Baseball leather treatment process

Abstract

The invention discloses a baseball leather treatment process. The baseball leather treatment process comprises the following steps: S1, soaking and fleshing; s2, unhairing expansion and re-liming; s3, decolorizing and bleaching; s4, pickling treatment; s5, carrying out chrome-free tanning, taking out of a drum and squeezing water; s6, slicing and peeling, rinsing and neutralizing; s7, fat liquoring and retanning; and S8, vacuum milling. According to the method, the defects in the prior art are overcome, two-step shaping is adopted in the chrome-free tanning step and the drum-out wringing step, the leather treated according to the scheme is in a half-cooked state instead of being treated to be in a full-cooked state, and the baseball made of the leather can be shrunk when being hit in the hitting process, so that the leather is more comfortable to wear. However, leather tanned in the prior art can expand and loosen after being used for a period of time, and the leather tanning agent has high social use value and application prospects.

Description

Technical Field

[0001] The invention relates to the technical field of leather processing, in particular to a baseball leather processing process. Background Art

[0002] As a sport widely played around the world, the market demand for baseball continues to grow. Whether it is professional baseball games, amateur baseball leagues or daily training and entertainment activities of baseball enthusiasts, high requirements are placed on the quality and performance of baseballs. Baseballs are mainly composed of a core, a winding layer and a leather cover, among which the leather cover directly affects the key characteristics of the baseball, such as touch, durability, flight stability and appearance quality.

[0003] Leather is a denatured and non-perishable animal skin obtained through physical and chemical processes such as depilation and tanning. It has a history of thousands of years and is widely used in shoes, clothing, bags, furniture and other fields because of its wide variety of patterns and colors, good waterproof performance and relatively low price compared to genuine leather. Chrome-free leather completely eliminates heavy metal chromium pollution in the leather making process from the source, promotes green development and achieves the purpose of environmental protection.

[0004] However, since leather contains a large amount of protein, it lacks antibacterial ability. Leather sports equipment, shoes and other products are easily stained with sweat and dirt. In a humid environment, bacteria are easily bred, which is harmful to human health and even mildewed, greatly shortening the service life of the leather. In the existing cowhide leather manufacturing process, the surface of the final product made of cowhide is relatively smooth. When this relatively smooth leather is applied to a baseball, the friction coefficient between the surface of the baseball and the bat will be small, and it is easy to slip when swinging the bat to hit the ball, which is not conducive to the baseball player's hitting.

[0005] In the leather processing process, it is generally necessary to add fatliquor. The oil component in the fatliquor has a certain hydrophobicity and can form a continuous waterproof layer on the surface of the leather fiber to prevent the intrusion of water. This allows the leather to remain in a relatively dry state when in a humid environment or when exposed to water, preventing problems such as leather expansion, deformation, and mildew caused by water absorption, thereby ensuring that the performance and appearance of the baseball are not affected. Summary of the invention

[0006] In order to solve the problems mentioned in the above background technology, the present invention provides a baseball leather processing process.

[0007] In order to achieve the above object, the present invention adopts the following technical solutions:

[0008] A baseball leather processing process comprises the following steps:

[0009] S1 soaking and meat removal:

[0010] The raw hide of yellow cattle is immersed in deionized water, and a composite degreasing agent is added to perform flesh removal treatment;

[0011] S2 hair removal swelling and graying:

[0012] After the raw hide of cattle is de-fleshed, deionized water, sodium sulfide and slaked lime are added to carry out dehairing, swelling and re-liming; then the de-fleshing equipment is used to de-flesh the gray hide, and the skin splitting machine is used to slice the gray hide;

[0013] S3 decolorization and bleaching:

[0014] Then add deionized water and oxalic acid for deashing and softening, and add formaldehyde and titanium dioxide for decolorization and bleaching;

[0015] S4 pickling treatment:

[0016] After bleaching and decoloring, the cowhide is pickled by adding deionized water, sodium chloride and sulfuric acid;

[0017] S5 chrome-free tanning, squeezing out of drum:

[0018] After the acid treatment, the leather material is added with urotropine and polyaluminium chloride for setting for 1 hour, then the chrome-free zirconium tanning agent is added, and the temperature is controlled at 35-42°C for reaction for 4-6 hours, acetic acid chloride is added for setting for 1 hour, and finally the tanning is completed by standing for 1 day;

[0019] S6. Peel, rinse and neutralize:

[0020] The tanned leather is sliced ​​and evenly peeled, and then deionized water and sodium bicarbonate are added for rinsing and neutralization;

[0021] S7, fatliquoring and retanning:

[0022] Adding chrome-free retanning agent and fatliquor to the rinsed and neutralized leather to carry out fatliquor retanning;

[0023] S8, Vacuum softening:

[0024] The leather after fatliquoring and retanning is taken out of the drum to dry, vacuum tumbled, trimmed and graded, and the finished products are stored.

[0025] Preferably, the composite degreasing agent is prepared by compounding a surfactant, a modified biological enzyme, and sodium dodecyl sulfate in a mass ratio of 7-10:3-5:1-3.

[0026] Preferably, the surfactant is a nonionic surfactant, and the nonionic surfactant is selected from one or a combination of fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, octanol polyoxyethylene ether, and lauryl alcohol polyoxyethylene ether.

[0027] Preferably, the preparation method of the modified bioenzyme is as follows:

[0028] S1-1, dissolving chitosanase in phosphate buffer to obtain a chitosanase solution with a concentration of 3.0-6.5 g / L;

[0029] S1-2, prepare a nano-titanium dioxide suspension with a concentration of 4.5-6.0 mg / ml, and drop the chitosanase solution in S1-1 into the nano-titanium dioxide suspension, stir and mix evenly;

[0030] S1-3, adding bismaleimide to carry out cross-linking curing reaction to ensure that the enzyme molecules are firmly fixed on the surface of nano-titanium dioxide; washing with deionized water to remove unbound enzyme molecules and small molecule impurities, and vacuum drying the washed modified bio-enzyme preparation to remove moisture to obtain a dry powdered modified bio-enzyme preparation.

[0031] Preferably, the particle size of the nano titanium dioxide is 45-55 nm.

[0032] Preferably, the mass ratio of the composite degreasing agent to deionized water is 7-10:100.

[0033] Preferably, the fatliquor is one or more of sulfonated oil, castor oil, castor oil phosphate, and sulfited neat's foot oil.

[0034] Compared with the prior art, the present invention has the following beneficial effects:

[0035] 1. The present invention adopts two-step shaping in the chrome-free tanning and water-extrusion steps, so that the leather treated according to the above scheme is in a half-cooked state, instead of other leathers treated to a fully cooked state, so that the baseball made of the leather can shrink more and more during the hitting process, while the leather treated by the prior art tanning will swell and loosen after being used for a period of time.

[0036] 2. The composite degreasing agent of the present invention is compounded with surfactant, modified biological enzyme and sodium dodecyl sulfate, wherein the nonionic surfactant has good emulsification and dispersing ability, can decompose grease into tiny particles and make it uniformly dispersed in the solution; the modified biological enzyme can specifically catalyze the hydrolysis reaction of grease molecules, decompose macromolecular grease into small molecular substances, which are easier to remove; and sodium dodecyl sulfate, as an anionic surfactant, has strong decontamination ability and penetration ability, can penetrate into the leather and accelerate the removal of grease. After the three are compounded, they play a synergistic role, greatly improve the degreasing efficiency, can quickly and effectively remove the natural grease and impurities in baseball leather, and make the leather cleaner.

[0037] 3. Compared with the traditional strong alkaline or strong acidic degreasing agent, the composite degreasing agent prepared in the present invention is relatively mild and will not cause excessive erosion to leather fibers; the modified biological enzyme has high selectivity and only acts on grease without damaging the protein fiber structure of the leather. Therefore, while effectively degreasing, the original performance and quality of the leather can be protected to the greatest extent, avoiding the problems of leather strength reduction and fiber breakage caused by the degreasing process, and ensuring the durability of baseball leather.

[0038] The modified bio-enzyme itself has good biodegradability and can be quickly decomposed in the natural environment after use without causing environmental pollution. At the same time, the selection of surfactants and sodium dodecyl sulfate also takes into account their environmental friendliness. Compared with some difficult-to-degrade chemical degreasing agents, the composite degreasing agent has less pressure on the environment during production, use and waste treatment, conforms to modern environmental protection concepts and sustainable development requirements, and has high social use value and application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0040] Figure 1 It is a schematic diagram of the process flow of the present invention; DETAILED DESCRIPTION

[0041] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0042] The chrome-free retanning agent was purchased from Guangdong Demei Fine Chemical Group Co., Ltd., model TWN, cationic. Other raw materials were purchased from Aladdin and Alibaba.

[0043] Preparation Example 1

[0044] The preparation method of the modified bioenzyme is as follows:

[0045] S1-1, dissolving 10 g of chitosanase in 3.3 L of phosphate buffer to obtain a chitosanase solution with a concentration of 3.0 g / L;

[0046] S1-2, prepare a nano-titanium dioxide suspension with a concentration of 5 mg / ml, and drop the chitosanase solution in S1-1 into the nano-titanium dioxide suspension, stir and mix evenly;

[0047] S1-3, adding bismaleimide to carry out cross-linking curing reaction, then washing with deionized water, and then removing moisture by vacuum drying to obtain a modified bio-enzyme.

[0048] The particle size of nano titanium dioxide is 45nm.

[0049] Preparation Example 2

[0050] The preparation method of the modified bioenzyme is as follows:

[0051] S1-1, dissolving 10 g of chitosanase in 2 L of phosphate buffer to obtain a chitosanase solution with a concentration of 5.0 g / L;

[0052] S1-2, prepare a nano-titanium dioxide suspension with a concentration of 4.5 mg / ml, and drop the chitosanase solution in S1-1 into the nano-titanium dioxide suspension, stir and mix evenly;

[0053] S1-3, adding bismaleimide to carry out cross-linking curing reaction, then washing with deionized water, and then removing moisture by vacuum drying to obtain a modified bio-enzyme.

[0054] The particle size of nano titanium dioxide is 50nm.

[0055] Preparation Example 3

[0056] The preparation method of the modified bioenzyme is as follows:

[0057] S1-1, dissolving 10 g of chitosanase in 1.5 L of phosphate buffer to obtain a chitosanase solution with a concentration of 6.5 g / L;

[0058] S1-2, prepare a nano-titanium dioxide suspension with a concentration of 6 mg / ml, and drop the chitosanase solution in S1-1 into the nano-titanium dioxide suspension, stir and mix evenly;

[0059] S1-3, adding bismaleimide to carry out cross-linking curing reaction, then washing with deionized water, and then removing moisture by vacuum drying to obtain a modified bio-enzyme.

[0060] The particle size of nano titanium dioxide is 55nm.

[0061] Preparation Example 4

[0062] The composite degreasing agent is prepared by compounding fatty alcohol polyoxyethylene ether, the modified biological enzyme prepared in Preparation Example 1, and sodium dodecyl sulfate in a mass ratio of 7:3:1.

[0063] Preparation Example 5

[0064] The composite degreasing agent is prepared by compounding octanol polyoxyethylene ether, the modified biological enzyme prepared in Preparation Example 2, and sodium dodecyl sulfate in a mass ratio of 8:3:2.

[0065] Preparation Example 6

[0066] The composite degreasing agent is prepared by compounding lauryl alcohol polyoxyethylene ether, the modified biological enzyme prepared in Preparation Example 3, and sodium dodecyl sulfate in a mass ratio of 8:5:3.

[0067] Example 1

[0068] Reference Figure 1 , a baseball leather processing process, comprising the following steps:

[0069] S1 soaking and meat removal:

[0070] 50 g of yellow cattle hide was immersed in 100 g of deionized water, and 7 g of the composite degreasing agent prepared in Preparation Example 4 was added to perform flesh removal treatment;

[0071] S2 hair removal swelling and graying:

[0072] After the raw hide of the yellow cattle is de-fleshed, 100g of deionized water, 10g of sodium sulfide and 5g of slaked lime are added to perform dehairing, swelling and re-liming; then the de-fleshing equipment is used to de-flesh the gray hide, and the skin splitting machine is used to slice the gray hide;

[0073] S3 decolorization and bleaching:

[0074] Then add 100g of deionized water and 15g of oxalic acid for deashing and softening, and add 5g of formaldehyde and 5g of titanium dioxide for decolorization and bleaching;

[0075] S4 pickling treatment:

[0076] After the cowhide is bleached and decolorized, 100 g of deionized water, 8 g of sodium chloride and 13 g of sulfuric acid are added for pickling treatment;

[0077] S5 chrome-free tanning, squeezing out of drum:

[0078] Add 5g of urotropine and 8g of polyaluminium chloride to the leather after pickling for 1 hour, then add 7g of chromium-free zirconium tanning agent, control the temperature to react at 35°C for 4 hours, add acetic acid chloride for 1 hour, and finally let it stand for 1 day to complete the tanning;

[0079] The chrome-free zirconium tanning agent is selected from Dawitan ZR05 zirconium tanning agent, wherein the ZrO2 content is 32% and the pH value is 1.0;

[0080] S6. Peel, rinse and neutralize:

[0081] The tanned leather is sliced ​​and evenly peeled, and then 30g of deionized water and 8g of sodium bicarbonate are added for rinsing and neutralization;

[0082] S7, fatliquoring and retanning:

[0083] Add 5g of chrome-free retanning agent and 5g of castor oil phosphate to the rinsed and neutralized leather for fatliquoring;

[0084] S8, Vacuum softening:

[0085] The leather after fatliquoring and retanning is taken out of the drum and aired to dry, and then vacuum softened with a vacuum degree of -0.07MPa, a temperature controlled at 40°C, and a softening time of 3h. It is then trimmed, graded, and the finished products are put into storage.

[0086] Example 2

[0087] Reference Figure 1 , a baseball leather processing process, comprising the following steps:

[0088] S1 soaking and meat removal:

[0089] 50 g of yellow cattle hide was immersed in 100 g of deionized water, and 7 g of the composite degreasing agent prepared in Preparation Example 5 was added to perform flesh removal treatment;

[0090] S2 hair removal swelling and graying:

[0091] After the raw hide of the yellow cattle is de-fleshed, 100g of deionized water, 8g of sodium sulfide and 6g of slaked lime are added to perform dehairing, swelling and re-liming; then the de-fleshing equipment is used to de-flesh the gray hide, and the skin splitting machine is used to slice the gray hide;

[0092] S3 decolorization and bleaching:

[0093] Then add 100g of deionized water and 13g of oxalic acid for deashing and softening, and add 6g of formaldehyde and 6g of titanium dioxide for decolorization and bleaching;

[0094] S4 pickling treatment:

[0095] After the cowhide is bleached and decolorized, 100 g of deionized water, 10 g of sodium chloride and 14 g of sulfuric acid are added for pickling treatment;

[0096] S5 chrome-free tanning, squeezing out of drum:

[0097] After pickling, add 6g of urotropine and 10g of polyaluminium chloride to the leather for 1 hour, then add 8g of chromium-free zirconium tanning agent, and control the temperature to react for 4 hours at 35°C, add chloroacetic acid to fix for 1 hour, and finally let it stand for 1 day to complete the tanning;

[0098] The chrome-free zirconium tanning agent is selected from Dawitan ZR05 zirconium tanning agent, wherein the ZrO2 content is 32% and the pH value is 1.0;

[0099] S6. Peel, rinse and neutralize:

[0100] The tanned leather is sliced ​​and evenly peeled, and then 40g of deionized water and 10g of sodium bicarbonate are added for rinsing and neutralization;

[0101] S7, fatliquoring and retanning:

[0102] Add 5g of chrome-free retanning agent and 5g of castor oil phosphate to the rinsed and neutralized leather for fatliquoring;

[0103] S8, Vacuum softening:

[0104] The leather after fatliquoring and retanning is taken out of the drum and aired to dry, and then vacuum softened with a vacuum degree of -0.08MPa, a temperature controlled at 45°C, and a softening time of 3h. It is then trimmed, graded, and the finished products are put into storage.

[0105] Example 3

[0106] Reference Figure 1 , a baseball leather processing process, comprising the following steps:

[0107] S1 soaking and meat removal:

[0108] 50 g of yellow cattle hide was immersed in 100 g of deionized water, and 8 g of the composite degreasing agent prepared in Preparation Example 6 was added to perform flesh removal treatment;

[0109] S2 hair removal swelling and graying:

[0110] After the raw hide of the yellow cattle is de-fleshed, 100g of deionized water, 12g of sodium sulfide and 8g of slaked lime are added to perform dehairing, swelling and re-liming; then the de-fleshing equipment is used to de-flesh the gray hide, and the skin splitting machine is used to slice the gray hide;

[0111] S3 decolorization and bleaching:

[0112] Then add 100g of deionized water and 16g of oxalic acid for deashing and softening, and add 6g of formaldehyde and 8g of titanium dioxide for decolorization and bleaching;

[0113] S4 pickling treatment:

[0114] After the cowhide is bleached and decolorized, 100 g of deionized water, 11 g of sodium chloride and 15 g of sulfuric acid are added for pickling treatment;

[0115] S5 chrome-free tanning, squeezing out of drum:

[0116] Add 5g of urotropine and 8g of polyaluminium chloride to the leather after pickling for 1 hour, then add 7g of chromium-free zirconium tanning agent, control the temperature to react at 35°C for 4 hours, add acetic acid chloride for 1 hour, and finally let it stand for 1 day to complete the tanning;

[0117] The chrome-free zirconium tanning agent is selected from Dawitan ZR05 zirconium tanning agent, wherein the ZrO2 content is 32% and the pH value is 1.0;

[0118] S6. Peel, rinse and neutralize:

[0119] The tanned leather is sliced ​​and evenly peeled, and then 30g of deionized water and 8g of sodium bicarbonate are added for rinsing and neutralization;

[0120] S7, fatliquoring and retanning:

[0121] Add 5g of chrome-free retanning agent and 5g of castor oil phosphate to the rinsed and neutralized leather for fatliquoring;

[0122] S8, Vacuum softening:

[0123] The leather after fatliquoring and retanning is taken out of the drum and aired to dry, and then vacuum softened with a vacuum degree of -0.07MPa, a temperature controlled at 40°C, and a softening time of 3h. It is then trimmed, graded, and the finished products are put into storage.

[0124] Example 4

[0125] Reference Figure 1 , a baseball leather processing process, comprising the following steps:

[0126] S1 soaking and meat removal:

[0127] 50 g of yellow cattle hide was immersed in 100 g of deionized water, and 7 g of the composite degreasing agent prepared in Preparation Example 4 was added to perform flesh removal treatment;

[0128] S2 hair removal swelling and graying:

[0129] After the raw hide of the yellow cattle is de-fleshed, 100g of deionized water, 10g of sodium sulfide and 5g of slaked lime are added to perform dehairing, swelling and re-liming; then the de-fleshing equipment is used to de-flesh the gray hide, and the skin splitting machine is used to slice the gray hide;

[0130] S3 decolorization and bleaching:

[0131] Then add 100g of deionized water and 15g of oxalic acid for deashing and softening, and add 5g of formaldehyde and 5g of titanium dioxide for decolorization and bleaching;

[0132] S4 pickling treatment:

[0133] After the cowhide is bleached and decolorized, 100 g of deionized water, 8 g of sodium chloride and 13 g of sulfuric acid are added for pickling treatment;

[0134] S5 chrome-free tanning, squeezing out of drum:

[0135] Add 5g of urotropine and 8g of polyaluminium chloride to the leather after pickling for 1 hour, then add 7g of chromium-free zirconium tanning agent, control the temperature to react at 35°C for 4 hours, add acetic acid chloride for 1 hour, and finally let it stand for 1 day to complete the tanning;

[0136] The chrome-free zirconium tanning agent is selected from Dawitan ZR05 zirconium tanning agent, wherein the ZrO2 content is 32% and the pH value is 1.0;

[0137] S6. Peel, rinse and neutralize:

[0138] The tanned leather is sliced ​​and evenly peeled, and then 30g of deionized water and 8g of sodium bicarbonate are added for rinsing and neutralization;

[0139] S7, fatliquoring and retanning:

[0140] Add 5g of chrome-free retanning agent and 5g of sulfited neat's foot oil to the rinsed and neutralized leather for fatliquoring;

[0141] S8, Vacuum softening:

[0142] The leather after fatliquoring and retanning is taken out of the drum and aired to dry, and then vacuum softened, with the vacuum degree of -0.09MPa, the temperature controlled at 50℃, and the softening time of 4h. It is then trimmed, graded, and the finished products are put into storage.

[0143] Example 5

[0144] Reference Figure 1 , a baseball leather processing process, comprising the following steps:

[0145] S1 soaking and meat removal:

[0146] 50 g of yellow cattle hide was immersed in 100 g of deionized water, and 7 g of the composite degreasing agent prepared in Preparation Example 5 was added to perform flesh removal treatment;

[0147] S2 hair removal swelling and graying:

[0148] After the raw hide of the yellow cattle is de-fleshed, 100g of deionized water, 10g of sodium sulfide and 8g of slaked lime are added to perform dehairing, swelling and re-liming; then the de-fleshing equipment is used to de-flesh the gray hide, and the skin splitting machine is used to slice the gray hide;

[0149] S3 decolorization and bleaching:

[0150] Then add 100g of deionized water and 15g of oxalic acid for deashing and softening, and add 8g of formaldehyde and 7g of titanium dioxide for decolorization and bleaching;

[0151] S4 pickling treatment:

[0152] After the cowhide is bleached and decolorized, 100 g of deionized water, 9 g of sodium chloride and 13 g of sulfuric acid are added for pickling treatment;

[0153] S5 chrome-free tanning, squeezing out of drum:

[0154] After pickling, add 6g of urotropine and 10g of polyaluminium chloride to the leather for 1 hour, then add 8g of chromium-free zirconium tanning agent, and control the temperature to react for 4 hours at 35°C, add chloroacetic acid to fix for 1 hour, and finally let it stand for 1 day to complete the tanning;

[0155] The chrome-free zirconium tanning agent is selected from Dawitan ZR05 zirconium tanning agent, wherein the ZrO2 content is 32% and the pH value is 1.0;

[0156] S6. Peel, rinse and neutralize:

[0157] The tanned leather is sliced ​​and evenly peeled, and then 40g of deionized water and 10g of sodium bicarbonate are added for rinsing and neutralization;

[0158] S7, fatliquoring and retanning:

[0159] Add 8g of chrome-free retanning agent and 7g of sulfonated oil to the rinsed and neutralized leather for fatliquoring;

[0160] S8, Vacuum softening:

[0161] The leather after fatliquoring and retanning is taken out of the drum and aired to dry, and then vacuum softened, with the vacuum degree of -0.09MPa, the temperature controlled at 50℃, and the softening time of 4h. It is then trimmed, graded, and the finished products are put into storage.

[0162] Example 6

[0163] Reference Figure 1 , a baseball leather processing process, comprising the following steps:

[0164] S1 soaking and meat removal:

[0165] 50 g of yellow cattle hide was immersed in 100 g of deionized water, and 8 g of the composite degreasing agent prepared in Preparation Example 6 was added to perform flesh removal treatment;

[0166] S2 hair removal swelling and graying:

[0167] After the raw hide of the yellow cattle is de-fleshed, 100g of deionized water, 11g of sodium sulfide and 7g of slaked lime are added to perform dehairing, swelling and re-liming; then the de-fleshing equipment is used to de-flesh the gray hide, and the skin splitting machine is used to slice the gray hide;

[0168] S3 decolorization and bleaching:

[0169] Then add 100g of deionized water and 15g of oxalic acid for deashing and softening, and add 6g of formaldehyde and 8g of titanium dioxide for decolorization and bleaching;

[0170] S4 pickling treatment:

[0171] After the cowhide is bleached and decolorized, 100 g of deionized water, 9 g of sodium chloride and 13 g of sulfuric acid are added for pickling treatment;

[0172] S5 chrome-free tanning, squeezing out of drum:

[0173] Add 5g of urotropine and 8g of polyaluminium chloride to the leather after pickling for 1 hour, then add 7g of chromium-free zirconium tanning agent, control the temperature to react at 35°C for 4 hours, add acetic acid chloride for 1 hour, and finally let it stand for 1 day to complete the tanning;

[0174] The chrome-free zirconium tanning agent is selected from Dawitan ZR05 zirconium tanning agent, wherein the ZrO2 content is 34% and the pH value is 2.0;

[0175] S6. Peel, rinse and neutralize:

[0176] The tanned leather is sliced ​​and evenly peeled, and then 40g of deionized water and 10g of sodium bicarbonate are added for rinsing and neutralization;

[0177] S7, fatliquoring and retanning:

[0178] Add 5g of chrome-free retanning agent and 5g of sulfited neat's foot oil to the rinsed and neutralized leather for fatliquoring;

[0179] S8, Vacuum softening:

[0180] The leather after fatliquoring and retanning is taken out of the drum and aired to dry, and then vacuum softened, with the vacuum degree of -0.09MPa, the temperature controlled at 50℃, and the softening time of 4h. It is then trimmed, graded, and the finished products are put into storage.

[0181] Comparative Example 1

[0182] The difference between this comparative example and Example 1 is that the composite degreasing agent prepared in Preparation Example 4 is replaced by a common commercially available degreasing agent purchased from Jinan Baoliyuan Chemical Co., Ltd. with a CAS number of 68439-39-4.

[0183] Comparative Example 2

[0184] The difference between this comparative example and Example 1 is that the composite degreasing agent is prepared by compounding fatty alcohol polyoxyethylene ether sodium dodecyl sulfonate in a mass ratio of 7:1.

[0185] Comparative Example 3

[0186] The difference between this comparative example and Example 1 is that the composite degreasing agent is prepared by compounding the modified biological enzyme prepared in Preparation Example 1 and sodium dodecyl sulfate in a mass ratio of 7:3:1.

[0187] The leathers obtained in Examples 1-6 and Comparative Examples 1-3 were respectively subjected to water repellency, oil repellency, wear resistance and weather resistance tests.

[0188] Water repellent test: Water repellent test is carried out by using the water repellency tester GT-7033N (standard ASTM-D1913-2000); Notes: 1. 250mL of water must be sprayed within 25-30 seconds; 2. The sample holder is at an angle of 45° to the horizontal plane; 3. The center of the lower surface of the nozzle and the center of the sample surface are kept at a distance of 152.4mm; 4. Avoid lifting the test instrument by hand during the test to avoid affecting the experimental results.

[0189] Oil-proof test: Test according to the AATCC118 (oil-proof) standard of 3M Company of the United States. Use the standard oil in AATCC118 as the test oil, drop the test oil on the leather surface with a dropper, the leather area is 20cm×20cm, the droplet diameter is 3mm, drop 3 drops on different parts of the leather, observe for 30 seconds, if 2 drops of oil droplets in each part are not absorbed, it means it has passed, test the low-grade oil first, then test the high-grade oil, until it fails.

[0190] Abrasion resistance test: In an environment of 25°C and 50% RH, the sample is subjected to abrasion test using an abrasion resistance tester, with a load of 500g and a rotation speed of 500 revolutions, and the condition of the artificial leather surface after abrasion is observed.

[0191] Weather resistance test: Place the sample in a constant temperature and humidity sample box at 85℃ and 90%RH for 24 hours for aging, and then use a wear resistance tester to perform a wear test on the sample at 25℃ and 50%RH, with a load of 500g and a rotation speed of 500 revolutions, and observe the condition of the artificial leather surface after wear.

[0192] The test results are shown in Table 1.

[0193]

[0194]

[0195] It can be seen from the above table that the dynamic waterproof performance and oil repellency of Examples 1-6 are improved compared with those of Comparative Examples 1-3, and the baseball leathers prepared in Examples 1-6 have good wear resistance and weather resistance, and the wear resistance is still retained after wet heat aging, indicating that they have good performance in high temperature resistance and moisture resistance, and have excellent comprehensive application performance.

[0196] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A baseball leather processing process, characterized in that: The following steps are involved: S1 soaking and meat removal: The raw hide of yellow cattle is immersed in deionized water, and a composite degreasing agent is added to perform flesh removal treatment; S2 hair removal swelling and graying: After the raw hide of cattle is de-fleshed, deionized water, sodium sulfide and slaked lime are added to carry out dehairing, swelling and re-liming; then the de-fleshing equipment is used to de-flesh the gray hide, and the skin splitting machine is used to slice the gray hide; S3 decolorization and bleaching: Then add deionized water and oxalic acid for deashing and softening, and add formaldehyde and titanium dioxide for decolorization and bleaching; S4 pickling treatment: After bleaching and decoloring, the cowhide is pickled by adding deionized water, sodium chloride and sulfuric acid; S5 chrome-free tanning, squeezing out of drum: After the acid treatment, the leather material is added with urotropine and polyaluminium chloride for setting for 1 hour, then the chrome-free zirconium tanning agent is added, and the temperature is controlled at 35-42°C for reaction for 4-6 hours, acetic acid chloride is added for setting for 1 hour, and finally the tanning is completed by standing for 1 day; S6. Peel, rinse and neutralize: The tanned leather is sliced ​​and evenly peeled, and then deionized water and sodium bicarbonate are added for rinsing and neutralization; S7, fatliquoring and retanning: Adding chrome-free retanning agent and fatliquor to the rinsed and neutralized leather to carry out fatliquor retanning; S8, Vacuum softening: The leather after fatliquoring and retanning is taken out of the drum to dry, vacuum tumbled, trimmed and graded, and the finished products are stored.

2. A baseball leather processing process according to claim 1, characterized in that: The composite degreasing agent is prepared by compounding a surfactant, a modified biological enzyme, and sodium dodecyl sulfate in a mass ratio of 7-10:3-5:1-3.

3. A baseball leather processing process according to claim 1, characterized in that: The surfactant is a nonionic surfactant, and the nonionic surfactant is selected from one or a combination of fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, octanol polyoxyethylene ether, and lauryl alcohol polyoxyethylene ether.

4. A baseball leather processing process according to claim 1, characterized in that: The preparation method of the modified bioenzyme is as follows: S1-1, dissolving chitosanase in phosphate buffer to obtain a chitosanase solution with a concentration of 3.0-6.5 g / L; S1-2, prepare a nano-titanium dioxide suspension with a concentration of 4.5-6.0 mg / ml, and drop the chitosanase solution in S1-1 into the nano-titanium dioxide suspension, stir and mix evenly; S1-3, adding bismaleimide to carry out cross-linking curing reaction, then washing with deionized water, and then removing moisture by vacuum drying to obtain a modified bio-enzyme.

5. A baseball leather processing process according to claim 4, characterized in that: The particle size of the nano titanium dioxide is 45-55 nm.

6. The baseball leather processing process according to claim 1, characterized in that: The mass ratio of the composite degreasing agent to the deionized water in S1 is 7-10:

100.

7. The baseball leather processing process according to claim 1, characterized in that: The fatliquor is one or more of sulfonated oil, castor oil, castor oil phosphate, and sulfited neat's foot oil.

8. The baseball leather processing process according to claim 1, characterized in that: The mass ratio of deionized water, sodium chloride and sulfuric acid in S4 is 100:8-11:13-15.

9. The baseball leather processing process according to claim 1, characterized in that: The ZrO2 content of the chrome-free zirconium tanning agent in S5 is 32%-34%, and the pH value is 1.0-2.

0.

10. The baseball leather processing process according to claim 1, characterized in that: The vacuum degree in S8 is -0.07MPa to -0.09MPa, the temperature is controlled at 40-50°C, and the softening time is 3-4h.

Images