阅读说明：本技术 一种足球革及其制备方法 (Football leather and preparation method thereof ) 是由 李炎 高国华 高金岗 于 2020-12-30 设计创作，主要内容包括：本发明涉及一种足球革及其制备方法,该足球革包括依次设置的基布层、干法PU底层、干法PU中间层、水性不黄变PU面层及表面处理层,其中,水性不黄变PU面层中的PU树脂采用特定水性脂肪族PU树脂,不仅解决耐黄变问题,且与PU中间层的接着力较好,大大降低现有的水性PU树脂层与PU中间层的分离现象,还具有不黄变性,同时配合特定表面处理层和PU底层、PU中间层及基布层的使用,使得该足球革不仅满足足球革的耐磨、耐紫外、耐水解、耐老化,还满足防油污、环保等性能,尤其是表面处理层的原料涂刷在PU面层经高温后树脂与交联剂进行交联反应形成致密膜,进一步提高足球革的防水及耐磨性能。(The invention relates to football leather and a preparation method thereof, the football leather comprises a base cloth layer, a dry-method PU bottom layer, a dry-method PU middle layer, a water-based non-yellowing PU surface layer and a surface treatment layer which are sequentially arranged, wherein the PU resin in the aqueous non-yellowing PU surface layer adopts specific aqueous aliphatic PU resin, which not only solves the yellowing resistance problem, and has better adhesion with the PU middle layer, greatly reduces the separation phenomenon of the prior waterborne PU resin layer and the PU middle layer, has no yellowing property, meanwhile, the football leather is matched with a specific surface treatment layer, a PU bottom layer, a PU middle layer and a base cloth layer, so that the football leather not only meets the performances of wear resistance, ultraviolet resistance, hydrolysis resistance and aging resistance, but also meets the performances of oil stain resistance, environmental protection and the like, particularly, after the raw material of the surface treatment layer is coated on the PU surface layer, the resin and a cross-linking agent are subjected to cross-linking reaction to form a compact film, and the waterproof and wear-resisting performances of the football leather are further improved.)

1. The utility model provides a football leather, includes the base cloth layer, its characterized in that: the football leather also comprises a dry PU bottom layer, a dry PU middle layer, a water-based non-yellowing PU surface layer and a surface treatment layer which are arranged on the base cloth layer in sequence, wherein,

the raw material formula of the water-based non-yellowing PU surface layer comprises the following components in parts by weight:

90-110 parts of waterborne aliphatic PU resin;

0.1-1 part of a thickening agent;

5-10 parts of water-based color paste;

0.5-1 part of a leveling agent;

the waterborne aliphatic PU resin is Huafeng JF-PDY-877 HY;

the raw material formula of the surface treatment layer comprises the following components in parts by weight:

5-10 parts of a first water-based resin;

1-5 parts of a second water-based resin;

0.01-0.05 part of printing auxiliary agent;

0.5-1 part of wear-resistant auxiliary agent;

0.1-0.5 part of a slipping auxiliary agent;

0.5-1 part of a crosslinking agent;

0.05-0.15 part of a leveling agent;

0.01-0.1 part of thickening agent;

0.5-2 parts of water;

the first aqueous resin is Rust-13-085, and the second aqueous resin is Rust-21-826.

2. The soccer leather of claim 1, wherein: the water-based non-yellowing PU surface layer is a dry-process PU surface layer, and the thickness of the surface layer is 0.03 +/-0.005 mm.

3. The soccer leather of claim 1, wherein: the water-based color paste is S19-LR 08.

4. The football leather of claim 1, wherein the raw material formula of the dry-process PU middle layer comprises the following components in parts by weight:

90-110 parts of first dry-method PU resin;

5-10 parts of second dry-process PU resin;

0.5-1 part of a leveling agent;

50-60 parts of a first filler;

5-15 parts of color paste;

the first dry-process PU resin is JF-HSY-F9176A of Huafeng, and the second dry-process PU resin is JX-25 of Huafeng.

5. The soccer leather of claim 4, wherein: the first filler is light calcium carbonate.

6. The football leather of claim 1, wherein the raw material formula of the dry-process PU bottom layer comprises the following components in parts by weight:

90-110 parts of a third dry-process PU resin;

0.5-2 parts of fourth dry method PU resin

0.1-1 part of dry process auxiliary agent;

10-30 parts of a second filler;

the third dry-process PU resin is JF-HSY-F9212A of Huafeng, and the fourth dry-process PU resin is JF-BY-100 of Huafeng.

7. The soccer leather of claim 6, wherein: the dry process auxiliary agent is BY-300, and the second filler is calcium powder.

8. The soccer leather of claim 1, wherein: the thickness of the dry-method PU bottom layer is 0.05 +/-0.005 mm, and the thickness of the dry-method PU middle layer is 0.2 +/-0.02 mm.

9. The soccer leather of claim 1, wherein: the thickness of the base cloth layer is 0.7 +/-0.03 mm.

10. A method for preparing football leather as claimed in any one of claims 1 to 9, comprising the steps of:

(1) according to the formula, uniformly stirring and mixing the aqueous aliphatic PU resin, the aqueous color paste, the thickening agent and the leveling agent to prepare first mixed slurry, coating the first mixed slurry on the surface of release paper, and drying to form an aqueous PU surface layer;

(2) according to the formula, uniformly stirring and mixing the first dry-process PU resin, the second dry-process PU resin, the color paste, the first filler and the leveling agent to prepare second mixed slurry, coating the second mixed slurry on the surface of the aqueous PU surface layer prepared in the step (1), drying, and forming a PU middle layer on the PU surface layer;

(3) according to the raw material formula of the PU bottom layer, mixing, stirring and defoaming a third dry-method PU resin, a fourth dry-method PU resin, a second filler and a dry-method auxiliary agent to prepare a third mixture slurry, coating the third mixture slurry on the surface of the dry-method PU middle layer prepared in the step (2), drying to be semi-dry, attaching a base fabric on the surface to form the dry-method PU bottom layer, and stripping release paper after drying to prepare a leather semi-finished product;

(4) according to the raw material formula of the surface treatment layer, uniformly stirring and mixing a first water-based resin, a second water-based resin, a printing auxiliary agent, a wear-resistant auxiliary agent, a slipping auxiliary agent, a cross-linking agent, a leveling agent, a thickening agent and water to prepare a first surface treatment agent, printing the first surface treatment agent on the surface of the water-based PU surface layer of the leather semi-finished product, and drying to form the surface treatment layer.

Technical Field

The invention belongs to the technical field of synthetic leather, and particularly relates to football leather and a preparation method thereof.

Background

In recent years, the application field of synthetic leather is continuously developed, and ball leather products are developed more and more widely, such as basketball leather, football leather, volleyball leather and the like, and physical properties required by different ball leather products are different, such as the requirement of the basketball leather on fullness and elasticity, mechanical strength, chemical resistance, moisture absorption and sweat releasing performance, slip resistance and the like; the volleyball leather is required to be fine in leather surface, full and elastic, uniform in thickness, small in elongation, basically consistent in longitudinal direction and transverse direction, lighter and softer than basketball leather, not loose and not cracked, and good in wear resistance and waterproofness; the football leather is slightly thicker than volleyball leather, and is required to have the properties of wear resistance, ultraviolet resistance, hydrolysis resistance, aging resistance, water resistance, oil resistance, environmental protection and the like.

However, the existing football leather is generally an oily PU product, a PVC product or a TPU product, which is deficient in environmental protection, and the dosage of the oily PU product, the PVC product or the TPU product is gradually reduced under the current situation of advocating environmental protection.

An environment-friendly football leather prepared by water-based PU (polyurethane) has also been developed, for example, a preparation method of an environment-friendly high-peel polyurethane/foam composite football leather disclosed in Chinese patent CN109023975A, wherein firstly, water-based polyurethane surface layer slurry is coated on release paper by scraping, a polyurethane synthetic leather surface layer is prepared after drying, then, closed aliphatic polyurethane middle layer slurry is coated on the surface layer by scraping, and a polyurethane synthetic leather middle layer is prepared after drying; and then, casting and coating the solvent-free bi-component polyurethane adhesive layer resin on the surface of the middle layer, attaching the foam elastic base material after drying to a semi-dry state, continuing to react, and finally stripping the synthetic leather from the release paper to obtain the football leather. However, the PU surface layer of the football leather is not treated, and the wear resistance and the scratch resistance are not ensured.

Chinese patent CN107558249A discloses a preparation method of special leather for football, which comprises the steps of firstly coating calcium nitrate treatment liquid on the surface of non-woven fabric, coating waterborne polyurethane batch foamed by a foaming machine on the surface of the treated non-woven fabric, and drying step by a 30-meter oven at the temperature of 110-135 ℃ to prepare a high-strength waterborne polyurethane foaming layer for later use; coating the thickness of the anti-bending waterborne polyurethane on the plain paper by using dry-method plain paper as a surface layer, drying the surface layer by using a 30-meter oven at the temperature of 95-125 ℃, coating an adhesive layer with the thickness of 0.13mm, drying the adhesive layer to be semi-dry, sticking the foaming layer for use on the adhesive layer by using a rubber wheel with proper pressure, drying the foaming layer in the 30-meter oven at the temperature of 125-145 ℃, and rolling and separating to prepare the plain synthetic leather; heating the plain synthetic leather by an embossing machine at 190-210 ℃ and then pressing football patterns to obtain the special football leather. However, the special football leather does not perform surface treatment on the PU surface layer, the wear resistance and the scratch resistance are not guaranteed, the base cloth is coated with calcium nitrate treatment liquid, the preparation method is complex in process, and the steps are complex.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide football leather with oil resistance, water resistance, ultraviolet resistance, yellowing resistance and high environmental protection and a preparation method thereof.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

a football leather, which comprises a base cloth layer, and also comprises a dry PU bottom layer, a dry PU middle layer, a water-based non-yellowing PU surface layer and a surface treatment layer which are arranged on the base cloth layer in sequence, wherein,

the raw material formula of the water-based non-yellowing PU surface layer comprises the following components in parts by weight:

the waterborne aliphatic PU resin is Huafeng JF-PDY-877 HY.

According to some preferred and specific embodiments of the present invention, the aqueous color paste is Maifang S19-LR 08.

According to some embodiments of the present invention, the raw material formulation of the surface treatment layer comprises the following components in parts by weight:

the first aqueous resin is Rust-13-085, and the second aqueous resin is Rust-21-826.

According to some preferred and specific embodiments of the invention, the cross-linking agent is Starter's XR-28-404.

According to some embodiment aspects of the invention, the printing aid is stahl DF-2459.

According to some preferred and specific embodiments of the present invention, the aqueous non-yellowing PU top layer is a dry PU top layer having a thickness of 0.03 ± 0.005 mm.

According to some embodiments of the invention, the raw material formulation of the dry-process PU interlayer comprises the following components in parts by weight:

the first dry-process PU resin is JF-HSY-F9176A of Huafeng, and the second dry-process PU resin is JX-25 of Huafeng.

According to some preferred and specific embodiments of the invention, the first filler is light calcium carbonate. The color paste is HP-FP-1849 of Huapu.

According to some embodiments of the invention, the raw material formula of the dry-process PU bottom layer comprises the following components in parts by weight:

the third dry-process PU resin is JF-HSY-F9212A of Huafeng, and the fourth dry-process PU resin is JF-BY-100 of Huafeng.

According to some preferred and specific embodiments of the present invention, the dry-process aid is BY-300 of Huafeng and the second filler is calcium powder.

According to some preferred and specific embodiments of the present invention, the thickness of the dry PU bottom layer is 0.05 ± 0.005mm, and the thickness of the dry PU middle layer is 0.2 ± 0.02 mm.

According to some preferred and specific embodiments of the present invention, the base fabric layer is a warp knit fabric having a thickness of 0.7 ± 0.03 mm. Such as 250g white warp knitted fabric of Jiangsu Beltefu new materials Co.

The invention adopts another technical scheme that: a preparation method of the football leather comprises the following steps:

(1) according to the formula, uniformly stirring and mixing the aqueous aliphatic PU resin, the aqueous color paste, the thickening agent and the leveling agent to prepare first mixed slurry, coating the first mixed slurry on the surface of release paper, and drying to form an aqueous PU surface layer;

(2) according to the formula, uniformly stirring and mixing the first dry-process PU resin, the second dry-process PU resin, the color paste, the first filler and the leveling agent to prepare second mixed slurry, coating the second mixed slurry on the surface of the aqueous PU surface layer prepared in the step (1), drying, and forming a PU middle layer on the PU surface layer;

(3) according to the raw material formula of the PU bottom layer, mixing, stirring and defoaming a third dry-method PU resin, a fourth dry-method PU resin, a second filler and a dry-method auxiliary agent to prepare a third mixture slurry, coating the third mixture slurry on the surface of the dry-method PU middle layer prepared in the step (2), drying to be semi-dry, attaching a base fabric on the surface to form the dry-method PU bottom layer, and stripping release paper after drying to prepare a leather semi-finished product;

(4) according to the raw material formula of the surface treatment layer, uniformly stirring and mixing a first water-based resin, a second water-based resin, a printing auxiliary agent, a wear-resistant auxiliary agent, a slipping auxiliary agent, a cross-linking agent, a leveling agent, a thickening agent and water to prepare a first surface treatment agent, printing the first surface treatment agent on the surface of the water-based PU surface layer of the leather semi-finished product, and drying to form the surface treatment layer.

Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:

the football leather is prepared by selecting the specific water-based aliphatic PU resin as the main body material of the PU surface layer, so that the PU surface layer not only can have better adhesion with the PU middle layer, the separation phenomenon of the existing water-based PU resin and the PU middle layer is greatly reduced, but also has no yellowing property, and the football leather not only meets the performances of wear resistance, ultraviolet resistance, hydrolysis resistance and aging resistance of the football leather, but also meets the performances of oil stain resistance, environmental protection and the like by matching with the specific surface treatment layer, the PU middle layer and the base cloth layer, particularly, the resin and the cross-linking agent are subjected to cross-linking reaction to form a compact film after the raw material of the surface treatment layer is coated on the PU surface layer at high temperature, and the waterproof and wear-resistant performances of the football leather are further improved.

Detailed Description

Specific embodiments of the present invention will be described in further detail with reference to specific examples, but the scope of the present invention is not limited thereto.

Example 1

The football leather that this embodiment provided, this football leather is including base cloth layer, dry process PU bottom, dry process PU intermediate level, waterborne no yellowing PU surface course and the surface treatment layer that sets gradually, and the raw materials formula of dry process PU bottom, dry process PU intermediate level and the surface treatment layer of this football leather is seen table 1~ 2 and is shown.

In this example, 250g of white warp knitted fabric from Jiangsu Beltefu New Material Co.

In this example, the raw materials of the aqueous non-yellowing PU top layer consisted of the following components: 100 parts of Huafeng JF-PDY-877HY aqueous aliphatic PU resin, 8 parts of wheat color S19-LR08 aqueous color paste, 0.8 part of levelling agent of ifenprodil and 0.4 part of thickener of ifenprodil.

The football leather is prepared by the following steps:

(1) according to the formula, uniformly stirring and mixing the aqueous aliphatic PU resin, the aqueous color paste, the thickening agent and the leveling agent to prepare first mixed slurry, coating the first mixed slurry on the surface of release paper, and drying at 100 ℃ to form an aqueous PU surface layer;

(2) according to the formula, uniformly stirring and mixing the first dry-method PU resin, the second dry-method PU resin, the color paste, the first filler and the flatting agent to prepare second mixed slurry, coating the second mixed slurry on the surface of the aqueous non-yellowing PU surface layer prepared in the step (1), drying at 130 ℃, and forming a PU middle layer on the PU surface layer;

(3) according to the raw material formula of the PU bottom layer, mixing, stirring and defoaming a third dry-method PU resin, a fourth dry-method PU resin, a second filler and a dry-method auxiliary agent to prepare a third mixture slurry, coating the third mixture slurry on the surface of the dry-method PU middle layer prepared in the step (2), drying to be semi-dry at 110 ℃, attaching a base fabric on the third mixture slurry to form a dry-method PU bottom layer, drying at 140 ℃, and peeling release paper to prepare a leather semi-finished product;

(4) according to the raw material formula of the surface treatment layer, uniformly stirring and mixing a first water-based resin, a second water-based resin, a printing auxiliary agent, a wear-resistant auxiliary agent, a slipping auxiliary agent, a cross-linking agent, a leveling agent, a thickening agent and water to prepare a first surface treatment agent, printing the first surface treatment agent on the surface of the water-based PU surface layer of the leather semi-finished product, and drying at 135 ℃ to form the surface treatment layer.

Comparative example 1

The football leather provided by the embodiment is different from the football leather provided by the embodiment 1 in that: the base cloth layer is selected differently, in this example, the base cloth layer adopts 100D double-sided healthy cloth.

Comparative example 2

The football leather provided by the embodiment is different from the football leather provided by the embodiment 1 in that: the first dry-process PU resin in the dry-process PU intermediate layer is different from the first dry-process PU resin in the dry-process PU intermediate layer in selection, and in the embodiment, the first dry-process PU resin in the dry-process PU intermediate layer adopts Huafeng JF-HSY-9041A resin.

Comparative example 3

The football leather provided by the embodiment is different from the football leather provided by the embodiment 1 in that: the PU resin in the PU surface layer is different, in the example, the JF-PDY-877HY waterborne aliphatic PU resin in the example 1 is replaced by Huafeng JF-PDY-850H.

Comparative example 4

The football leather provided by the embodiment is different from the football leather provided by the embodiment 1 in that: the PU resin in the PU surface layer is different, in the example, the JF-PDY-877HY waterborne aliphatic PU resin in the example 1 is replaced by Huafeng JF-PDY-846HY in the PU surface layer.

Comparative example 5

The football leather provided by the embodiment is different from the football leather provided by the embodiment 1 in that: the aqueous resin and the cross-linking agent in the surface treatment layer are different, in this example, the first aqueous resin adopts Sancheng SS-A to replace RU-13-085 in example 1, the second aqueous resin adopts Sancheng SMATT-700 to replace WD-21-826 in example 1, and the cross-linking agent adopts Sancheng SS-B to replace XR-28-404 in example 1, wherein the specific raw material formulA is shown in Table 1.

Comparative example 6

The football leather provided by the embodiment is different from the football leather provided by the embodiment 1 in that: the aqueous resin and the cross-linking agent in the surface treatment layer are different, in this example, the first aqueous resin adopts Sancheng SS-A to replace RU-13-085 in example 1, the second aqueous resin adopts Sancheng SMATT-700 to replace WD-21-826 in example 1, and the cross-linking agent adopts Sancheng SS-B to replace XR-28-404 in example 1, wherein the specific raw material formulA is shown in Table 1.

Comparative example 7

The football leather provided by the embodiment is different from the football leather provided by the embodiment 1 in that: no filler is added into the dry-method PU middle layer and the PU bottom layer, and the specific raw material formula is shown in Table 2.

Table 1 shows the raw material formulations of the surface treatment layers of example 1 and comparative examples 5 to 6

In Table 1, DF-2459 is selected as A printing aid, HM-186 is selected as an abrasion-resistant aid, HM-13-678 is selected as A slipping aid, LA-91-120 is selected as A leveling agent, RM-4456 is selected as A thickening agent, and both are from Stadel, RU-13-085 is derived from Stadel in example 1, WD-21-826 is derived from Stadel is derived from A first aqueous resin, XR-28-404 is derived from Stadel is derived from A crosslinking agent, SS-A is derived from Sandel, SMATT-700 is derived from Sandel and SS-B is derived from Sandel in comparative examples 5 and 6.

Table 2 shows the raw material formulations of the dry PU middle layer and the dry PU bottom layer of the soccer ball leather of example 1 and comparative example 7

In Table 2, the first dry-process PU resin, the second dry-process PU resin, the third dry-process PU resin, the fourth dry-process PU resin, the first filler, the second filler, the first leveling aid and the second leveling aid are all JF-HSY-F9176A, JX-25, JF-HSY-F9212 and 9212A, respectively, the first dry-process PU resin, the fourth dry-process PU resin, the first filler, the second filler, the first leveling aid and the second leveling aid are all JF-BY-100, respectively, the first filler, the second filler, the first leveling aid and the second leveling aid are all light calcium carbonate, the first leveling aid and the second leveling aid are all derived from Huafeng, the dry-process aids are all derived from BY-300, and the color paste is all derived from HP-FP-1849.

Evaluation method

The football leather prepared in example 1 and comparative examples 1-7 was subjected to performance tests, and the test results are shown in table 3.

Table 3 shows the results of the performance tests of the soccer leathers prepared in example 1 and comparative examples 1 to 7

The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.