JPH08134399A - Shoe coating liquid - Google Patents

Abstract

PURPOSE: To obtain a shoe coating liquid excellent in pigment dispersion stability, quick dryablllty, coatability, adhesiveness after coated and water resistance, capable of maintaining beautiful appearance for a long time after coated, thus suitable for coloring both natural and synthetic leather shoes, comprising an alcoholic solvent, coloring pigment and specific nitrogen-contg. copolymer. CONSTITUTION: This shoe coating liquid comprises (A) an alcoholic solvent such as methanol, ethanol or propanol (e.g. ethanol), (B) a coloring pigment such as titanium dioxide, carbon black, organic pigment or rake pigment (e.g. titanium dioxide), and (C) an N-methacryloylethyl N,N-dimethylammonium-α-N- methylcarboxybetaine-butyl methacrylate copolymer. The contents of the component B and C are e.g. 0.1-20wt.% and 0.1-30wt.% in the coating liquid, respectively. This shoe coating liquid is obtained, for example, by dissolving the component C in the component A followed by adding the component B to the resultant solution and then dispersing treatment of the system with e.g. a bead mill.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating liquid which is used for natural or artificial leather such as shoes and which is colored white or any color.

[0002]

2. Description of the Related Art Conventionally, when a shoe having a white color tone is particularly cared for, white and luster are imparted by coloring with a coating solution in which titanium oxide and waxes are dispersed in an aqueous solvent. In many cases, this coating solution is prepared by dispersing titanium oxide in a common water-soluble acrylic resin or the like and mixing an O / W type wax emulsion. However, this coating solution has a poor dispersion of titanium oxide, and the pigment easily aggregates and precipitates over time. Further, since an aqueous solvent is used, it takes a long time to dry at a time of low temperature or high humidity and lacks convenience.

[0003]

The object of the present invention is to use a dispersion resin which is quick-drying, has good pigment dispersibility, excellent adhesion, and water resistance, so that the pigment is stable for a long period of time when not in use. The object of the present invention is to provide a coating solution for shoes, which is maintained in good dispersion and keeps a beautiful gloss for a long time even after being applied on the shoes.

[0004]

Means for Solving the Problems As a result of intensive research on the above problems, the present inventors have found that N-methacryloylethyl N, N.dimethylammonium.alpha.-N-methylcarboxybetaine.butyl methacrylate copolymer is used. Due to
We succeeded in stably dispersing not only titanium oxide but also other coloring pigments in a low-grade alcoholic solvent, and completed the present invention.

It is essential to use N-methacryloylethyl N, N.dimethylammonium.alpha.-N-methylcarboxybetaine.butyl methacrylate copolymer in this shoe coating liquid, and even if it is used alone, it is dispersed. Although good results can be obtained in terms of adhesiveness and stickiness, it is also possible to use only the effect as a dispersant and to use it together with a urethane resin, a phenol resin, a ketone resin or the like to obtain stickiness. In this case, the amount of urethane resin, phenol resin, ketone resin, etc. added is 5% to 30%. If it is less than 5%, the effect of improving the stickiness and glossiness cannot be obtained, and if it exceeds 30%, the viscosity of the coating solution becomes high, so that the coatability is significantly impaired. Further, as long as the resin is soluble in alcohol and has water resistance, it does not impair the purpose of the present invention even if it is not a urethane resin, a phenol resin or a ketone resin.

N-methacryloylethyl N, N.dimethylammonium.α-N-methylcarboxybetaine.
The butyl methacrylate copolymer is effective as a dispersant from about 0.1% or more, though it depends on the kind of the disperse pigment and the required amount. Below this, a stable dispersion effect cannot be obtained, or the required amount of pigment cannot be dispersed.

N-methacryloylethyl N, N.dimethylammonium.α-N-methylcarboxybetaine
When a large amount of butyl methacrylate copolymer is added, the water resistance, glossiness, and sedimentation stability of the pigment are excellent, but
Since the stability with time as a coating liquid becomes slightly inferior, the coating film becomes too thick and easily peels off from the coating surface, the viscosity becomes high, and the coating property deteriorates. It is considered that 40% is the maximum addition amount.

N-methacryloylethyl N, N.dimethylammonium.α-N-methylcarboxybetaine.
Practically, the amount of the butyl methacrylate copolymer added is in the range of 0.1% to 30%. This is because even if titanium oxide having a high hiding power of 0.2 μm to 0.5 μm in diameter is used, the minimum compounding amount is about 0.1%, and the minimum resin compounding amount corresponding to it is 0.1%. . Titanium oxide can form a stable dispersion up to about 30%, but when a large amount of pigment is dispersed in a large amount of resin, the viscosity becomes high and the coatability deteriorates. Addition of more than 30% is not preferable because it may cause peeling and other adverse effects.

N-methacryloylethyl N, N.dimethylammonium.α-N-methylcarboxybetaine
The most preferable addition amount range of the butyl methacrylate copolymer is 0.1% to 18%. Although the fixability is insufficient with a low addition amount such as when using less than 1%, the dispersion stability of the pigment is good, and when used in combination with other resins and waxes, the same gloss and fixability as conventional products can be obtained. can get. Also, N-
Methacryloylethyl N, N ・ dimethylammonium ・
The α-N-methylcarboxybetaine / butyl methacrylate copolymer gives higher sticking properties than conventional products when added in an amount of 5% or more, but there is a difference in the amount of dispersed pigment, but it is applied when it exceeds 18% in general. The sex becomes worse.

As the main solvent of the shoe coating liquid of the present invention, methanol, ethanol, propanol and the like are preferable, but N-
Methacryloylethyl N, N ・ dimethylammonium ・
Any solvent may be used as long as it dissolves the α-N-methylcarboxybetaine / butyl methacrylate copolymer. However, since it is a coating liquid used for natural and artificial leather, a solvent that does not adversely affect them is preferable. Ethanol is the most preferable main solvent from the viewpoint of safety to human body and quick drying property.

Titanium oxide is mainly used as a coloring component, but carbon black, titanium black, zinc white, in order to make the color dull or to color it in any color by utilizing the hiding power of titanium oxide, Red iron oxide, chromium oxide,
Iron black, cobalt blue, alumina white, iron oxide yellow,
Viridian, zinc sulfide, lithopone, cadmium yellow,
Red, gadmium red, yellow lead, molybdate orange,
Inorganic pigments such as zinc chromate, strontium chromate, white carbon, ultramarine blue, lead white, navy blue, manganese violet, aluminum powder, brass powder, CI16185
, CI45430, CI16255, CI45410, CI45440
, CI45100, CI19140, CI15985, CI42053
, CI42090, CI73015, CI15850, CI15585
, CI15630, CI45170, CI15800, CI15880
, CI12120, CI45380, CI26100, CI73360
, CI17200, CI12085, CI45370, CI12075
, CI21110, CI15510, CI45425, CI45350
, CI47005, CI47000, CI21090, CI61570
, CI61565, CI59040, CI42095, CI73000
, CI42052, CI69825, CI42090, CI20170
, CI60725, CI45190, CI15865, CI26105
, CI16155, CI16150, CI14700, CI12140
, CI15620, CI11725, CI14600, CI12100
, CI11680, CI18950, CI10316, CI11380
, CI11390, CI13065, CI18820, CI10020
, CI42085, CI61520, CI74160, CI60730
, CI20470 and the like, lake pigments of acid dyes, fish scale foil, various mica titanium, pearl pigments such as sericite, mascopite, pearl oyster powder, abalone shell powder and Takase shell powder.

If desired, additives such as surfactants, fragrances, oils and fats, and hardly volatile hydrocarbons can be added to the shoe coating liquid of the present invention. Surfactants are expected to have favorable effects such as those acting on the interface between the leather and the coating film to increase the physical adhesive force, and those improving the water resistance at the interface between the coating film surface and air and water. The fragrance can be expected to have an effect of masking an unpleasant odor when applied, or conversely improving the usability. In addition, surfactants and fragrances which are hardly volatile, oils and fats and hard volatile hydrocarbons are N-methacryloylethyl N, N.dimethylammonium.α-N.
-Methylcarboxybetaine-butyl methacrylate copolymer and urethane resin, there are also useful as a plasticizer such as phenolic resin and ketone resin, brittleness of the coating film is suppressed when the plasticizer exerts an effect moderately, The coating film is flexible and has high adhesiveness and excellent durability.

The shoe coating liquid of the present invention is prepared by dissolving N-methacryloylethyl N, N.dimethylammonium.alpha.-N-methylcarboxybetaine.butyl methacrylate copolymer in ethanol or the like, and then adding a pigment or the like. , A ball mill, a bead mill, a sand mill, a roll mill, a kneader, a homogenizer, an ultrasonic disperser, etc. to perform a dispersion treatment to prepare a colored liquid, and further consider the performance as a coating liquid for shoes such as stickiness and resin and surfactant. Basically, fragrances and the like are added as needed, but there is no problem even if all the materials are mixed at once and dispersed. In addition, a pigment having good wettability with a solvent and weak secondary aggregation, a pigment which has been previously treated so as to be easily dispersed, or the like can provide a shoe coating solution having sufficient performance even by stirring.

[0014]

EXAMPLES Next, the present invention will be described in more detail with reference to examples.

The following coloring liquid and wax emulsion were prepared to prepare Examples and Comparative Examples. In the examples and comparative examples, the N-methacryloylethyl N, N.dimethylammonium.α-N-methylcarboxybetaine / butyl methacrylate copolymer is “Yukaformer AM75”.
Is a 30% or 40% ethanol solution supplied under the trade name of. (Coloring liquid 1) Ethanol 60% Yucaformer AM75 201 (40% ethanol solution; Mitsubishi Petrochemical product name) 20% Titanium oxide 20% or more was kneaded with a bead mill for 1 hour to obtain a coloring liquid 1. (Coloring liquid 2) Ethanol 39.95% Yucaformer AM75 202 (30% ethanol solution; Mitsubishi Petrochemical trade name) 30% Titanium oxide 30% Yellow iron oxide 0.05% Kneaded with a bead mill for 1 hour, Coloring liquid 2 was obtained. (Coloring liquid 3) Ethanol 70% Yukaformer AM75 204 (40% ethanol solution; Mitsubishi Petrochemical product name) 10% Titanium oxide 15% Red 204 (CI15585) 5% or more is kneaded with a bead mill for 1 hour and colored. Liquid 3 was obtained. (Coloring liquid 4) Ethanol 79.9% Yukaformer AM75 R205 (30% ethanol solution; Mitsubishi Yuka product name) 10% Titanium oxide 10% Yellow No. 5 Al lake (CI15985) 0.1% or more with a bead mill. The mixture was kneaded for 1 hour to obtain a colored liquid 4. (Coloring liquid 5) Water 60% Cybinol X951 · 299W (water-soluble urethane resin; product name of Saiden Chemical Co., Ltd.) 10% Titanium oxide 20% or more was kneaded with a bead mill for 1 hour to obtain a coloring liquid 5. (Coloring liquid 6) Water 49.95% Paraloid WR-748 (water-soluble acrylic resin; trade name of ROHM & HAAS company) 20% Titanium oxide 30% Yellow iron oxide 0.05% Kneading the above with a bead mill for 1 hour, and coloring liquid Got 6. (Coloring liquid 7) Water 70% Julimer AC10NP (sodium polyacrylate; trade name of Nippon Pure Chemicals Co., Ltd.) 10% Titanium oxide 15% Red No. 204 5% or more was kneaded with a bead mill for 1 hour to obtain a coloring liquid 7. (Coloring liquid 8) Water 79.9% Paraloid WR-748 10% Titanium oxide 10% Yellow No. 5 Al lake 0.1% The above components were kneaded with a bead mill for 1 hour to obtain a coloring liquid 8. (Wax emulsion 1) Hoechst wax LP (wax; Hoechst trade name) 20% triethanolamine 3.4% water (hot water) 76.6% Heat wax to 100 ° C and add triethanolamine while stirring. It was saponified and hot water was gradually added to obtain a wax emulsion 1. <Example formulation> (Example 1) Ethanol 63% Hirac 110H (ketone resin; Hitachi Chemical product name) 25% Coloring liquid 1 10% Timiron Supersilk (mica titanium: manufactured by Merck) 2% or more with a homogenizer for 1 hour. Stir to obtain Example 1. (Example 2) Ethanol 60% Hitanol 1501 (Alkylphenol resin; Hitachi Chemical trade name) 20% Coloring liquid 3 20% or more was stirred with a homogenizer for 1 hour to obtain Example 2. (Example 3) Ethanol 55% Yucaformer AM75 202 30% Coloring liquid 2 10% Shell pal H (natural pearl pigment; Kakuhachi scale foil trade name) 5% or more was stirred with a homogenizer for 1 hour, and Example 3 Got (Example 4) Methanol 75% Tamanor 510 (phenol resin; Arakawa Chemical Co., Ltd. trade name) 15% Coloring liquid 4 10% or more was stirred with a homogenizer for 1 hour to obtain Example 4. (Example 5) Ethanol 50% Yucaformer AM75 R205S (30% ethanol solution) 40% Titanium oxide 5% The above components were stirred for 1 hour with a homogenizer to obtain Example 5. (Example 6) Isopropanol 80% Yucaformer AM75 206 (30% ethanol solution) 5% Burnock 12-406 (urethane resin; Dainippon Ink and Chemicals, Inc. trade name) 5% Carbon black 10% or more with a homogenizer for 1 hour Stir to obtain Example 6. (Comparative Example 1) Water 63% Wax emulsion 125% Coloring liquid 5 10% Timiron Supersilk (mica titanium: made by Merck) 2% or more was stirred for 1 hour with a homogenizer to obtain Comparative Example 1. (Comparative Example 2) Water 60% Hoechst emulsion T-730 (66% wax emulsion; trade name of Hoechst Company) 5% Coloring liquid 620% or more was stirred for 1 hour with a homogenizer to obtain Comparative Example 2. (Comparative Example 3) Water 75% Wax emulsion 1 10% Coloring liquid 7 10% Shell pal H (natural pearl pigment; Kakuhachi scale foil product name) 5% or more was stirred with a homogenizer for 1 hour, and Comparative Example 3 Got (Comparative Example 4) Water 75%, wax emulsion 1 15%, coloring liquid 8 10% or more were stirred with a homogenizer for 1 hour to obtain Comparative Example 4. (Comparative Example 5) Water 80% Cybinol X591.299W 5% Hoechst emulsion T-730 10% Titanium oxide 5% The above components were stirred for 1 hour with a homogenizer to obtain Comparative Example 5. (Comparative Example 6) Water 60% Julimer AC10NP 20% Wax emulsion 1 10% Carbon black 10% The above components were stirred for 1 hour with a homogenizer to obtain Comparative Example 6.

The following tests were conducted using Examples 1-6 and Comparative Examples 1-6. Test 1--Redispersibility Test 1 (Settling Test) 100 mm of Examples 1 to 6 and Comparative Examples 1 to 6 were placed in a test tube with an inner diameter of 1 cm and a closed cap, and allowed to stand at room temperature for 1 month to give a precipitate and a supernatant. Measure the height of the interface. The higher the value, the more bulky the sediment and the better the redispersibility. Test 2--Redispersibility test 2 (actual use test over time) Examples 1 to 6 and Comparative Examples 1 to 6 were filled in the applicator of FIG. 1 and allowed to stand still for 1 month in an upward direction, and then vertically. About 20 cm,
After applying vibration for about 1 minute at a speed of about 1 Hz, write on a glass plate, compare the initial drawing line with the hue and density, and visually judge the difference. {○} ... Almost unchanged. {△} ・ ・ ・ Slight change in hue or density {×} ・ ・ ・ Extremely thin or unwritable. {-} ...
Test that cannot be written from the beginning 3--Adhesion test Examples 1 to 6 and Comparative Examples 1 to 6 were filled in the applicator of FIG. 1 and applied to the shoes of 20 monitors, and after 6 hours, changes in the coating film were observed. Examined. {○} ... Almost no change. {△} ... There is a change but there is a coating film remaining. {X} ... Almost no coating film remains. Test 4--Immediate Drying Test Examples 1 to 6 and Comparative Examples 1 to 6 were filled in the applicator of FIG. 1 and applied to 10 pairs of shoes, and the average time until drying was examined.

[Table 1]

As described above, the present invention has excellent quick-drying property, good dispersibility, good adhesion, and can be filled in a simple applicator, and thus has good applicability.

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[Procedure amendment]

[Submission date] March 7, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Brief description of the drawing

[Correction method] Added

[Correction content]

[Brief description of drawings]

FIG. 1 is a vertical cross-sectional view of a shoe applicator filled with a shoe coating liquid according to the present invention.

Claims (2)

[Claims] 1. A shoe coating liquid containing at least an alcoholic solvent, a color pigment, and an N-methacryloylethyl N, N.dimethylammonium.alpha.-N-methylcarboxybetaine.butyl methacrylate copolymer. 2. At least ethanol and 0.1% to 20.
% Of titanium oxide and 0.1-30% of N-methacryloylethyl N, N.dimethylammonium.alpha.-N-methylcarboxybetaine.butyl methacrylate copolymer.