JPH10101989A - Shoe coating fluid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a coating fluid which can impart highly persistent stainproofing properties to shoes and is also excellent in heat, water and chemical resistances by mixing a self-cross-linking acrylic emulsion with a specified acrylic ester copolymer. SOLUTION: This fluid comprises a self-cross-linking acrylic emulsion containing an acrylic resin, desirably a copolymer of an acrylic ester with an methylol compound represented by formula I (wherein R1 and R2 are each H, a 1-6C alkyl or allyl; and R3 is H or a 1-8C alkyl) or a Mannich compound represented by formula II (wherein R4 and R5 are each H, an alkyl, an aralkyl or allyl; R6 and R7 are each a 1-5 C alkyl, a cycloalkyl, an aralkyl or a heterocyclic group) and a perfluoroalkylated acrylic ester copolymer, desirably a copolymer of a compound represented by formula III (wherein n is 1 or 2; and m is 6 or greater). The Mannich compound is prepared from formaldehyde, acrylamide, dimethylamine, diethylamine, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to silvered leather, suede,
The present invention relates to a shoe coating liquid used as a care and finishing agent for shoes using natural leather such as nubuck and buckskin for uppers.

[0002]

2. Description of the Related Art Generally, a shoe cream used for cleaning leather shoes is prepared by adding a surfactant to a solution of a wax and an organic solvent, stirring the solution, and adding a small amount of water to the solution. An acrylic synthetic resin emulsion or a blend of the above-mentioned wax emulsion with an acrylic synthetic resin emulsion is used as a wax emulsion or a finishing agent for leather shoes.

[0003]

However, the above-mentioned shoe cream or shoe finishing agent has a leather-retaining action and a polishing effect, but does not have an antifouling property when muddy water or oils adhere thereto. However, there is a disadvantage that the film strength of the shoe cream is weak and the adhesiveness is weak, and further, since the fastness is poor, there is also a problem of color transfer to clothes such as pants. An object of the present invention is to provide a shoe coating solution for imparting a highly persistent antifouling property which solves the problems of conventional shoe creams and shoe finishes at once.

[0004]

The shoe coating solution of the present invention is characterized in that it contains a self-crosslinking acrylic emulsion and a copolymer of an acrylic ester having a perfluoroalkyl group.

[0005] The shoe coating solution of the present invention comprises a self-crosslinking acrylic emulsion, a copolymer of an acrylic ester having a perfluoroalkyl group, a colorant, a glossy base,
And water.

The acrylic emulsion used in the present invention can be made three-dimensional by heating even when a reactive functional group is copolymerized without adding a thermosetting resin such as methylolmelamine. It is a self-crosslinking acrylic emulsion. When this type of acrylic emulsion is heated after forming a film, the functional groups react with each other to improve heat resistance, water resistance, chemical resistance, and elastic recovery. Optimum as a coating solution for

The self-crosslinking acrylic emulsion used in the present invention is a copolymer of an acrylic ester whose acrylic resin is composed of an acrylic ester and the following general formula 4
Or a copolymer with a Mannich compound represented by Chemical Formula 5.

Embedded image (Wherein R ₁ is H, an alkyl group or allyl group having 1 to 6 carbon atoms, R ₂ is H, an alkyl group or allyl group having 1 to 6 carbon atoms, R ₃ is H, Or 1
Represents an alkyl group having up to 8 carbon atoms)

Embedded image (Wherein R ₄ and R ₅ are H, an alkyl group or an aralkyl group or an allyl group, R ₆ and R ₇ are an alkyl group having 1 to 5 carbon atoms, or a cycloalkyl group,
Represents a member of an aralkyl group or a heterocyclic ring)

The methylol compounds used as copolymers characterized above include, for example, methylol methyl ether, methylol butyl ether and methylol allyl ether of acrylamide or methacrylamide,
Further, there are methylol methyl ether, methylol butyl ether and methylol allyl ether of acryl- or methacryl-N-methylamide.

As the Mannich base corresponding to the above formula,
For example, a-formaldehyde and b-acryl- or methacrylamide or acryl- or methacryl-N-
Methylamide and c-dimethylamine, diethylamine,
Mannich bases consisting of amines such as dibutylamine, morpholine or piperidine.

When an emulsion obtained by copolymerizing an acrylic acid ester and the above-mentioned methylol compound or Mannich compound is applied to leather, the surface coating layer shows excellent bonding with the leather substrate, and its surface is not tacky. When the surface coating layer is further heated, and the coating layer is exposed to a high temperature of up to about 120 ° C., the effect of the weak acidity of the leather is also added, causing reticulation and cross-linking, heat resistance, water resistance, and chemical resistance. Etc. are improved.

The copolymer of an acrylic ester having a perfluoroalkyl group used in the shoe coating liquid of the present invention is a copolymer of a compound represented by the following general formula (6). I do.

Embedded image (In the formula, n is 1 or 2, and m is 6 or more.)

A fluorinated acrylic resin is used as the fluorine-based water repellent or oil repellent. An acrylic resin containing fluorine in the alcohol portion (side chain) of the ester is important for the fluorinated acrylic resin. In the above, an acrylic ester copolymer having a long-chain perfluoroalkyl group in the side chain of the acrylic ester is used. The mechanical strength of the fluorinated acrylic resin is determined by the structure of the main chain, and since the main chain is an acrylate ester, the fluorinated acrylic resin has high flexibility, low glass transition point, and flexibility.

The water repellency and oil repellency of the fluorinated acrylic resin are determined by the structure of the side chain, and the terminal is CF ₃ and has 6 carbon atoms.
The above-mentioned polymer containing a perfluoroalkyl group has a low critical surface tension rc of 10 to 12 dyn / cm, and repels not only water but also hydrocarbon oil. An acrylic acid ester having a perfluoroalkyl group is represented by the general formula (6), wherein (CH ₂ ) _n (CF ₂ ) _m F is CH ₂ C
_{7 F 15, CH 2 C 8} F 17, CH 2 C 6 F 13, C 2 H 4 C
₈ H ₁₇ or the like is selected.

The copolymer of acrylic acid ester having a perfluoroalkyl group used in the present invention is used in the form of an aqueous emulsion, and the water repellency and oil repellency are improved by heating after coating and drying. The heating condition is a temperature of 100 to 150 ° C. for about 1 to 3 minutes.

[0015] The content of the copolymer of the acrylic ester containing a perfluoroalkyl group is preferably 5 to 30 parts by weight based on 100 parts by weight of the solid content of the self-crosslinked acrylic emulsion. When the content of the copolymer of the acrylate ester containing a perfluoroalkyl group is less than 5 parts by weight, water repellency and oil repellency are insufficient, and when the content exceeds 60 parts by weight, water repellency and oil repellency are increased. Conversely, the strength of the coating film is reduced, and the adhesiveness and durability when used for the upper of leather shoes are reduced.

The glossy base used in the shoe coating composition of the present invention is a waxy substance or a mixture of a waxy substance and an oily substance. The waxy substance is selected from carnauba wax, microcrystalline wax, shellac wax, synthetic ester wax based on montan wax and paraffin wax.

The oily substance is selected from lanolin, spermaceti, liquid paraffin, olive oil, palm oil and tallow. The gloss base is used for imparting a moist gloss or a deep gloss when the shoe coating liquid of the present invention is applied to leather. The content is preferably 5 to 30 parts by weight with respect to 100 parts by weight of the solid content of the emulsion containing the acrylate copolymer. If the content of the brightener is less than 5, the glossiness is insufficient, and if it exceeds 30 parts by weight, the adhesion to the shoe as a film and the durability are reduced.

Colorants used in the shoe coating liquid of the present invention include dyes and pigments. Dyes are generally organic compounds that can be dissolved in water, oils, solvents and the like, and can be fixed on the surface of leather. Acid dyes, direct dyes, basic dyes, gold-containing dyes and diazotized dyes are used as dyes.

On the other hand, pigments are generally fine powders of white or colored inorganic and organic compounds which are insoluble in water, oils and solvents, and which do not adhere or coat the leather surface as it is, thus reducing the power of the binder. Borrow and disperse on the leather surface and attach and color. The role of the pigment as a leather finish is to first paint a mixture with binders to create a somewhat continuous colored film on the leather surface, thereby giving the desired color tone and It imparts the properties of moisture resistance, oil resistance, and chemical resistance, and gives the surface smoothness and luster by the effect of hiding power that makes it difficult to see the scratch on the surface of the leather. It is.

[0020]

【Example】

[Table 1]

The composition of * 1 is an aqueous emulsion composed of 40 parts by weight of a self-crosslinking acrylic resin, 10 parts by weight of a coloring agent, 70 parts by weight of water, and 10 parts by weight of other components. * 2 The composition is a self-crosslinked acrylic resin; 40
An aqueous emulsion consisting of 10 parts by weight, 10 parts by weight of water, 70 parts by weight of water, and other components; * 3 is a cationic aqueous emulsion containing 24% of a copolymer of ethyl perfluoroalkyl acrylate as an active ingredient.

Each compounding agent was prepared as shown in Table 1 and stirred with a homogenizer to obtain a coating solution for shoes. The content of the perfluoroalkylacrylic acid copolymer in this shoe coating solution was determined based on the solid content of the self-crosslinked acrylic resin emulsion.
It was 19.5% based on 00 parts by weight.

[0023]

[Comparative example]

[Table 2]

As a comparative example, a compounding agent shown in Table 2 was prepared, a surfactant was added to a solution obtained by mixing a molten wax and an organic solvent, and the mixture was stirred. / O type wax emulsion was obtained.

[0025]

[Comparison of performance between the coating solution of Example and Comparative Example] The coating solution for shoes of Example was applied to a leather sheet with silver by spraying, and dried and heated for 3 minutes with a home hair dryer so that the surface temperature would be around 130 ° C. did. Next, the W / O type wax emulsion of the comparative example was applied to the same silvered leather sheet with a sponge, and dried and heated with a household hair dryer so that the surface temperature was around 100 ° C. for 2 minutes.

From the leather sheet treated with the shoe coating liquid of the example and the leather sheet treated with the W / O type wax emulsion of the comparative example, samples of predetermined sizes were taken, and the water repellency test and the oil repellency were performed. Test and wet friction fastness test, and the results in Table 3 were obtained.

[0027]

[Table 3]

The water repellency test was carried out according to JIS-L-109.
According to 25-2 water repellency (spray test). The oil repellency test is based on the AATCC method 118 oil repellency test. The measurement of the wet friction fastness is based on a JIS-L-1849 wet friction fastness test 6.2 Gakushin type friction tester. The brush was rubbed 100 times with a load of 200 g using the moistened # 2004 gold brush as a brush. As can be seen from the above results, the shoes to which the coating solution for shoes of the present invention has been applied and subjected to heat treatment are excellent in water repellency and oil repellency, and are excellent in stain resistance without discoloration.

[0029]

The shoe coating liquid of the present invention contains a self-crosslinking acrylic emulsion and a copolymer of an acrylic ester having a perfluoroalkyl group, and is applied to leather by the action of the self-crosslinking acrylic emulsion. And
By heating after drying, the film is crosslinked and heat resistance, water resistance and chemical resistance are improved.

When an emulsion of a self-crosslinking acrylic emulsion copolymerized with an acrylate ester and a methylol compound or a Mannich compound is applied to leather, it exhibits excellent bonding with the leather substrate and forms a soft and strong shoe film. I do. Also, since it contains a copolymer of an acrylic ester having a perfluoroalkyl group, which is highly effective as a water repellent and an oil repellent, it exhibits excellent water repellency and oil repellency.

The shoe coating liquid of the present invention contains a self-crosslinking acrylic emulsion, an acrylic ester copolymer having a perfluoroacryl group, a colorant, a gloss base, and water. As a finishing agent, the glossing effect is large, and in addition to the above-described antifouling effect, the glossy base material can give a moist gloss and a deep gloss, thereby finishing a luxurious leather shoe.

Claims (7)

[Claims] 1. A shoe coating liquid comprising: a self-crosslinking acrylic emulsion; and a copolymer of an acrylic ester having a perfluoroalkyl group. 2. A shoe comprising a self-crosslinking acrylic emulsion, a copolymer of an acrylic ester having a perfluoroalkyl group, a colorant, a glossy base, and water. Coating liquid. 3. The acrylic resin contained in the self-crosslinking acrylic emulsion is a copolymer of an acrylate and a methylol compound represented by the following general formula 1 or a Mannich compound represented by the following chemical formula 2. The coating liquid for shoes according to claim 1 or 2, wherein: Embedded image (Wherein R ₁ is H, an alkyl group or allyl group having 1 to 6 carbon atoms, R ₂ is H, an alkyl group or allyl group having 1 to 6 carbon atoms, R ₃ is H, Or 1
Represents an alkyl group having up to 8 carbon atoms) (Wherein R ₄ and R ₅ are H, alkyl, aralkyl or allyl, R ₆ and R ₇ are alkyl having 1 to 5 carbon atoms, cycloalkyl, aralkyl or heteroalkyl) Represents a member of the ring) 4. The copolymer according to claim 1, wherein the copolymer of an acrylic ester having a perfluoroalkyl group is a copolymer of a compound represented by the following general formula (3). Coating solution for shoes. Embedded image (In the formula, n = 1 or 2, m is 6 or more) 5. The content of the copolymer of an acrylic ester containing a perfluoroalkyl group is 5 to 100 parts by weight of the solid content of the self-crosslinked acrylic emulsion.
The coating liquid for shoes according to claim 1 or 2, which is 30 parts by weight. 6. The glossy base material is a wax-like substance or
3. The shoe coating composition according to claim 2, which is a mixture of a waxy substance and an oily substance. 7. The content of the gloss base is 5 parts by weight based on 100 parts by weight of the solid content of the self-crosslinking acrylic emulsion.
3. The coating liquid for shoes according to claim 2, wherein the amount is from 30 to 30 parts by weight.