阅读说明：本技术 一种原色鳄鱼皮表面的涂饰工艺 (Coating process for surface of primary color crocodile skin ) 是由 张晓玲 于 2021-08-05 设计创作，主要内容包括：本发明涉及皮革处理技术领域,具体地说是一种原色鳄鱼皮表面的涂饰工艺。一种原色鳄鱼皮表面的涂饰工艺,其特征在于包括如下步骤：S1,清洁；S2,封底、填充；S3,上色；S4,抛光；S5,效应；S6,二次抛光；S7,上光；S8,三次抛光。同现有技术相比,上色前对鳄鱼皮进行封底、填充,有利于后续材料的渗透和接着的连续性,最终保证染料的接着牢度。(The invention relates to the technical field of leather treatment, in particular to a coating process for the surface of primary-color crocodile skin. A coating process for the surface of crocodile skin with primary color is characterized by comprising the following steps: s1, cleaning; s2, sealing bottom and filling; s3, coloring; s4, polishing; s5, effect; s6, secondary polishing; s7, glazing; s8, three polishings. Compared with the prior art, carry out back cover, packing to crocodile skin before coloring, be favorable to the infiltration of follow-up material and the continuity that follows, finally guarantee the fastness of following of dyestuff.)

1. A coating process for the surface of crocodile skin with primary color is characterized by comprising the following steps:

s1, cleaning: cleaning the crocodile skin with the primary color, and cleaning grease on the surface of the crocodile skin with the primary color;

s2, bottom sealing and filling: carrying out bottom sealing on the crocodile skin with primary color and filling;

s3, coloring: uniformly coloring the crocodile skin with primary color;

s4, polishing: adjusting the rotating speed of the polishing machine to 800-1000 revolutions per minute, polishing the crocodile skin, and removing redundant floating wax on the crocodile skin;

s5, effect: forming an effect layer on the crocodile skin;

s6, secondary polishing: adjusting the rotating speed of the polishing machine to 800-1000 revolutions per minute, polishing the crocodile skin, and removing redundant floating wax on the crocodile skin;

s7, glazing: glazing the crocodile skin;

s8, three polishing: and adjusting the rotating speed of the polishing machine to be 1000-1200 rpm, and polishing the surface of the crocodile skin.

2. A process of coating a surface of a primary color crocodile skin according to claim 1, wherein: in step S5, the effect layer is formed by a line drawing or focus wiping method, which specifically includes: spraying dark line-drawing paint on the crocodile skin by using a line-drawing gun according to the original lines of the crocodile skin, and making a two-color effect layer on the surface of the crocodile skin; the coke wiping method specifically comprises the following steps: and (3) polishing the surface of the crocodile skin by a polishing machine to coat the deep-color water-based coloring agent on natural lines of the crocodile skin to deepen the color of the raised lines so as to achieve the deep and light double-color coke wiping effect and make a double-color effect layer.

3. A process of coating a surface of a primary color crocodile skin according to claim 1, wherein: in the step S2, an adhesion type filler is used for bottom sealing and filling, wherein the adhesion type filler comprises the following raw materials in parts by weight: 50-60 parts of water, 10-15 parts of aromatic polyurethane resin, 15-20 parts of acrylic resin, 15-20 parts of alcohol and 1-3 parts of penetrating agent, wherein the sum of the contents of all the components is 100 parts.

4. A process of coating a surface of a primary color crocodile skin according to claim 1, wherein: in the step S3, an aqueous coloring agent is used for coloring, and the aqueous coloring agent includes the following raw materials in parts by weight: 10-20 parts of water, 35-45 parts of first modified rice bran wax emulsion, 15-25 parts of modified polyurethane resin, 10-15 parts of alcohol ether solvent, 3-6 parts of auxiliary agent, 2-5 parts of thickening agent and 15-20 parts of metal complex dye water, wherein the sum of the contents of all the components is 100 parts, and the auxiliary agent is one or more of penetrating agent, hand feeling agent, mildew preventive and essence.

5. A process of coating a surface of a primary color crocodile skin according to claim 1, wherein: in the step S5, an effect layer is formed by using an aqueous effect agent, wherein the aqueous effect agent comprises the following raw materials in parts by weight: 10-20 parts of water, 35-45 parts of first modified rice bran wax emulsion, 15-25 parts of modified polyurethane resin, 10-15 parts of alcohol ether solvent, 3-6 parts of auxiliary agent, 10-15 parts of thickening agent and 15-20 parts of metal complex dye water, wherein the sum of the contents of all the components is 100 parts, and the auxiliary agent is one or more of a flatting agent, a hand feeling agent, a mildew preventive and essence.

6. A process of coating a surface of a primary color crocodile skin according to claim 1, wherein: in the step S1, a strong cleaning agent and an aqueous cleaning agent are respectively used for cleaning the raw cowhide, wherein the strong cleaning agent comprises the following raw materials in parts by weight: 50-60 parts of alcohol, 30-35 parts of acetone and 10-15 parts of ethylene glycol ethyl ether, wherein the sum of the contents of all the components is 100 parts; the water-based cleaning agent comprises the following raw materials in parts by weight: 55-65 parts of water, 3-6 parts of surfactant, 25-35 parts of water-soluble organic solvent, 3-8 parts of acrylic resin and 3-8 parts of metal complex dye water, wherein the sum of the contents of all the components is 100 parts.

7. A process of coating a surface of a primary color crocodile skin according to claim 1, wherein: in the steps S4 and S6, polishing treatment is carried out by using polishing wax blocks, wherein the polishing wax blocks comprise the following raw materials in parts by weight: 40-50 parts of palm wax, 25-35 parts of second modified rice bran wax, 1-3 parts of chlorinated paraffin, 25-30 parts of preformed metal complex dye wax agent and 1 part of essence, wherein the sum of the contents of all the components is 100 parts; in step S8, polishing is performed by using soft filling wax and polishing wax block, where the soft filling wax includes the following raw materials in parts by weight: 40-50 parts of oxidized paraffin, 20-30 parts of palm wax, 15-20 parts of kaolin, 3-5 parts of chlorinated paraffin and 15-20 parts of preformed metal complex dye wax agent, wherein the sum of the contents of all the components is 100 parts.

8. A process according to claim 7, wherein the crocodile skin surface finish comprises: the preformed metal complex dye wax agent comprises the following raw materials in parts by weight: 35-38 parts of metal complex dye powder, 40-50 parts of stearic acid and 20-25 parts of palm wax; the sum of the contents of all the components is 100 parts.

9. A process of coating a surface of a primary color crocodile skin according to claim 1, wherein: in step S7, high gloss wax water and polishing wax oil are respectively used for polishing, where the high gloss wax water includes the following raw materials in parts by weight: 12-20 parts of emulsion-shaped second modified rice bran wax, 25-35 parts of modified polyurethane resin emulsion, 35-45 parts of deionized water, 6-10 parts of alcohol ether solvent, 8-10 parts of metal complex dye water and 3-5 parts of auxiliary agent, wherein the sum of the contents of all the components is 100 parts; the polishing wax oil comprises the following raw materials in parts by weight: 48-55 parts of third modified rice bran wax emulsion, 5-10 parts of modified acrylic resin emulsion, 20-30 parts of deionized water, 10-15 parts of alcohol ether solvent, 8-10 parts of metal complex dye water and 3-5 parts of auxiliary agent, wherein the sum of the contents of all the components is 100 parts.

10. A process of painting a surface of crocodile skin in primary color according to claim 4, 5 or 9, wherein: the preparation method of the first modified rice bran wax emulsion, the second modified rice bran wax in the emulsion state and the third modified rice bran wax emulsion specifically comprises the following steps:

step A, adding concentrated sulfuric acid with the concentration of 75% into a first enamel reaction kettle, keeping the continuous heating state, adding rice bran wax into the first enamel reaction kettle, continuously heating the rice bran wax to 90-100 ℃ to melt the rice bran wax, slowly adding a hydrogen peroxide solution with the concentration of 35% under the stirring state, continuously stirring for 12-14 hours under the constant temperature condition of 90-100 ℃ to completely oxidize the rice bran wax, naturally cooling the rice bran wax, standing for 1 hour to separate the wax from water, and discharging the water at the lower layer;

step B, heating the enamel reaction kettle to 90-100 ℃, re-melting the oxidized rice bran wax on the upper layer into liquid, adding water under the stirring state, continuously stirring for 30-40 minutes, standing for 1-3 hours, separating the wax and the water, and discharging the water on the lower layer;

step C, repeating the step B for 3-5 times, wherein the upper layer is the high-acid-value synthetic wax, and the lower layer is water recycled;

step D, taking the high-acid-value synthetic wax and the methyl isopropyl ketone for mixing and dissolving, heating to a high-acid-value synthetic wax for completely dissolving, slowly cooling the mixed solution under continuous slow stirring to a constant temperature of 45-55 ℃, keeping the constant temperature for 30-40 minutes, and separating solid and liquid;

step E, carrying out vacuum distillation on the solid to obtain high-melting-point synthetic wax;

step F, carrying out vacuum distillation on the liquid to obtain synthetic wax with a low melting point, wherein the distilled liquid is methyl isopropyl ketone and is reserved for subsequent recycling;

step G, putting the low-melting-point synthetic wax and zinc oxide into a second enamel reaction kettle, heating to 150-160 ℃ to melt the low-melting-point synthetic wax, adding high-molecular polyethylene glycol, reacting for 5-8 hours, slowly cooling to normal temperature after the reaction is finished, and filtering to obtain a first modified rice bran wax emulsion;

step H, putting the high-melting-point synthetic wax and zinc oxide into a third enamel reaction kettle, heating to 150-160 ℃ to melt the high-melting-point synthetic wax, adding calcium oxide to react for 5-8 hours, and washing with water after the reaction is finished to obtain second modified rice bran wax;

step I, mixing and heating second modified rice bran wax, first modified rice bran wax emulsion and emulsifier to be melted at 110 ℃ at 100 ℃, slowly adding deionized water at 100 ℃ in a stirring state, stirring to be uniform milky white liquid, homogenizing for 30-60 minutes by using a homogenizer, and filtering to obtain emulsion-shaped second modified rice bran wax;

and step J, putting the high-melting-point synthetic wax and zinc oxide into a fourth enamel reaction kettle, heating to 150-160 ℃ to melt the high-melting-point synthetic wax, adding ethylene glycol to react for 5-8 hours, washing after the reaction is finished to obtain third modified rice bran wax, mixing and heating the third modified rice bran wax, the first modified rice bran wax emulsion and an emulsifier to 100-110 ℃ to melt, slowly adding 100 ℃ deionized water under a stirring state, stirring to obtain uniform milky liquid, homogenizing for 30-60 minutes by using a homogenizer, and filtering to obtain third modified rice bran wax emulsion.

Technical Field

The invention relates to the technical field of leather treatment, in particular to a coating process for the surface of primary-color crocodile skin.

Background

The crocodile skin is long and narrow, thick and hard scales cover the body surface, tiny and staggered textures can appear in gaps among the textures, the surface is uneven, and crocodile skin fibers are knitted very densely. When the crocodile skin surface is coated, various materials are difficult to permeate and then the colored color is easy to scab and paint.

Therefore, the process for coating the surface of the crocodile skin in primary color is designed, and the crocodile skin is subjected to bottom sealing and filling before coloring, so that the subsequent material penetration and the subsequent continuity are facilitated, and the bonding fastness of the dye is finally ensured.

Disclosure of Invention

The invention provides a coating process for the surface of primary-color crocodile skin to overcome the defects of the prior art, wherein the crocodile skin is subjected to bottom sealing and filling before coloring, so that the subsequent material permeation and the subsequent continuity are facilitated, and the bonding fastness of the dye is finally ensured.

In order to realize the purpose, the coating process for the surface of the crocodile skin with the primary color is designed, and is characterized by comprising the following steps:

s1, cleaning: cleaning the crocodile skin with the primary color, and cleaning grease on the surface of the crocodile skin with the primary color;

s2, bottom sealing and filling: carrying out bottom sealing on the crocodile skin with primary color and filling;

s3, coloring: uniformly coloring the crocodile skin with primary color;

s4, polishing: adjusting the rotating speed of the polishing machine to 800-1000 revolutions per minute, polishing the crocodile skin, and removing redundant floating wax on the crocodile skin;

s5, effect: forming an effect layer on the crocodile skin;

s6, secondary polishing: adjusting the rotating speed of the polishing machine to 800-1000 revolutions per minute, polishing the crocodile skin, and removing redundant floating wax on the crocodile skin;

s7, glazing: glazing the crocodile skin;

s8, three polishing: and adjusting the rotating speed of the polishing machine to be 1000-1200 rpm, and polishing the surface of the crocodile skin.

In the step S2, an adhesion type filler is used for bottom sealing and filling, wherein the adhesion type filler comprises the following raw materials in parts by weight: 50-60 parts of water, 10-15 parts of aromatic polyurethane resin, 15-20 parts of acrylic resin, 15-20 parts of alcohol and 1-3 parts of penetrating agent, wherein the sum of the contents of all the components is 100 parts.

In the step S3, an aqueous coloring agent is used for coloring, and the aqueous coloring agent includes the following raw materials in parts by weight: 10-20 parts of water, 35-45 parts of first modified rice bran wax emulsion, 15-25 parts of modified polyurethane resin, 10-15 parts of alcohol ether solvent, 3-6 parts of auxiliary agent, 2-5 parts of thickening agent and 15-20 parts of metal complex dye water, wherein the sum of the contents of all the components is 100 parts, and the auxiliary agent is one or more of penetrating agent, hand feeling agent, mildew preventive and essence.

In the step S5, an effect layer is formed by using an aqueous effect agent, wherein the aqueous effect agent comprises the following raw materials in parts by weight: 10-20 parts of water, 35-45 parts of first modified rice bran wax emulsion, 15-25 parts of modified polyurethane resin, 10-15 parts of alcohol ether solvent, 3-6 parts of auxiliary agent, 10-15 parts of thickening agent and 15-20 parts of metal complex dye water, wherein the sum of the contents of all the components is 100 parts, and the auxiliary agent is one or more of a flatting agent, a hand feeling agent, a mildew preventive and essence.

In the step S1, a strong cleaning agent and an aqueous cleaning agent are respectively used for cleaning the raw cowhide, wherein the strong cleaning agent comprises the following raw materials in parts by weight: 50-60 parts of alcohol, 30-35 parts of acetone and 10-15 parts of ethylene glycol ethyl ether, wherein the sum of the contents of all the components is 100 parts; the water-based cleaning agent comprises the following raw materials in parts by weight: 55-65 parts of water, 3-6 parts of surfactant, 25-35 parts of water-soluble organic solvent, 3-8 parts of acrylic resin and 3-8 parts of metal complex dye water, wherein the sum of the contents of all the components is 100 parts.

In the steps S4 and S6, polishing treatment is carried out by using polishing wax blocks, wherein the polishing wax blocks comprise the following raw materials in parts by weight: 40-50 parts of palm wax, 25-35 parts of second modified rice bran wax, 1-3 parts of chlorinated paraffin, 25-30 parts of preformed metal complex dye wax agent and 1 part of essence, wherein the sum of the contents of all the components is 100 parts.

In step S7, high gloss wax water and polishing wax oil are respectively used for polishing, where the high gloss wax water includes the following raw materials in parts by weight: 12-20 parts of emulsion-shaped second modified rice bran wax, 25-35 parts of modified polyurethane resin emulsion, 35-45 parts of deionized water, 6-10 parts of alcohol ether solvent, 8-10 parts of metal complex dye water and 3-5 parts of auxiliary agent, wherein the sum of the contents of all the components is 100 parts; the polishing wax oil comprises the following raw materials in parts by weight: 48-55 parts of third modified rice bran wax emulsion, 5-10 parts of modified acrylic resin emulsion, 20-30 parts of deionized water, 10-15 parts of alcohol ether solvent, 8-10 parts of metal complex dye water and 3-5 parts of auxiliary agent, wherein the sum of the contents of all the components is 100 parts.

In step S8, polishing is performed by using soft filling wax and polishing wax, where the soft filling wax includes the following raw materials in parts by weight: 40-50 parts of oxidized paraffin, 20-30 parts of palm wax, 15-20 parts of kaolin, 3-5 parts of chlorinated paraffin and 15-20 parts of preformed metal complex dye wax agent, wherein the sum of the contents of all the components is 100 parts.

The preformed metal complex dye wax agent comprises the following raw materials in parts by weight: 35-38 parts of metal complex dye powder, 40-50 parts of stearic acid and 20-25 parts of palm wax; the sum of the contents of all the components is 100 parts.

The preparation method of the first modified rice bran wax emulsion, the second modified rice bran wax in the emulsion state and the third modified rice bran wax emulsion specifically comprises the following steps:

step A, adding concentrated sulfuric acid with the concentration of 75% into a first enamel reaction kettle, keeping the continuous heating state, adding rice bran wax into the first enamel reaction kettle, continuously heating the rice bran wax to 90-100 ℃ to melt the rice bran wax, slowly adding a hydrogen peroxide solution with the concentration of 35% under the stirring state, continuously stirring for 12-14 hours under the constant temperature condition of 90-100 ℃ to completely oxidize the rice bran wax, naturally cooling the rice bran wax, standing for 1 hour to separate the wax from water, and discharging the water at the lower layer;

step B, heating the enamel reaction kettle to 90-100 ℃, re-melting the oxidized rice bran wax on the upper layer into liquid, adding water under the stirring state, continuously stirring for 30-40 minutes, standing for 1-3 hours, separating the wax and the water, and discharging the water on the lower layer;

step C, repeating the step B for 3-5 times, wherein the upper layer is the high-acid-value synthetic wax, and the lower layer is water recycled;

step D, taking the high-acid-value synthetic wax and the methyl isopropyl ketone for mixing and dissolving, heating to a high-acid-value synthetic wax for completely dissolving, slowly cooling the mixed solution under continuous slow stirring to a constant temperature of 45-55 ℃, keeping the constant temperature for 30-40 minutes, and separating solid and liquid;

step E, carrying out vacuum distillation on the solid to obtain high-melting-point synthetic wax;

step F, carrying out vacuum distillation on the liquid to obtain synthetic wax with a low melting point, wherein the distilled liquid is methyl isopropyl ketone and is reserved for subsequent recycling;

step G, putting the low-melting-point synthetic wax and zinc oxide into a second enamel reaction kettle, heating to 150-160 ℃ to melt the low-melting-point synthetic wax, adding high-molecular polyethylene glycol, reacting for 5-8 hours, slowly cooling to normal temperature after the reaction is finished, and filtering to obtain a first modified rice bran wax emulsion;

step H, putting the high-melting-point synthetic wax and zinc oxide into a third enamel reaction kettle, heating to 150-160 ℃ to melt the high-melting-point synthetic wax, adding calcium oxide to react for 5-8 hours, and washing with water after the reaction is finished to obtain second modified rice bran wax;

step I, mixing and heating second modified rice bran wax, first modified rice bran wax emulsion and emulsifier to be melted at 110 ℃ at 100 ℃, slowly adding deionized water at 100 ℃ in a stirring state, stirring to be uniform milky white liquid, homogenizing for 30-60 minutes by using a homogenizer, and filtering to obtain emulsion-shaped second modified rice bran wax;

and step J, putting the high-melting-point synthetic wax and zinc oxide into a fourth enamel reaction kettle, heating to 150-160 ℃ to melt the high-melting-point synthetic wax, adding ethylene glycol to react for 5-8 hours, washing after the reaction is finished to obtain third modified rice bran wax, mixing and heating the third modified rice bran wax, the first modified rice bran wax emulsion and an emulsifier to 100-110 ℃ to melt, slowly adding 100 ℃ deionized water under a stirring state, stirring to obtain uniform milky liquid, homogenizing for 30-60 minutes by using a homogenizer, and filtering to obtain third modified rice bran wax emulsion.

Compared with the prior art, the crocodile skin is subjected to back sealing and filling before coloring, so that the subsequent material permeation and the continuous adhesion are facilitated, and the adhesion fastness of the dye is finally ensured.

Detailed Description

The first embodiment is as follows:

in this embodiment, the coating of the surface of the crocodile skin with the primary color specifically includes the following steps:

s1, cleaning: cleaning primary crocodile skin by using a powerful cleaning agent and a water-based cleaning agent respectively, and cleaning grease on the surface of the primary crocodile skin;

s2, bottom sealing and filling: bottom sealing and filling the primary color crocodile skin by using a following filler;

s3, coloring: uniformly coloring the crocodile skin with primary color by using an aqueous coloring agent;

s4, polishing: adjusting the rotating speed of the polishing machine to 800-1000 revolutions per minute, polishing the crocodile skin, and removing redundant floating wax on the crocodile skin;

s5, effect: spraying dark line-drawing paint on the crocodile skin by using a small-caliber line-drawing gun according to the original lines of the crocodile skin, and making a two-color effect layer on the surface of the crocodile skin;

s6, secondary polishing: adjusting the rotating speed of the polishing machine to 800-1000 revolutions per minute, polishing the crocodile skin, and removing redundant floating wax on the crocodile skin;

s7, glazing: polishing the crocodile skin by using high-gloss wax water and polishing wax oil;

s8, three polishing: and adjusting the rotating speed of the polishing machine to be 1000-1200 rpm, and polishing the surface of the crocodile skin.

In step S4, step S6, and step S8, the crocodile skin is polished three times in total. In the coloring step S3, an aqueous coloring agent that is easy to polish is used, and the first rice bran wax emulsion in the aqueous coloring agent is polished to exhibit clear brightness. Therefore, step S4, polishing after drying, is beneficial to show through brightness, give the crocodile skin base bottom gloss, and remove the excessive floating wax on the skin surface, which is beneficial to the follow-up of materials. The secondary polishing in the step S6 is to make the luster of the sprayed effect layer more transparent, highlight the texture of the effect layer, and also remove floating wax to facilitate the subsequent following action. In step S7, the crocodile skin is polished by using high-gloss wax water and polishing wax oil, so as to emphasize the transparent luster of the crocodile skin. The second modified rice bran wax in the emulsion state in the high gloss wax water and the third modified rice bran wax emulsion in the polishing wax oil have the characteristics of more bright polishing and more transparent light sensation, so that the step S8 is used for polishing for three times, and the crocodile skin texture is favorably improved.

Crocodile skin has a special fine fiber weave structure, which makes penetration and attachment of chemical materials difficult, resulting in colored colors that are easily scabbed and lacquered. This embodiment improves the penetration of the subsequent material into the crocodile skin fibers by the bottoming and filling of step S2. And then, through the coloring in the step S3, the base color is made for the primary color crocodile skin. Finally, through the effect layer of the step S5, a required special effect layer is made on the surface of the primary color crocodile skin.

In step S2, an adhesion type filler is used for bottom sealing and filling, wherein the adhesion type filler comprises the following raw materials in parts by weight: 55 parts of water, 12 parts of polyurethane resin, 17 parts of acrylic resin, 15 parts of alcohol and 1 part of penetrant. The preparation method of the follow-up filler comprises the following steps: weighing the raw materials in sequence at normal temperature, adding the raw materials into a stirrer, keeping the rotating speed of the stirrer at 40r/min, stirring for 30 minutes until the materials are uniformly mixed, and filtering. Wherein water is the primary solvent and alcohol is the aqueous solvent, which facilitates penetration of other materials and thus bonding of the other materials to the crocodile skin fibers. The type of the polyurethane resin is UW 02. The acrylic resin is model AR 624.

The molecular of the acrylic resin is small, the acrylic resin can easily enter the crocodile skin tight fiber weaving, the acrylic resin is attached to the surface of the fiber inside the crocodile skin after being dried, the crocodile skin fiber is bonded, the penetration is carried out, the depth is followed, but the follow-up material cannot be guaranteed to be followed by the acrylic resin alone, and the follow-up material cannot be penetrated into the crocodile skin. Therefore, the aromatic polyurethane resin is selected and is a strong adhesion type resin, a high-strength adhesion layer can be formed on the surface of the crocodile skin, the adhesion performance of the surface of the crocodile skin is enhanced, the subsequent materials are adhered upwards, and the subsequent materials are firmly adhered downwards to the surface of the crocodile skin. Acrylic resin and aromatic polyurethane resin are mixed and overlapped, acrylic acid bonding is guaranteed to exist between fibers inside crocodile skin, the outer surface of the crocodile skin is bonded through the aromatic polyurethane, permeation and continuity of subsequent materials are guaranteed, and finally fastness is guaranteed, so that peeling and slurry cracking of the whole coating on the surface of the crocodile skin are avoided.

In step S3, the primary color crocodile skin is colored with an aqueous colorant. The water-based coloring agent comprises the following raw materials in parts by weight: 20 parts of water, 28 parts of first rice bran wax emulsion, 20 parts of modified polyurethane resin, 10 parts of ethanol, 3 parts of penetrating agent, 2 parts of thickening agent and 17 parts of metal complex dye water. The preparation method of the water-based coloring agent comprises the following steps: at normal temperature, respectively weighing water, the first modified rice bran wax emulsion, the modified polyurethane resin, ethanol, a penetrating agent, a thickening agent and metal complex dye water in sequence, adding into a stirrer, keeping the rotating speed of the stirrer at 40r/min, stirring for 30min, and filtering after all materials are uniformly mixed. The first modified rice bran wax emulsion has good self-emulsifying property, the particle size of emulsified particles is small, the particles can be matched with other materials to permeate into crocodile skin fibers together, and the first modified rice bran wax emulsion has excellent leveling property, so that the coloring uniformity of the water-based coloring agent can be greatly enhanced, and the problems of color fading and the like can be avoided. In addition, the first modified rice bran wax emulsion also provides excellent polishing performance for the aqueous coloring agent, so that the polished primary color crocodile skin has natural and clear luster. The type of the modified polyurethane resin is UW-10. The modified polyurethane resin has strong penetrability, can permeate into crocodile skin fibers, is fixed on the crocodile skin fibers together with the first modified rice bran wax emulsion, ensures the adhesive force of metal complex dye molecules and the crocodile skin fibers, and gives a certain luster to the surfaces of the crocodile skins. The alcohol ether solvent can promote permeation and adhesion, so that the first modified rice bran wax emulsion is more easily permeated into crocodile skin fibers and is stored for a longer time. The thickening agent can increase the consistency of the whole material, ensure that the whole material has better storage stability and is not easy to run off.

In step S6, a two-color effect is made on the primary crocodile skin using an aqueous effector. The water-based effect agent comprises the following raw materials in parts by weight: 10 parts of water, 37 parts of first rice bran wax emulsion, 15 parts of modified polyurethane resin, 10 parts of ethanol, 3 parts of a flatting agent, 10 parts of a thickening agent and 15 parts of metal complex dye water. The preparation method of the water-based effector comprises the following steps: at normal temperature, respectively weighing water, the first modified rice bran wax emulsion, the modified polyurethane resin, ethanol, the flatting agent, the thickening agent and the metal complex dye water in sequence, adding into a stirrer, keeping the rotating speed of the stirrer at 40r/min, stirring for 30min, and filtering after all the materials are uniformly mixed. The type of the modified polyurethane resin is UW-10.

The metal complex dye water comprises the following raw materials in parts by weight: 20 parts of metal complex dye powder, 50 parts of ethanol and 30 parts of water. The preparation method of the metal complex dye water comprises the following steps: at normal temperature, metal complex dye powder, ethanol and water are respectively weighed in sequence and added into a stirrer for uniform stirring. The metal complex dye powder is used for reflecting color, dyeing leather surface and increasing color vividness, the ethanol is used as a main solvent and is used for dissolving the metal complex dye, and the water can enable the mixture of the metal complex dye powder and the ethanol to present better water solubility. The metal complex dye powder has poor water solubility, and the embodiment selects ethanol to complete the oil-to-water operation of the metal complex dye, so that the water solubility of the metal complex dye is improved.

The components of the aqueous effect agent used in this example are the same as those of the aqueous coloring agent, but the mixture ratio of the materials is different. Because the aqueous coloring agent uses more first modified rice bran wax emulsion, and the wax emulsion is not beneficial to the permeation and adhesion of subsequent materials after being dried, a material similar to the aqueous coloring agent is selected to prepare the aqueous effect agent, and the first modified rice bran wax emulsion with better self-emulsifying property is also used in the aqueous effect agent, so that the first modified rice bran wax emulsion can be mutually mixed and dissolved with the first modified rice bran wax emulsion in the aqueous coloring agent in the drying process, the adhesion of the aqueous effect agent is promoted, and the adhesion fastness is enhanced. The components of the aqueous effector agent are therefore the same as the aqueous colouring agent. However, the aqueous coloring agent focuses on the uniformity of coloring and the penetration of the aqueous coloring agent into the crocodile skin, so that the crocodile skin surface can look bright and new only by uniform coloring, and if the penetration is not good, the crocodile skin can be discolored in subsequent use. The aqueous effect agent is considered to be intuitive and obvious for the special effect layer, and the contrast of colors in the special effect layer is highlighted by the aqueous effect agent, so the aqueous effect agent should avoid uniformity. And if the permeability of the aqueous effect agent is too strong, materials and dyes in the aqueous effect layer rapidly penetrate into the crocodile skin fibers, so that the special effect layer on the surfaces of the crocodile skin fibers is not obvious. Therefore, the proportion of the water-based effect agent and the water-based coloring agent is different, so as to meet the safety of the primary color crocodile skin leather shoe in subsequent use and the durability of the special effect layer.

In step S1, primary crocodile skin is cleaned with a powerful cleaner and an aqueous cleaner, respectively.

The powerful cleaning agent is used for cleaning grease on the surface of the original-color crocodile skin, so that various materials in the subsequent steps can permeate into crocodile skin fibers, and a permeation channel is opened. The powerful detergent comprises the following raw materials in parts by weight: 55 parts of alcohol, 30 parts of acetone and 15 parts of ethylene glycol ethyl ether. The preparation method of the powerful detergent comprises the following steps: at normal temperature, sequentially weighing alcohol, acetone and ethylene glycol ethyl ether respectively, adding into a stirrer, keeping the rotation speed of the stirrer at 40r/min, stirring for 30min, and filtering after all materials are uniformly mixed. In the strong cleaning agent, alcohol is used as a water-oil amphoteric solvent, so that acetone can be dissolved, the oily basis after acetone cleaning is converted into a water-based basis, and the basis is laid for water-based treatment in the subsequent steps. The acetone has strong dissolving power, can clean grease substances on the surface of the crocodile skin, is quickly volatilized, and prevents the adverse effect caused by the fact that the acetone stays on the surface of the crocodile skin for a long time. The ethylene glycol ethyl ether is water-oil amphoteric, has strong dissolving power, can be guaranteed to stay on the surface of the crocodile skin for a long time due to the high boiling point of the ethylene glycol ethyl ether, is favorable for dissolving oil stains on the surface of the crocodile skin and swelling crocodile skin fibers, and thus opens a permeation channel for various materials in the subsequent steps to permeate into the crocodile skin fibers.

The aqueous cleanser further opens the permeation pathways within the crocodile skin fibers and renders the crocodile skin surface, crocodile skin fibers hydrophilic. The water-based cleaning agent comprises the following raw materials in parts by weight: 60 parts of water, 5 parts of OP-15 surfactant, 25 parts of ethanol, 5 parts of acrylic resin and 5 parts of metal complex dye water. The preparation method of the water-based cleaning agent comprises the following steps: at normal temperature, water, OP-15 surfactant, ethanol, acrylic resin and metal complex dye water are respectively weighed and added into a stirrer in sequence, the stirrer keeps the rotating speed at 40r/min, the stirring is carried out for 30min, and the materials are filtered after being uniformly mixed. In the aqueous cleaning agent, water is a main solvent, and the surfactant promotes the penetration of crocodile skin fibers, reduces the surface tension of water and is beneficial to the penetration and the following of aqueous materials. The water-soluble organic solvent is an aqueous solvent, so that the penetration of the crocodile skin fibers is promoted, the swelling of the crocodile skin fibers is accelerated, and the subsequent material penetration into the crocodile skin fibers is facilitated. The type of the acrylic resin is AR624, the micromolecular acrylic resin permeates into crocodile skin fibers and is in a mutual soluble state with dye water, metal complex dye molecules can be wrapped after drying, and the metal complex dye molecules are wrapped and fixed in the crocodile skin fibers, so that the metal complex dye molecules can be tightly combined with the crocodile skin fibers.

In the steps S4 and S6, polishing treatment is carried out by using polishing wax blocks, wherein the polishing wax blocks comprise the following raw materials in parts by weight: 48 parts of palm wax, 25 parts of second modified rice bran wax, 1 part of chlorinated paraffin, 25 parts of a preformed metal complex dye wax agent and 1 part of essence. The preparation method of the polishing wax block comprises the following steps: all raw materials are first heated to melt to a fluid state and then mixed together with continuous stirring. And then slowly cooling to 90 ℃ under stirring until the mixed liquid is gradually thickened but is not coagulated. Keeping the mold in a horizontal state again, injecting the cooled mixed liquid into the mold at a constant temperature of 85 ℃, finally standing the mold and completely cooling to room temperature, and demolding after the wax block is completely hardened.

In the step S7, high gloss wax water and polishing wax oil are respectively used for glazing treatment, and the high gloss wax water comprises the following raw materials in parts by weight: 12 parts of emulsion-shaped second modified rice bran wax, 28 parts of modified polyurethane resin emulsion, 40 parts of deionized water, 6 parts of alcohol ether solvent, 9 parts of metal complex dye water and 5 parts of auxiliary agent, wherein the auxiliary agent comprises 1 part of penetrating agent, 1 part of flatting agent, 1 part of hand feeling agent, 1 part of mildew preventive and 1 part of essence. The preparation method of the high-gloss wax water specifically comprises the following steps of keeping a stirrer in a stirring state, sequentially adding the raw materials into the stirrer, stirring until the materials are uniformly mixed, and filtering.

The polishing wax oil comprises the following raw materials in parts by weight: 50 parts of third modified rice bran wax emulsion, 5 parts of modified acrylic resin emulsion, 21 parts of deionized water, 12 parts of alcohol ether solvent, 9 parts of metal complex dye water and 3 parts of auxiliary agent, wherein the auxiliary agent comprises 1 part of flatting agent, 0.5 part of hand feeling agent, 0.5 part of mildew preventive and 1 part of essence. The preparation method of the polishing wax oil comprises the following steps of keeping a stirrer in a stirring state, sequentially adding the raw materials into the stirrer, stirring until the materials are uniformly mixed, and filtering.

The alcohol ether solvent in the polishing wax block, the high-gloss wax water and the polishing wax oil can be one or more of ethanol, butanol, ethylene glycol ethyl ether and ethylene glycol butyl ether. The modified polyurethane resin emulsion is UW-10. The modified acrylic resin emulsion is AR-332.

And S9, polishing by using soft filling wax and polishing wax blocks respectively, wherein the soft filling wax comprises the following raw materials in parts by weight: 40 parts of oxidized paraffin, 25 parts of palm wax, 15 parts of kaolin, 3 parts of chlorinated paraffin and 17 parts of a preformed metal complex dye wax agent. The preparation method of the soft filling wax comprises the following steps: all raw materials are first heated to melt to a fluid state and then mixed together with continuous stirring. And then slowly cooling to 73 ℃ under stirring until the mixed liquid is gradually thickened but is not coagulated. Keeping the mold in a horizontal state again, injecting the cooled mixed liquid into the mold at a constant temperature of 70 ℃, finally standing the mold and completely cooling to room temperature, and demolding after the wax block is completely hardened.

The preformed metal complex dye wax agent in the soft filling wax and the polishing wax block comprises the following raw materials in parts by weight: 35 parts of metal complex dye powder, 40 parts of stearic acid and 25 parts of palm wax. The preparation method of the preformed metal complex dye wax agent comprises the following steps: firstly, dissolving metal complex dye powder in an acetone solvent with the mass of 1 time, and uniformly stirring until the metal complex dye powder is completely dissolved and no particles exist; secondly, adding stearic acid and palm wax, fully and slowly stirring, and heating until the wax is completely dissolved; thirdly, continuously heating until the liquid is boiled and evaporated; fourthly, slowly cooling to 50 ℃ after the steam is completely evaporated; and fifthly, pouring the mixture into a mold, and cooling to normal temperature to finish the preparation. In the third step, steam boiled out can be collected by a recovery cooling device, and the steam is cooled into liquid for storage and can be recycled.

In the prefabricated metal complex dye wax agent, acetone and stearic acid are used as intermediates, so that metal complex dye powder can be dispersed in palm wax, and the leather surface is colored while polishing is guaranteed. The prefabricated metal complex dye wax agent is prepared in advance and is convenient to take and use due to the long period of the manufacturing process and the complex process; and in the subsequent specific use process, the preformed metal complex dye wax agent is repeatedly heated and melted, so that the mutual fusion of the metal complex dye powder and the palm wax is facilitated.

The preparation method of the aqueous effect agent, the first modified rice bran wax emulsion in the aqueous coloring agent, the second modified rice bran wax in the polishing wax block, the second modified rice bran wax in the emulsion state in the high gloss wax water and the third modified rice bran wax emulsion in the polishing wax oil specifically comprises the following steps:

step A, adding 500kg of natural rice bran wax into a first enamel reaction kettle filled with 2200ml of concentrated sulfuric acid with concentration of 75% in a heating state, continuously heating to 90 ℃ to melt the rice bran wax, slowly adding 5000ml of hydrogen peroxide solution with concentration of 35% in a stirring state, continuously stirring for 12 hours at a constant temperature of 90 ℃ to completely oxidize the rice bran wax, changing the color of the rice bran wax into light beige, naturally cooling, standing for 1 hour to separate the wax from water, and discharging the lower-layer water;

step B, heating the enamel reaction kettle to 90 ℃, so that the oxidized rice bran wax on the upper layer is re-melted into liquid, adding water under the stirring state, continuously stirring for 30 minutes, standing for 1 hour, so that the wax and the water are separated, and the water on the lower layer is discharged;

step C, repeating the step B for 3-5 times, wherein the upper layer is the high-acid-value synthetic wax, and the lower layer is water recycled;

step D, taking the high-acid-value synthetic wax and the methyl isopropyl ketone for mixing, heating to a high-acid-value synthetic wax for complete dissolution, slowly cooling the mixed solution under continuous slow stirring to a constant temperature of 45 ℃, keeping the temperature for 30 minutes, and separating solid and liquid, wherein the mass ratio of the high-acid-value synthetic wax to the methyl isopropyl ketone is 1: 5;

step E, carrying out vacuum distillation on the solid to obtain high-melting-point synthetic wax;

step F, carrying out vacuum distillation on the liquid to obtain synthetic wax with a low melting point, wherein the distilled liquid is methyl isopropyl ketone and is reserved for subsequent recycling;

step G, putting 200kg of low-melting-point synthetic wax and 2kg of zinc oxide into a second enamel reaction kettle, heating to 150 ℃ to melt the low-melting-point synthetic wax, adding 6kg of high-molecular polyethylene glycol with the molecular weight of 400, reacting for 5-8 hours, slowly cooling to normal temperature after the reaction is finished, and filtering to obtain a first modified rice bran wax emulsion;

step H, putting 200kg of high-melting-point synthetic wax and 2kg of zinc oxide into a third enamel reaction kettle, heating to 150 ℃ to melt the high-melting-point synthetic wax, adding 5kg of calcium oxide, reacting for 5-8 hours, and washing with water after the reaction is finished to obtain second modified rice bran wax;

step I, mixing and heating 96 parts of second modified rice bran wax, 3 parts of first modified rice bran wax emulsion and 1 part of emulsifier OP-15 to melt at 100 ℃, slowly adding 500 parts of deionized water at 100 ℃ in a stirring state, stirring to obtain uniform milky liquid, homogenizing for 30-60 minutes by using a homogenizer, and filtering to obtain emulsion-shaped second modified rice bran wax;

step J, putting 200kg of high-melting-point synthetic wax and 2kg of zinc oxide into a fourth enamel reaction kettle, heating to 150 ℃ to melt the high-melting-point synthetic wax, adding 10kg of ethylene glycol, reacting for 5-8 hours, and washing with water after the reaction is finished to obtain third modified rice bran wax; and (3) mixing 96 parts of third modified rice bran wax, 3 parts of first modified rice bran wax emulsion and 1 part of emulsifier OP-15, heating to 100 ℃ for melting, slowly adding 500 parts of 100 ℃ deionized water under a stirring state, stirring to obtain uniform milky white liquid, homogenizing for 30-60 minutes by using a homogenizer, and filtering to obtain the third modified rice bran wax emulsion.

In the step D, the high-melting point synthetic wax is precipitated in a solid state at the temperature of 45 ℃, and the low-melting point synthetic wax is continuously present in a solution state. After the wax is distinguished by melting points, high-melting point synthetic wax and low-melting point synthetic wax with different brightness and properties are obtained.

The high-melting-point synthetic wax has high brightness, and the brightness can be enhanced again through subsequent synthetic treatment on the basis to prepare the high-melting-point, high-hardness and high-brightness synthetic wax without causing uncontrollable or inconspicuous brightness improvement of a final product due to interference of the low-melting-point wax.

The self-emulsifying synthetic wax prepared by subsequent treatment of the low-melting-point synthetic wax has stable self-emulsifying performance and can not cause incomplete emulsification due to the existence of the high-melting-point wax with limited self-emulsifying performance.

In the step G, the low-melting-point synthetic wax and the high-molecular polyethylene glycol are subjected to dehydration esterification reaction under the catalytic action of zinc oxide to obtain the first modified rice bran wax emulsion with self-emulsifying property, and the first modified rice bran wax emulsion is soft and smooth in luster.

In the step H, the high-melting-point synthetic wax and calcium oxide are subjected to saponification reaction under the catalytic action of zinc oxide, so that the second modified rice bran wax with high hardness, good polishing performance and high gloss is obtained.

In the step J, the high-melting-point synthetic wax and ethylene glycol undergo a dehydration esterification reaction under the catalytic action of zinc oxide, so that a third modified rice bran wax which is high in gloss, high in hardness and easy to emulsify is obtained.

The crocodile skin is subjected to back cover and filling before coloring, so that the penetration of a longitudinal and transverse subsequent material and the continuity of the connection are avoided, and the connection fastness of the dye is finally ensured.

Example two:

in this example, the surface of the original-color crocodile skin is coated, and the steps and the materials used in the steps are the same as those in the step 5.

The specific method of step S5 in this embodiment is as follows: s5, effect: and (3) polishing the water-based coloring agent which is darker than the color of the crocodile skin on the surface of the crocodile skin through a polishing machine to deepen the color of the raised grains so as to achieve the deep and light double-color wiping effect and make a double-color effect layer.