CN113736358A - Antifouling high-glossiness bright-surface leather, preparation method thereof and fashionable women's shoes - Google Patents

Abstract

The application relates to the technical field of leather manufacturing, and particularly discloses antifouling high-glossiness bright-surface leather, a preparation method of the antifouling high-glossiness bright-surface leather and fashionable women's shoes. The antifouling high-glossiness shiny leather comprises base leather and an antifouling photocuring shiny surface treating agent, wherein the antifouling photocuring shiny surface treating agent is prepared from the following raw materials in parts by weight: 40-60 parts of polyurethane acrylic dispersion liquid, 20-30 parts of allyl silicone oil, 15-30 parts of hydroxyl acrylate monomer, 10-20 parts of hydroxyl fluorine-containing acrylic resin, 3-5 parts of nano glass powder, 3-5 parts of flatting agent, 0.1-0.5 part of photoinitiator, 0.1-0.3 part of ultraviolet absorbent and 1-2 parts of pigment. The antifouling photocuring bright surface treating agent is cured to form a film on the substrate leather, has better antifouling and wear-resisting properties, enables the leather to have mirror glossiness in vision, and has higher aesthetic value.

Description

Antifouling high-glossiness bright-surface leather, preparation method thereof and fashionable women's shoes

Technical Field

The application relates to the technical field of leather manufacturing, in particular to antifouling high-glossiness bright-surface leather and a preparation method thereof and fashionable women's shoes.

Background

The bright leather is a leather material with higher glossiness on the surface, and is commonly used in the fields of fashion shoes, bags and the like. The surface of the bright leather is provided with a layer of paint film with high reflectivity, so that the bright leather has a mirror surface gloss visual effect on a macroscopic scale.

The bright leather generally includes a base leather layer and a paint film layer attached to the base leather layer, the base leather layer is made of polyurethane leather, and the paint film layer is generally formed by curing a leather surface treating agent, such as: the patent with the application number of CN201210593330.7 discloses yellowing-resistant moisture-cured polyurethane mirror gloss oil and a preparation method thereof, wherein the yellowing-resistant moisture-cured polyurethane mirror gloss oil is prepared from 24-45 parts of polyether polyol, 18-40 parts of isocyanate, 2.9-10 parts of trihydroxy polyol, 3.3-5.5 parts of cellulose acetate butyrate, 0.02-0.06 part of antioxidant, 0.02-0.2 part of catalyst, 30-42 parts of solvent and 0.001-0.01 part of terminator, and the polyurethane mirror gloss oil has good glossiness after being cured into a film.

However, in the above related art, the antifouling property of the paint film formed by curing the polyurethane mirror gloss oil is poor, and the paint film contains a large amount of hydroxyl groups, so that part of the organic solvent is easy to permeate into the paint film, and the residual stains on the surface of the paint film are difficult to remove.

Disclosure of Invention

In order to improve the antifouling performance of the bright leather, the application provides antifouling high-glossiness bright leather and a preparation method thereof.

In a first aspect, the present application provides an antifouling high-gloss glossy leather, which adopts the following technical scheme:

the antifouling high-glossiness shiny leather comprises base leather and an antifouling photocuring shiny surface treating agent, wherein the antifouling photocuring shiny surface treating agent is prepared from the following raw materials in parts by weight: 40-60 parts of polyurethane acrylic dispersion liquid, 20-30 parts of allyl silicone oil, 15-30 parts of hydroxyl acrylate monomer, 10-20 parts of hydroxyl fluorine-containing acrylic resin, 3-5 parts of nano glass powder, 3-5 parts of flatting agent, 0.1-0.5 part of photoinitiator, 0.1-0.3 part of ultraviolet absorbent and 1-2 parts of pigment.

By adopting the technical scheme, the polyurethane acrylic acid dispersion liquid, the allyl silicone oil, the acrylic resin and the hydroxyl fluorine-containing acrylic resin are cured and crosslinked under the action of the photoinitiator and are firmly attached to the substrate leather (polyurethane leather) to form a paint film with mirror surface gloss visual effect, and the paint film has high gloss and better aesthetic value; meanwhile, the surface energy of a paint film is low, the hardness is moderate, and the paint film has better antifouling and wear-resisting properties; the polyurethane acrylic dispersion liquid soaks the substrate leather, so that the adhesion capacity of the allyl silicone oil, the hydroxyl acrylate monomer and the hydroxyl fluorine-containing acrylic resin on the substrate leather is improved, and meanwhile, the allyl silicone oil, the hydroxyl acrylate monomer and the hydroxyl fluorine-containing acrylic resin can be well compatible in the polyurethane acrylic dispersion liquid through the action of hydrogen bonds, so that the polyurethane acrylic dispersion liquid is firmly adhered to the substrate leather, and the adhesion durability of a paint film is improved;

the allyl silicone oil, the hydroxyl acrylate monomer and the hydroxyl fluorine-containing acrylic resin all contain double bonds, have better refractive index, and have synergistic effect in the aspect of improving the glossiness of a paint film by compounding the allyl silicone oil, the hydroxyl acrylate monomer and the hydroxyl fluorine-containing acrylic resin; the allyl silicone oil, the hydroxyl acrylate monomer and one end of the hydroxyl fluorine-containing acrylic resin with a C ═ C double bond participate in a photo-crosslinking reaction, and are linked on the base leather under the action of the polyurethane acrylic dispersion liquid, so that the crosslinking density of a paint film is high, the surface water contact angle is large, and the solvent is difficult to infiltrate the surface of the paint film; the other ends of the allyl silicone oil and the hydroxyl fluorine-containing acrylic resin are enriched on the surface of the coating, and are directionally arranged polymer brushes, so that the interaction force of the solvent on the surface of the paint film is reduced, and the paint film has antifouling performance;

fluorine atoms of the hydroxyl fluorine-containing acrylic resin can play a space shielding role on the siloxane chain segment, so that the structural stability of a paint film is good; the nano-glass powder has small granularity, can be fully dispersed in the antifouling photocuring bright surface treating agent, has a certain filling effect on pores on the surface of the substrate leather, reduces the surface roughness of the substrate leather and improves the glossiness of the bright surface leather, and has good wear resistance and high hardness, so that a paint film has moderate hardness and excellent wear resistance, and can be attached to the surface of the substrate leather for a long time even under the impact of external force;

the hydroxy acrylate monomer and the leveling agent can improve the workability of the antifouling photocuring bright surface treating agent, so that the antifouling photocuring bright surface treating agent has good flowing property, uniform paint film thickness and smooth surface; the ultraviolet absorbent absorbs ultraviolet rays to protect C ═ C double bonds in the antifouling photocuring bright surface treatment agent, so that the bright surface leather is not easy to yellow after being exposed outdoors for a long time and has high glossiness; in addition, the corresponding pigment can be selected according to the actual processing requirement to cover the ground color of the base leather.

In addition, the photoinitiator includes but is not limited to 2-hydroxy-methyl phenyl propane-1-ketone, 2,4, 6-trimethyl benzoyl diphenyl phosphorus oxide, 2-isopropyl thioxanthone and 4-isopropyl thioxanthone, and has better photoinitiation effect.

Preferably, the weight ratio of the allyl silicone oil to the hydroxyl acrylate monomer to the hydroxyl fluorine-containing acrylic resin is 25 (20-25) to 15-20.

By adopting the technical scheme, the gloss and the antifouling performance of the bright leather are better within the weight ratio range.

Preferably, the allyl silicone oil has a molecular weight of 550.

By adopting the technical scheme, on the premise of ensuring that the antifouling performance of the glossy leather is not reduced, the lower the molecular weight of the hydroxypropyl silicone oil is, the higher the content of C-C double bonds is, the lower the surface energy of a paint film is, and the higher the glossiness is.

Preferably, the fluorine content of the hydroxyl fluorine-containing acrylic resin is 14%.

Preferably, the leveling agent is polydimethylsiloxane and/or polyacrylate solution.

By adopting the technical scheme, the nano glass powder is fully dispersed in the antifouling photocuring bright surface treatment agent by the leveling agent, and the leveling agent can promote the antifouling photocuring bright surface treatment agent to form a uniform and smooth paint film on the surface of the substrate leather, so that the glossiness of the bright surface leather is improved; meanwhile, the leveling agent further reduces the surface energy of the antifouling photocuring bright surface treatment agent, so that the antifouling performance of the antifouling photocuring bright surface treatment agent is improved.

Preferably, the leveling agent is polydimethylsiloxane.

By adopting the technical scheme, the glass transition temperature of the polydimethylsiloxane is low, so that the polydimethylsiloxane chain segment can move flexibly at room temperature, the polydimethylsiloxane forms a polymer brush capable of creeping on the surface of the paint film, and when the paint film is impacted by the outside, the polydimethylsiloxane creeps, the damaged part heals automatically, and the wear resistance of the paint film is further improved.

Preferably, the ultraviolet absorbent is one or more of 2-hydroxy-4-methoxybenzophenone, tris (1,2,2,6, 6-pentamethylpiperidinyl) phosphite and 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole.

By adopting the technical scheme, the ultraviolet absorbent and the antifouling photocuring surface finishing agent have good compatibility and high light transmittance, and almost have no influence on the surface glossiness of a paint film.

Preferably, the raw materials also comprise an antioxidant, and the weight part of the antioxidant is 1-5.

By adopting the technical scheme, the antioxidant comprises but is not limited to the antioxidant 3032, and the antioxidant 3032 and the ultraviolet absorbent play a synergistic effect in the aspect of yellowing resistance.

In a second aspect, the present application provides a method for preparing an antifouling high-gloss glossy leather, which adopts the following technical scheme:

a preparation method of antifouling high-glossiness bright leather comprises the following steps:

s1, weighing the polyurethane acrylic acid dispersion liquid, the allyl silicone oil, the hydroxyl acrylate monomer, the hydroxyl fluorine-containing acrylic resin, the nano glass powder, the leveling agent, the photoinitiator, the ultraviolet absorbent and the pigment according to the formula ratio, and homogenizing and emulsifying to obtain the antifouling photocuring bright surface treating agent;

s2, molding: and (3) coating the antifouling photocuring bright surface treating agent on base leather, and curing by ultraviolet irradiation to obtain the antifouling high-glossiness bright surface leather.

The antifouling photocuring bright surface treating agent prepared by the technical scheme is quickly cured on the base leather to form a paint film, the paint film has low surface energy, large contact angle and difficult adhesion of a solvent, and polymer brushes are enriched on the surface of the paint film, so that the paint film has better antifouling and wear-resisting properties, and in addition, the paint film has higher aesthetic value and brings mirror glossiness due to vision.

The third aspect, the application provides a fashion woman's shoe, adopts following technical scheme:

the utility model provides a fashion woman's shoe, includes the sole, with sole fixed connection's vamp, the vamp is formed by the preparation of aforementioned antifouling high gloss finish leather.

Through adopting above-mentioned technical scheme, the woman's shoe vamp glossiness that makes is high, and is pleasing to the eye.

In summary, the present application has the following beneficial effects:

1. in the application, the polyurethane acrylic acid dispersion liquid, the allyl silicone oil, the acrylic resin and the hydroxyl fluorine-containing acrylic resin are cured and crosslinked under the action of the photoinitiator and are firmly attached to the substrate leather to form a paint film with mirror surface gloss visual effect, and the paint film has high gloss and better aesthetic value; meanwhile, the paint film has low surface energy, moderate hardness and better antifouling and wear-resisting properties.

2. The leveling agent is polydimethylsiloxane, the glass transition temperature of the polydimethylsiloxane is low, the polydimethylsiloxane chain segment can move flexibly at room temperature, the polydimethylsiloxane forms a polymer brush capable of creeping on the surface of a paint film, when the paint film is impacted by the outside, the polydimethylsiloxane creeps, the damaged part heals automatically, and the wear resistance of the paint film is further improved.

3. The anti-fouling high-gloss bright-surface leather further comprises an antioxidant, and the antioxidant 3032 and the ultraviolet absorbent play a synergistic effect in the aspect of anti-yellowing, so that the anti-fouling high-gloss bright-surface leather has lasting gloss.

Detailed Description

The raw material sources of the examples and comparative examples in this application are as follows:

polyurethane acrylic dispersion: the trade name is Neopac E-106, purchased from fast commerce, Inc. in Guangzhou city; allyl silicone oil:

model No. NJ-Y1155, molecular weight 550, purchased from sentencing and niu new materials gmbh;

model No. NJ-F6, molecular weight 1200, purchased from sentencing and niu new materials gmbh;

hydroxyl fluorine-containing acrylic resin:

HD-827, with a fluorine content of 9%, purchased from Shanghai trained New materials science and technology, Inc.;

the model is HD-8666, the fluorine content is 14 percent, and the fluorine is purchased from Shanghai Dynasty New Material science and technology Limited;

hydroxyl acrylate monomer: model HEA, purchased from Haekley chemical, Inc., Changzhou;

nano-glass powder, cat # T801, purchased from new materials science and technology ltd, guangdong, chen;

polydimethylsiloxane: viscosity 10cs, purchased from hangzhou zhuoli chemical;

polyacrylate solution: the trade name is BYK-390, and the product is purchased from great-industry Korea company of Taiyuan;

2-isopropyl thioxanthone: purchased from chemical reagents ltd, wuweng, guangdong;

2-hydroxy-4-methoxybenzophenone: purchased from Shanghai spectral vibration biology, Inc.;

pigment: brand K3540, purchased from basf;

antioxidant 3032: purchased from Guangzhou Zhi chemical Co., Ltd.

Examples

Example 1

An antifouling high-glossiness bright leather is prepared according to the following steps:

s1, preparation of antifouling photocurable polishing agent: weighing 4kg of polyurethane acrylic dispersion liquid Neopac E-106, 2kg of allyl silicone oil NJ-F6, 1.5kg of hydroxyl acrylate monomer, 1kg of hydroxyl fluorine-containing acrylic resin HD-827, 0.3kg of nano glass powder T801, 0.3kg of polyacrylate solution BYK-390, 0.01kg of 2-isopropyl thioxanthone, 0.01kg of 2-hydroxy-4-methoxy benzophenone and 0.1kg of pigment K3540, putting the raw materials into a homogenizer, and shearing at a high speed for 20min at a linear speed of 40m/s to obtain the antifouling photocuring bright surface treating agent;

s2, molding: and (3) coating the antifouling photocuring bright surface treatment agent on the polyurethane leather, controlling the coating thickness of the antifouling photocuring bright surface treatment agent to be 30 +/-10 mu m, and curing by an ultraviolet lamp illuminator after coating to obtain the antifouling high-glossiness bright surface leather.

Examples 2 to 8

An antifouling high gloss glossy leather is different from example 1 in the composition of the antifouling photocurable glossy surface treating agent, and the specific composition is shown in table 1 below.

TABLE 1 composition of antifouling photocuring gloss finish

Note that: the antioxidant 3032 is fed into the homogenizer together with the urethane acrylic dispersion and the like in step S1, and emulsified and dispersed.

Example 9

An antifouling high gloss glossy leather differs from example 8 in the molecular weight of the allylic silicone oil, and the allylic silicone oil used in example 9 is NJ-Y1155 in type and 550 in molecular weight.

Example 10

An antifouling high-gloss glossy leather is different from example 9 in the fluorine content of the hydroxyl fluorine-containing acrylic resin, and the hydroxyl fluorine-containing acrylic resin used in example 9 has a model number of HD-8666 and a fluorine content of 14%.

Example 11

An antifouling high-gloss glossy leather differs from example 10 in the type of leveling agent and is obtained by replacing polyacrylate solution BYK-390 with polydimethylsiloxane or the like.

Comparative example

Comparative examples 1 to 5

An antifouling high gloss glossy leather is different from example 1 in the composition of the antifouling photocurable glossy surface treatment agent, and the specific composition is shown in table 2 below.

TABLE 2 composition of antifouling photocuring gloss finish

Performance test

Detection method

And (3) performance detection:

1. gloss: the glossy leathers prepared in examples 1 to 11 and comparative examples 1 to 5 were examined using a gloss meter at an incident angle of 60 ° in GU;

2. antifouling performance: the glossy leathers obtained in examples 1 to 11 and comparative examples 1 to 5 were coated with a black water-based pen and a black oil-based pen, respectively, in an area of 1 cm. times.1 cm, and it was observed whether the stains were completely removed by wiping immediately and wiping after drying.

3. Solvent wiping resistance: repeatedly wiping the bright leather by using cotton cloth stained with acetone, and recording the wiping frequency of the exposed substrate leather;

4. wear resistance: wiping the bright leather for 1 time by using sand paper (simulating the external force abrasion of the bright leather), and observing whether marks are left; repeatedly using abrasive paper on the bright leather by using abrasive paper, and recording the wiping times of the exposed substrate leather;

5. anti-yellowing performance: and (5) continuously irradiating the ultraviolet lamp for 2000h and 3600h, and observing whether yellowing occurs or not.

The result of the detection

TABLE 3 measurement results of gloss and antifouling Properties

TABLE 4 test results of solvent-resistant wiping properties, abrasion resistance and yellowing resistance

Note that: the smaller the number of solvent-resistant wipes and the number of sandpaper wipes, the poorer the surface adhesion ability of the paint film, and the shorter the adhesion time.

Data analysis

Combining example 1 and comparative examples 1-3 with tables 3-4, it can be seen that the allyl silicone oil was not incorporated in comparative example 1, the hydroxy acrylate monomer was not incorporated in comparative example 2, and the hydroxy fluoroacrylic resin was not incorporated in comparative example 3; the glossiness of the comparative examples 1 to 3 is smaller than that of the example 1, and the combination of the three is proved to play a role in synergy in the aspect of improving the glossiness of a paint film;

meanwhile, the comparative examples 1 to 3 have poor removal effects on stains formed after the drying of the oil pen and the water pen, and marks are remained on the stains, while the stains formed after the drying of the oil pen and the water pen in the example 1 can be completely removed without marks, so that the combination of the three materials is proved to have a synergistic effect on the aspect of improving the antifouling performance.

Combining example 1 and comparative example 4 with tables 3 to 4, it can be seen that the gloss of comparative example 4 is reduced compared to example 1 without adding a leveling agent in comparative example 4, demonstrating that the leveling agent has an accelerating effect on the improvement of the gloss of the glossy leather.

It can be seen by combining example 1 and comparative example 5 and tables 3-4 that the nano-glass powder is not added in comparative example 5, the glossiness of comparative example 5 is reduced compared with example 1, and the nano-glass powder can improve the glossiness of the bright leather, and meanwhile, the abrasion resistance of the bright leather is detected by using sand paper, and the scratch is obvious after one-time wiping, so that the hardness improvement effect of the nano-glass powder on the bright leather is obvious, and the times of abrasion resistance of the bright leather and the times of solvent resistance friction are obviously improved.

It can be seen from the combination of examples 1-8 and tables 3-4 that the bright leather without antioxidant is yellow after 3600h of ultraviolet lamp irradiation, while the bright leather with antioxidant 3032 still maintains the original color after 3600h of ultraviolet lamp irradiation, which proves that the antioxidant and the ultraviolet absorber have synergistic effect in anti-yellowing.

Combining examples 10-11 and tables 3-4, it can be seen that example 11 uses polydimethylsiloxane as the leveling agent, sand paper is used for scraping example 11, no trace remains on example 11, and the polydimethylsiloxane chain segments are proved to be capable of moving flexibly, so that self-healing is carried out after the paint film is damaged.

The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.

Claims (10)

1. The antifouling high-glossiness shiny leather comprises base leather and an antifouling photocuring shiny surface treating agent, and is characterized in that the antifouling photocuring shiny surface treating agent is prepared from the following raw materials in parts by weight: 40-60 parts of polyurethane acrylic dispersion liquid, 20-30 parts of allyl silicone oil, 15-30 parts of hydroxyl acrylate monomer, 10-20 parts of hydroxyl fluorine-containing acrylic resin, 3-5 parts of nano glass powder, 3-5 parts of flatting agent, 0.1-0.5 part of photoinitiator, 0.1-0.3 part of ultraviolet absorbent and 1-2 parts of pigment.

2. The stain resistant high gloss glossy leather of claim 1, wherein: the weight ratio of the allyl silicone oil to the hydroxyl acrylate monomer to the hydroxyl fluorine-containing acrylic resin is 25 (20-25) to 15-20.

3. The stain resistant high gloss glossy leather of claim 1, wherein: the molecular weight of the allyl silicone oil is 550.

4. The stain resistant high gloss glossy leather of claim 1, wherein: the fluorine content of the hydroxyl fluorine-containing acrylic resin is 14 percent.

5. The stain resistant high gloss glossy leather of claim 1, wherein: the leveling agent is polydimethylsiloxane and/or polyacrylate solution.

6. The stain resistant high gloss glossy leather of claim 5, wherein: the leveling agent is polydimethylsiloxane.

7. The stain resistant high gloss glossy leather of claim 1, wherein: the ultraviolet absorbent is one or more of 2-hydroxy-4-methoxybenzophenone, tris (1,2,2,6, 6-pentamethylpiperidinyl) phosphite and 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole.

8. The stain resistant high gloss glossy leather of claim 1, wherein: the raw materials also comprise an antioxidant, and the weight part of the antioxidant is 1-5.

9. The method for preparing an antifouling high gloss glossy leather according to any one of claims 1 to 8, comprising the steps of:

s1, preparation of antifouling photocurable polishing agent: weighing the polyurethane acrylic acid dispersion liquid, the allyl silicone oil, the hydroxyl acrylate monomer, the hydroxyl fluorine-containing acrylic resin, the nano glass powder, the leveling agent, the photoinitiator, the ultraviolet absorbent and the pigment according to the formula ratio, and homogenizing and emulsifying to obtain the antifouling photocuring bright surface treating agent;

s2, molding: and (3) coating the antifouling photocuring bright surface treating agent on base leather, and curing by ultraviolet irradiation to obtain the antifouling high-glossiness bright surface leather.

10. A fashionable woman's shoe, comprising a sole and an upper fixedly connected with the sole, wherein the upper is made of the antifouling high-gloss glossy leather according to any one of claims 1 to 8.