阅读说明：本技术 高耐光老化性能的聚氨酯超细纤维革及其制备方法与用途 (Polyurethane superfine fiber leather with high light aging resistance and preparation method and application thereof ) 是由 付丹 刘洲 郭刚 吴勇 杨银龙 于 2020-05-22 设计创作，主要内容包括：本发明公开了一种高耐光老化性能的聚氨酯超细纤维革及其制备方法与用途,属于高分子材料技术领域。该聚氨酯超细纤维革包括在基布层表面依次层叠的由聚氨酯树脂作为主要原料的皮层和表皮层,其中,皮层中含有红外光反射填料,表皮层中分散有红外光透射颜料。该超细纤维革不需要添加任何的紫外线吸收剂、抗氧剂,就具备优良的耐光老化性能,有效避免了超纤革在使用过程中由于紫外线吸收剂、抗氧剂等小分子物质迁移而产生的不良影响。其在汽车内饰产品中具备较好应用。(The invention discloses polyurethane superfine fiber leather with high light aging resistance, a preparation method and application thereof, and belongs to the technical field of high polymer materials. The polyurethane superfine fiber leather comprises a leather layer and an epidermal layer which are sequentially laminated on the surface of a base cloth layer and take polyurethane resin as a main raw material, wherein the leather layer contains infrared light reflection fillers, and infrared light transmission pigments are dispersed in the epidermal layer. The superfine fiber leather has excellent light aging resistance without adding any ultraviolet absorbent and antioxidant, and effectively avoids adverse effects caused by migration of small molecular substances such as the ultraviolet absorbent and the antioxidant in the use process of the superfine fiber leather. It has better application in the automotive interior products.)

1. The polyurethane superfine fiber leather with high light aging resistance is characterized by comprising a skin layer and a skin layer which are sequentially laminated on the surface of a base fabric layer and take polyurethane resin as a main raw material, wherein the skin layer contains infrared light reflection fillers, and infrared light transmission pigments are dispersed in the skin layer.

2. The polyurethane superfine fiber leather with high light aging resistance as claimed in claim 1, wherein the mass ratio of the polyurethane resin to the infrared light reflecting filler in the skin layer is 100 (1-40).

3. The polyurethane microfiber leather with high light aging resistance according to claim 2, wherein the infrared light reflective filler is at least one of pearlescent pigment, rutile type titanium dioxide or glass microsphere reflective pigment.

4. The polyurethane superfine fiber leather with high light aging resistance as claimed in claim 1, wherein the skin layer further contains a wetting dispersant for ensuring the dispersibility of the infrared light transmitting pigment, and the mass ratio of the polyurethane resin, the infrared light transmitting pigment and the wetting dispersant is 100 (1-20): 0.01-2.

5. The polyurethane ultrafine fiber leather with high light aging resistance according to claim 4, wherein the infrared light transmitting pigment is at least one of isoindolinone pigments, quinacridone pigments, lactam pigments or perylene pigments.

6. The polyurethane microfiber leather with high light aging resistance according to any one of claims 1 to 5, wherein an adhesive layer comprising a polyurethane adhesive is further disposed between the skin layer and the base fabric layer.

7. The polyurethane superfine fiber leather with high light aging resistance as claimed in any one of claims 1 to 5, wherein the base fabric layer is a superfine fiber synthetic leather base fabric which is prepared by taking a non-woven fabric as a base, soaking polyurethane solution in fiber gaps, solidifying, washing with water, reducing, drying and sizing.

8. The preparation method of the polyurethane superfine fiber leather with high light aging resistance is characterized by comprising an adhesive layer, a leather layer and a skin layer, wherein the adhesive layer is sequentially laminated on the surface of a base fabric layer, and the skin layer are mainly made of polyurethane resin, and the preparation method specifically comprises the following steps:

1) preparing epidermal layer slurry, skin layer slurry and adhesive layer slurry according to corresponding formulas, and selecting base cloth and release paper;

2) coating the surface layer slurry on the surface of release paper, and drying at 70-160 ℃; the epidermal layer slurry comprises the following components in parts by weight: 100 parts of polyurethane resin, 20-100 parts of solvent, 0.01-2 parts of wetting dispersant and 1-20 parts of infrared light transmission pigment;

3) coating the surface layer slurry on the surface of the product obtained in the step 2), and drying at 70-160 ℃; the cortex slurry comprises the following components in parts by weight: 100 parts of polyurethane resin, 20-100 parts of solvent and 1-40 parts of infrared light reflecting filler;

4) coating adhesive layer slurry on the surface of the product obtained in the step 3), attaching base cloth, drying, and removing release paper to obtain the polyurethane superfine fiber leather.

9. The method for preparing polyurethane microfiber leather with high light aging resistance according to claim 8, wherein the polyurethane resin in the skin layer slurry is the same or different from the polyurethane resin in the skin layer slurry, and the solvent is the same or different;

the polyurethane resin is a high-molecular polymer containing urethane groups on the main chain;

the solvent is at least one of toluene, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide or dimethylacetamide.

10. The application of the polyurethane superfine fiber leather with high light aging resistance is characterized by comprising the application in automobile interior decoration products.

Technical Field

The invention relates to a polyurethane fiber leather material, belongs to the technical field of high polymer materials, and particularly relates to polyurethane superfine fiber leather with high light aging resistance, and a preparation method and application thereof.

Background

Polyurethane superfine fiber leather, called microfiber leather for short, has been widely used as coating leather for parts such as seats, side door panels, steering wheels and the like of automobiles at present due to excellent texture and excellent wear resistance.

Among them, since the steering wheel of an automobile is directly irradiated with sunlight, the coated leather used as the steering wheel has a high demand for the light-resistant property of the material. At present, the light-resistant treatment of microfiber leather mainly has two approaches: (1) the surface coating material is polyurethane synthesized by adopting non-aromatic isocyanate and dihydric alcohol which does not contain easily yellowing groups such as ether groups, benzene ring groups and the like. The polyurethane coating prepared by the method has poor wear resistance and solvent resistance and high cost. (2) And adding light-resistant auxiliaries such as an antioxidant and an ultraviolet absorbent on the surface coating material to improve the light resistance of the material. The main problem of lightfast treatments in this way is that these treatments tend to cause the migration of certain chemical bonds in the auxiliary agents during use, which can affect the appearance and feel of the material, and sometimes can even be tacky.

The Chinese invention patent application (application publication No. CN109111840A, application publication date: 2019-01-01) discloses a photoaging resistance water-based surface treatment agent for automobile leather and a preparation method thereof, wherein the photoaging resistance water-based surface treatment agent comprises the following raw materials in parts by weight: 100 parts of waterborne polyurethane, 0.01-0.06 part of graphene, 2-8 parts of a waterborne cross-linking agent, 0.2-1 part of a waterborne flatting agent, 0.2-1 part of a waterborne defoaming agent, 0.3-3 parts of a waterborne hand feeling agent and 0.5-5 parts of a thickening agent; the symmetrical and perfect hexagonal connection of the graphene ensures that the structure of the graphene is very stable, and the graphene has good chemical stability and mechanical property; the invention greatly improves the light aging resistance of the automobile leather by utilizing the special structure of the graphene.

The Chinese invention patent application (application publication No. CN110077077A, application publication date: 2019-08-02) discloses a method for manufacturing a superfine fiber leather material for an automobile steering wheel. The method comprises the following steps of preparing the following raw materials by weight: the surface layer of the graphene polycarbonate is 15-25 g, the surface layer of the polycarbonate is 25-35 g, the foaming layer of the polyether polyurethane resin is 15-25 g, the bonding layer of the polyether polyurethane resin is 25-35 g, and the bottom layer of the flame-retardant microfiber bass is 575-585 g. The product of the invention has excellent weather resistance, chemical resistance and mechanical property; the wear resistance and the flame retardance are good; the tearing strength and the peeling strength are higher.

However, the above-mentioned research does not essentially solve the light aging resistance of microfiber leather.

The material aging caused by illumination is that the energy of light actually causes the destruction of some chemical bonds in the chemical structure of the material. In daily sunlight, the visible light accounts for 50%, the infrared light accounts for 43%, and the ultraviolet light accounts for 7% in terms of energy ratio. The content of infrared light is high, and if a method for preventing infrared light from acting on the material can be developed, the light aging resistance of the material can be greatly improved.

Disclosure of Invention

In order to solve the technical problems, the invention discloses polyurethane superfine fiber leather with high light aging resistance, a preparation method and application thereof. The superfine fiber leather has excellent light aging resistance without adding any ultraviolet absorbent and antioxidant, and effectively avoids adverse effects caused by migration of small molecular substances such as the ultraviolet absorbent and the antioxidant in the use process of the superfine fiber leather.

In order to achieve the purpose, the invention discloses polyurethane superfine fiber leather with high light aging resistance, which is characterized by comprising a skin layer and a skin layer which are sequentially laminated on the surface of a base fabric layer and take polyurethane resin as a main raw material, wherein the skin layer contains an infrared light reflection filler, and an infrared light transmission pigment is dispersed in the skin layer.

Furthermore, the mass ratio of the polyurethane resin to the infrared light reflecting filler in the skin layer is 100 (1-40).

Further, the infrared light reflecting filler is at least one of pearlescent pigment, rutile type titanium dioxide or glass bead reflecting pigment.

Furthermore, the surface layer also contains a wetting dispersant for ensuring the dispersibility of the infrared light transmission pigment, and the mass ratio of the polyurethane resin, the infrared light transmission pigment and the wetting dispersant is (1-20) to (0.01-2).

Further, the infrared light transmitting pigment is at least one of an isoindolinone pigment, a quinacridone pigment, a lactam pigment, or a perylene pigment.

Furthermore, an adhesive layer composed of polyurethane adhesive is arranged between the skin layer and the base cloth layer.

Furthermore, the base fabric layer is superfine fiber synthetic leather base fabric which is formed by taking non-woven fabric as a base, soaking polyurethane solution in fiber gaps, solidifying, washing, reducing, drying and sizing.

In order to better achieve the technical purpose of the invention, the invention also discloses a preparation method of the polyurethane superfine fiber leather with high light aging resistance, the polyurethane superfine fiber leather comprises an adhesive layer which is sequentially laminated on the surface of a base fabric layer, and a skin layer which take polyurethane resin as main raw materials, and the preparation method specifically comprises the following steps:

1) preparing epidermal layer slurry, skin layer slurry and adhesive layer slurry according to corresponding formulas, and selecting base cloth and release paper;

2) coating the surface layer slurry on the surface of release paper, and drying at 70-160 ℃; the epidermal layer slurry comprises the following components in parts by weight: 100 parts of polyurethane resin, 20-100 parts of solvent, 0.01-2 parts of wetting dispersant and 1-20 parts of infrared light transmission pigment;

3) coating the surface layer slurry on the surface of the product obtained in the step 2), and drying at 70-160 ℃; the cortex slurry comprises the following components in parts by weight: 100 parts of polyurethane resin, 20-100 parts of solvent and 1-40 parts of infrared light reflecting filler;

4) coating adhesive layer slurry on the surface of the product obtained in the step 3), attaching base cloth, drying, and removing release paper to obtain the polyurethane superfine fiber leather.

Further, the polyurethane resin in the skin layer slurry and the polyurethane resin in the skin layer slurry are the same or different, and the solvent is the same or different;

the polyurethane resin is a high-molecular polymer containing urethane groups on the main chain;

the solvent is at least one of toluene, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide or dimethylacetamide.

In addition, the invention also discloses application of the polyurethane superfine fiber leather with high light aging resistance, which is characterized by comprising application in automotive interior products. Particularly including use in an automotive steering wheel.

Has the advantages that:

1. the polyurethane superfine fiber leather designed by the invention comprises the surface layer and the skin layer, wherein the surface layer can be used for normally using colors and skin lines and can also allow infrared light to penetrate, the energy of the infrared light is prevented from damaging the structure of a leather coating material, the surface layer of the superfine fiber leather has excellent illumination aging resistance, and the skin layer has excellent infrared light reflection capacity, so that the infrared light can be effectively prevented from generating adverse effects on the interior of the superfine fiber leather coating, and the effect of improving the whole light resistance of the superfine fiber leather coating is achieved.

2. The polyurethane wetting dispersant is adopted in the surface layer of the polyurethane superfine fiber leather designed by the invention, and the assistant ensures that the infrared light transmission pigment is well dispersed in the surface layer slurry, the formed coating slurry has low viscosity and excellent color spreading of the coating, has excellent compatibility with the main polyurethane resin, and prevents the wetting dispersant from migrating to influence the quality of the material.

3. The polyurethane superfine fiber leather designed by the invention has excellent light aging resistance without adding any ultraviolet absorbent and antioxidant.

Drawings

FIG. 1 is a schematic structural diagram of microfiber leather designed according to the present invention;

wherein, each part in fig. 1 is numbered as follows:

base cloth layer 1, adhesive layer 2, skin layer 3, epidermal layer 4.

Detailed Description

The invention discloses polyurethane superfine fiber leather with high light aging resistance, which aims to solve the technical problems of the superfine fiber leather in the light-resistant treatment at present, and hopes to ensure the excellent light resistance, good wear resistance and good solvent resistance of the superfine fiber leather on the basis of not adding any micromolecular substances such as ultraviolet absorbent, antioxidant and the like.

A polyurethane superfine fiber leather with high light aging resistance is shown in figure 1, and comprises a skin layer 3 and a skin layer 4 which are sequentially laminated on the surface of a base fabric layer 1 and take polyurethane resin as a main raw material, wherein the skin layer 3 contains infrared light reflection fillers, and the skin layer 4 is dispersed with infrared light transmission fillers. The infrared light transmitting filler in the skin layer 4 helps to transmit infrared light through the skin layer and contributes to increase breathability of the overall fibrous leather material. Meanwhile, infrared light rays penetrate through the surface layer 4, enter the leather layer 3, are reflected by the infrared light reflection filler, and penetrate through the surface layer 4 again, so that the energy of the infrared light rays is not absorbed, and the phenomenon that the infrared light energy damages the structure of the leather coating material is effectively avoided. Wherein the mass ratio of the polyurethane resin to the infrared light reflecting filler in the skin layer is 100 (1-40). The components within this mass range enable the infrared light reflective filler to be dispersed sufficiently uniformly in the urethane resin molecular gaps.

Meanwhile, an adhesive layer 2 composed of polyurethane adhesive is arranged between the skin layer 3 and the base cloth layer 1.

Furthermore, in order to ensure that the infrared light reflecting filler in the skin layer 3 is well dispersed in the polyurethane resin, the infrared light reflecting filler is dissolved in the solvent. The solvent is at least one of toluene, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide or dimethylacetamide.

The polyurethane resin refers to a high molecular polymer containing urethane groups on the main chain, and specifically includes aromatic polyurethanes, such as polyurethane synthesized by aromatic isocyanate, aliphatic polyurethanes, such as polyurethane synthesized by aliphatic isocyanate, alicyclic polyurethanes, such as polyurethane synthesized by alicyclic isocyanate;

the infrared light reflecting filler is at least one of pearlescent pigment, rutile type titanium dioxide or glass bead reflecting pigment. The filler plays a role in reflecting infrared light, is beneficial to improving the wear resistance, heat resistance and flame retardance of the material, and the particle size of the filler is preferably 1-100 mu m.

In addition, the surface layer contains a wetting dispersant for ensuring the dispersibility of the infrared light transmission filler, and the wetting dispersant is a polyurethane dispersant and is characterized in that a series of carbamate groups or chain segments are uniformly distributed in a molecular chain, and tertiary amine groups and ring structures are used as anchoring groups. Meanwhile, the dispersant ensures that the infrared light transmission pigment is well dispersed in the epidermal layer slurry, so that the formed coating slurry has low viscosity and excellent color spreading of the coating, has excellent compatibility with the main polyurethane resin, and effectively avoids the influence on the quality of the material caused by the migration of the wetting dispersant.

The infrared light transmitting pigment is at least one of isoindolinone pigments, quinacridone pigments, lactam pigments or perylene pigments. Wherein the isoindolinone pigment comprises pigment yellow 109, pigment yellow 110, pigment yellow 138 or pigment yellow 139, and the quinacridone pigment comprises pigment red 122. The pigment not only has the function of infrared light transmission, but also has good color development effect in visible light.

In addition, a solvent is also added into the epidermal layer, and the solvent is at least one of toluene, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide or dimethylacetamide. The polyurethane resin in the skin layer refers to a high molecular polymer containing urethane groups in the main chain, and specifically includes aromatic polyurethanes such as polyurethane synthesized with aromatic isocyanate, aliphatic polyurethanes such as polyurethane synthesized with aliphatic isocyanate, and alicyclic polyurethanes such as polyurethane synthesized with alicyclic isocyanate. It is within the scope of the present invention to select the polyurethane resin and the solvent in the skin layer and the skin layer either simultaneously or differently. Meanwhile, the mass ratio of the polyurethane resin, the infrared light transmission filler and the wetting dispersant in the surface layer is 100 (1-20) to 0.01-2. The components in the mass range are beneficial to ensuring that the infrared light can be conveniently transmitted to the maximum degree on the basis of not influencing the resin property of the polyurethane.

The polyurethane adhesive is one of a liquid polyurethane resin or a two-liquid polyurethane resin.

The base cloth layer is superfine fiber synthetic leather base cloth which is formed by taking non-woven cloth as a base, soaking polyurethane solution in fiber gaps, solidifying, washing, reducing, drying and shaping.

In order to better achieve the technical purpose of the invention, the invention also discloses a preparation method of the polyurethane superfine fiber leather with high light aging resistance, the polyurethane superfine fiber leather comprises an adhesive layer which is sequentially laminated on the surface of a base fabric layer, and a skin layer which take polyurethane resin as main raw materials, and the preparation method specifically comprises the following steps:

1) preparing epidermal layer slurry, skin layer slurry and adhesive layer slurry according to corresponding formulas, and selecting base cloth and release paper;

2) coating the surface layer slurry on the surface of release paper, and drying at 70-160 ℃; the epidermal layer slurry comprises the following components in parts by weight: 100 parts of polyurethane resin, 20-100 parts of solvent, 0.01-2 parts of wetting dispersant and 1-20 parts of infrared light transmission pigment;

3) coating the surface layer slurry on the surface of the product obtained in the step 2), and drying at 70-160 ℃; the cortex slurry comprises the following components in parts by weight: 100 parts of polyurethane resin, 20-100 parts of solvent and 1-40 parts of infrared light reflecting filler;

4) coating adhesive layer slurry on the surface of the product obtained in the step 3), attaching base cloth, drying, and removing release paper to obtain the polyurethane superfine fiber leather.

Meanwhile, the polyurethane superfine fiber leather prepared by the invention can be used in automobile interior products, such as surface materials of automobile steering wheels.

In order to better describe the present invention, the following detailed description is given in conjunction with specific examples.

The following examples employ polyurethane resins: JF-S-8030 (aromatic polyurethane which is disclosed by Zhejiang Huafeng synthetic resin Co., Ltd.), JF-S-AH7040 (alicyclic polyurethane which is disclosed by Zhejiang Huafeng synthetic resin Co., Ltd.), JF-S-AH7090 (aliphatic polyurethane which is disclosed by Zhejiang Huafeng synthetic resin Co., Ltd.) JF-A-WV2010 (adhesive layer polyurethane resin which is disclosed by Zhejiang Huafeng synthetic resin Co., Ltd.).

The polyurethane type dispersant is DH-A035 dispersant of Federal Fine chemical Co., Ltd.

The perylene pigments are each of the type of PasteurBlack L0086 pigment andblack S0084 pigment.

Rutile titanium dioxide is an Altiris 550 pigment and an Altiris 800 pigment from hensmei.

The infrared light reflecting pigment is BasffSeries of pigments and

series of pigments.

Pearlescent pigment: y402 silver black (hangzhou yayo technologies ltd).

The common carbon black pigment is MA-100 black pigment from Mitsubishi corporation of Japan.

The base cloth is as follows: the black flame-retardant polyurethane superfine fiber synthetic leather base cloth with the thickness of 1.2 mm can be purchased from the market, and can also be prepared by a method disclosed in the literature synthetic leather materials and technology (Qujiabo et al. synthetic leather materials and technology [ M ]. Beijing: chemical industry publishers, 2015.).

The release paper is DE-7C release paper of Dainippon printing DNP company.