃ . Silica-based fine particles I: an aminated silica dispersion obtained by adding 20 g of silica fine powder having a particle diameter of 60 nm and 0.2 g of γ-2-aminoethyl-aminopropyltrimethoxysilane to 80 g of water and mixing. The effective content of this dispersion is 20% in terms of SiO ₂ .・ Silica-based fine particles II: 25 g of 50% basic aluminum chloride (Al ₂ (OH) ₅ Cl) aqueous solution and 355 g of water are added to 750 g of a 30% aqueous silica dispersion having a particle size of 150 nm, and the mixture is added at 80 ° C. for 60 minutes. Heating,
An aluminum-coated silica dispersion obtained by adjusting the pH to 5 to 6 with magnesium hydroxide after cooling. The effective component in this dispersion is 20% in terms of SiO ₂ . -Silica-based fine particles III: Obtained in the same manner as the silica-based fine particles II, except that the silica particle diameter was changed to 60 nm.

<Component B> Under nitrogen atmosphere, 6 parts of stearyltrimethylammonium chloride (manufactured by Kao Corporation: Coatamine 86W, solid content 28%) (1.7 parts of solid content), 263.6 parts of ion-exchanged water at 60 ° C. , Isobutyl methacrylate
4.4 parts, 15.2 parts of butyl acrylate and 0.4 part of N-methylolacrylamide were added, and 0.4 part of 2,2′-azobis (2-amidinopropane) dihydrochloride was added to initiate polymerization.
Further, 13.2 parts of isobutyl methacrylate, 45.6 parts of butyl acrylate, 1.2 parts of N-methylolacrylamide and 50 parts of ion-exchanged water were dropped in one hour, and aged at 60 ° C. for two hours.
An emulsion having a solid content of 20% (polymer 1) was obtained. Also,
Polymers 2 to 5 were synthesized in the same manner as for Polymer 1 using the monomers shown in Table 1.

[0022]

[Table 1]

MMA: methyl methacrylate IBMA: isobutyl methacrylate TBMA: t-butyl methacrylate BA: butyl acrylate N-MAM: N-methylolacrylamide Q-86W: cotamine 86W V-50: 2,2′-azobis ( 2-amidinopropane) dihydrochloride.

<C component> Silicone compounds (I) to (III) 30 parts of silicone represented by the following general formula (I), (II) or (III) is converted to a secondary alcohol ethylene having 12 to 14 carbon atoms. Using 5 parts of an oxide adduct (average number of moles = 9),
Silicone emulsion emulsified in 65 parts of water.

[0025]

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[0026]

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[0027]

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1. Dark color processing test Examples 1 to 14 and Comparative Examples 1 to 5 having the compositions shown in Tables 2 and 3
Darkening agent (solid content 20%) diluted with water and solid content 0.6%
Was prepared. A polyester black dyed cloth is immersed in this treatment solution at 20 ° C. for 5 seconds, then squeezed to 100%, and dried at 120 ° C.
For 3 minutes and cured at 170 ° C. for 1 minute. L value (brightness) was measured using the obtained treated cloth. The L value was measured using a spectrophotometer (CM-3700d manufactured by Minolta).
Table 4 shows the results. The smaller the value compared to the L value of the untreated cloth, the greater the dark color effect.

2. Friction fastness test In accordance with the test method based on JIS L0849, using a Gakushin type friction fastness tester, a dark-colored cloth (cloth treated in the above 1. and cloth immersed in water) A dry and wet dyeing fastness test was carried out on the rubbing. The test results were graded from 1st (bad) to 5th (good) using a gray scale. Table 4 shows the results. The intermediate grade between the two grades was a grade obtained by adding 0.5 to the number of the worse grades.

3. Whitening test A dark-colored cloth (cloth treated in 1. above) is mounted on both the sample holder and the friction plate of an appearance retention type tester (pilling tester manufactured by Toyo Seiki Seisaku-Sho, Ltd.) based on JIS L1076, and room temperature. Under a load condition of 730 g for 10 minutes
(850 rotations) Rub the dark-colored fabrics together. L value of the rubbed part of the test cloth attached to the sample holder side,
The L value of the test cloth before the whitening test was measured, and the degree of whitening was calculated as: degree of whitening = (L value of rubbed portion) − (L value before test)
Value). The larger the value, the lower the whitening resistance, and the closer to 0, the higher the whitening resistance. The whitening resistance was determined based on the following criteria from the obtained values. Table 4 shows the results. ◎: 0 to 0.10 ○: 0.11 to 0.19 △: 0.20 to 0.30 ×: 0.31 to 0.40

[0031]

[Table 2]

[0032]

[Table 3]

[0033]

[Table 4]

[0034]

According to the present invention, a high dark color effect can be obtained.
A darkening agent that provides excellent friction fastness and anti-whitening properties is obtained.

Continued on the front page F term (reference) 4H057 AA01 AA02 CA37 CA38 CB08 CB38 CB46 CB47 CB54 CC03 DA01 HA18 HA20 JA10 JB03 4L031 BA09 BA19 BA20 BA31 DA00

Claims (5)

[Claims] An aqueous dispersion containing positively charged metal oxide fine particles (component A), a cationic acrylic resin (component B) having a refractive index of 1.50 or less and a glass transition point of 110 ° C. or less, and a silicone compound (component C). A darkening agent consisting of the body. 2. The color-enhancing agent according to claim 1, wherein the positively charged metal oxide fine particles are silica-based compounds. 3. The deep-coloring agent according to claim 1, wherein the positively charged metal oxide fine particles are produced by coating silica fine particles with alumina. 4. Component A is 5 to 55% by weight and component B is 5 to 80% by weight.
The deepening agent according to any one of claims 1 to 3, comprising 15 to 85% by weight of a C component. 5. A darkening method comprising applying the deepening agent according to any one of claims 1 to 4 to a fibrous structure and heat-treating the fibrous structure.