阅读说明：本技术 一种半硅合成革及其制备方法 (Semi-silicon synthetic leather and preparation method thereof ) 是由 赵永峰 汤立洋 王伟 于 2020-06-10 设计创作，主要内容包括：本发明公开了一种半硅合成革及其制备方法。半硅合成革依次由基布、粘接层、面层、表处层组成,面层由以下重量份数的组分组成：面层树脂100份；二甲基甲酰胺38-45份；丁酮18-21份；色料8-10份；所述面层树脂由20-50份的硅改性聚氨酯树脂和余量的基础树脂组成；表处层由以下重量份数的组分组成：侧链含氟乙烯基硅树脂40-75份；乙烯基聚硅氮烷2-25份；含氢硅油3-20份；有机溶剂30-70份；粘接附着剂0.5-18份；铂催化剂0.001-1份；促进剂0.5-10份；抑制剂0.0001-0.1份；填料8-40份。本发明的半硅合成革其具有防脏污,亲肤性好同时成本适宜的优点。(The invention discloses semi-silicon synthetic leather and a preparation method thereof. The semi-silicon synthetic leather sequentially comprises base cloth, an adhesive layer, a surface layer and a surface layer, wherein the surface layer comprises the following components in parts by weight: 100 parts of surface resin; 38-45 parts of dimethylformamide; 18-21 parts of butanone; 8-10 parts of a pigment; the surface layer resin consists of 20-50 parts of silicon modified polyurethane resin and the balance of base resin; the surface layer consists of the following components in parts by weight: 40-75 parts of side chain fluorine-containing vinyl silicon resin; 2-25 parts of vinyl polysilazane; 3-20 parts of hydrogen-containing silicone oil; 30-70 parts of an organic solvent; 0.5-18 parts of adhesive; 0.001-1 part of platinum catalyst; 0.5-10 parts of an accelerator; 0.0001 to 0.1 portion of inhibitor; 8-40 parts of a filler. The semi-silicon synthetic leather has the advantages of dirt resistance, good skin-friendly property and proper cost.)

1. The semi-silicon synthetic leather is characterized by sequentially comprising base cloth, an adhesive layer, a surface layer and a surface layer, wherein the surface layer comprises the following components in parts by weight:

100 parts of surface resin;

38-45 parts of dimethylformamide;

18-21 parts of butanone;

8-10 parts of a pigment;

the surface layer resin consists of 20-50 parts of silicon modified polyurethane resin and the balance of base resin;

the surface layer consists of the following components in parts by weight:

40-75 parts of side chain fluorine-containing vinyl silicon resin;

2-25 parts of vinyl polysilazane;

3-20 parts of hydrogen-containing silicone oil;

30-70 parts of an organic solvent;

0.5-18 parts of adhesive;

0.001-1 part of platinum catalyst; 0.5-10 parts of an accelerator;

0.0001 to 0.1 portion of inhibitor;

8-40 parts of a filler.

2. A semi-silicone synthetic leather according to claim 1, wherein the top resin is composed of 25-30 parts of silicone modified polyurethane resin and the balance of base resin.

3. The semi-silicone synthetic leather according to claim 2, wherein the base resin is prepared from the following components in parts by weight of 1: (0.2-0.3) polyurethane resin and thermosetting acrylic resin.

4. A semi-silicone synthetic leather according to claim 1, wherein the accelerator is polydimethylsiloxane, which contains silicon atoms connecting 3 hydrogen atoms, the hydrogen atoms are located at terminal positions or side chains, and the content of the hydrogen atoms is 0.3-1.6%.

5. The semi-silicone synthetic leather of claim 1, wherein the adhesive bonding agent is a hydrolysate of at least one of γ - (methacryloyloxy) propyltrimethoxysilane, 2- (3, 4-epoxycyclohexane) ethyltriethoxysilane, and tris (2-hydroxyethyl) isocyanurate triacrylate.

6. The semi-silicone synthetic leather according to claim 1, wherein the filler is at least one of aluminum hydroxide, aluminum oxide, magnesium hydroxide, zinc borate, aluminum silicate, calcium carbonate, magnesium carbonate, glass beads, white carbon black, silicone resin micro powder, silicon dioxide, calcium carbonate and magnesium oxide with a particle size of 800-1250 mesh.

7. A semi-silicone synthetic leather according to claim 1, wherein the adhesive layer is foamed solvent-free polyurethane.

8. The preparation method of the semi-silicon synthetic leather of claims 1 to 7, which is characterized by comprising the following steps:

preparing a surface layer: weighing surface layer resin, dimethyl formamide, butanone and pigment, and stirring at the temperature of 30-50 ℃ and the stirring speed of 800-1500r/min for 30min for later use;

preparation of the surface layer: weighing and mixing side chain fluorine-containing vinyl silicone resin, vinyl polysilazane, hydrogen-containing silicone oil, an organic solvent, an adhesive, an inhibitor and a filler, mixing at the temperature of 30-50 ℃ and under the stirring condition of 800-;

s1: coating the surface layer on release paper by 0.2 +/-0.02 mm, and drying at 70-130 ℃;

s2: coating a bonding layer with the thickness of 0.4 +/-0.05 mm on the surface layer, compounding the bonding layer with the base cloth, drying and curing at the temperature of 70-120 ℃ to realize the molding of the surface layer, the bonding layer and the base cloth;

s3: printing the surface layer on the surface layer by using a 80-200 mesh screen roller or a rolling way, and drying at the temperature of 130-150 ℃ for 1-3 min.

Technical Field

The invention relates to the technical field of synthetic leather, in particular to semi-silicon synthetic leather and a preparation method thereof.

Background

The synthetic leather is a plastic product which simulates the composition and structure of natural leather and can be used as a substitute material, the front and back surfaces of the synthetic leather are very similar to leather, and the synthetic leather has certain air permeability and is widely applied to shoes, boots, bags, vehicle decorations and clothes.

Due to the unique structure of the organic silicon, the organic silicon has the performances of inorganic materials and organic materials, and has excellent high and low temperature resistance, weather resistance, low surface tension, physiological inertia, good film forming property, air permeability and hydrophobicity; meanwhile, the peculiar anti-fouling function of the organic silicon product enables the organic silicon product to be widely applied to the preparation of leather with a self-cleaning function.

The Chinese patent with the publication number of CN109023984A and the publication number of 2018, 12 and 18 discloses high-weather-resistance environment-friendly organic silicon synthetic leather and a preparation method thereof, the organic silicon synthetic leather sequentially comprises a surface layer, an adhesive layer, base cloth and a surface treatment layer from top to bottom, wherein the surface layer comprises two-component polysiloxane surface layer resin, a wear-resistant assistant and color paste, the adhesive layer comprises two-component polysiloxane adhesive layer resin, an adhesive assistant and color paste, and the surface treatment layer comprises two-component polymethylsiloxane modified resin and a platinum metal catalyst.

Among the above-mentioned prior art, its main surface course component is organic silicon resin, though has fine antifouling easy clean function, but its mechanical properties is relatively poor, and wear resistance can be than PU synthetic leather and PVC synthetic leather commonly used by the ratio can be different by a lot, and the cost can be very high moreover, makes its application receive very big restriction.

Disclosure of Invention

Aiming at the defects in the prior art, the first purpose of the invention is to provide the semi-silicon synthetic leather which has the advantages of good mechanical property, good wear resistance and low cost.

The second purpose of the invention is to provide a preparation method of semi-silicon synthetic leather, which has the advantages of obtaining uniform synthetic leather with good bonding between layers.

In order to achieve the first object, the invention provides the following technical scheme: the semi-silicon synthetic leather sequentially comprises base cloth, an adhesive layer, a surface layer and a surface layer, wherein the surface layer comprises the following components in parts by weight:

100 parts of surface resin;

38-45 parts of dimethylformamide;

18-21 parts of butanone;

8-10 parts of a pigment;

the surface layer resin consists of 20-50 parts of silicon modified polyurethane resin and the balance of base resin;

the surface layer consists of the following components in parts by weight:

40-75 parts of side chain fluorine-containing vinyl silicon resin;

2-25 parts of vinyl polysilazane;

3-20 parts of hydrogen-containing silicone oil;

30-70 parts of an organic solvent;

0.5-18 parts of adhesive;

0.001-1 part of platinum catalyst;

0.5-10 parts of an accelerator;

0.0001 to 0.1 portion of inhibitor;

8-40 parts of a filler.

By adopting the technical scheme, the semi-silicon synthetic leather consists of the base cloth, the bonding layer, the surface layer and the surface layer, combines polyurethane and silicon, and has comprehensive mechanical property, cost and wear resistance. The surface layer resin in the surface layer comprises silicon modified polyurethane resin, the silicon modified polyurethane resin is formed by crosslinking organic silicon oligomer and polyurethane resin, the introduction of the organic silicon provides flexibility and skin-friendly property for the surface layer, and the polyurethane resin is crosslinked with the polyurethane resin, so that the polyurethane resin provides excellent mechanical property for the surface layer.

The top layer is attached to the outer surface of the top layer and consists of side chain fluorinated vinyl silicone resin and vinyl polysilazane. The side chain fluorine-containing vinyl silicon resin takes a-Si-O-bond as a main chain, is soft and smooth, is anti-fouling and easy to clean, contains vinyl and introduces fluorine atoms into the side chain, and the fluorine atoms of the side chain enable the surface of the synthetic leather to be smoother and are not easy to be stained and dirty, so that the synthetic leather with excellent performance in the aspects of easy cleaning and anti-fouling is obtained. Is very suitable for making baby products.

The vinyl polysilazane takes-Si-NH-Si-as a main chain, and a side chain is connected with vinyl; the-Si-NH-Si-can be cured at room temperature, and can promote the reaction with the Si-H bond of the silicon resin after being matched with the catalyst, so as to promote the curing and form a three-dimensional crosslinking structure. On the other hand, -Si-NH-Si-contains polar groups, and nitrogen atoms are easy to form intramolecular hydrogen bonds, so that the intermolecular bonding strength is improved; and-Si-NH-Si-can react with polar functional groups in the surface layer, can greatly improve the wear resistance of the surface layer, for example, hydroxyl, isocyanate and other polar functional groups of polyurethane resin react to improve the binding force with the surface layer, can reduce the problem of low surface tension of organic silicon materials, and improve the adhesive property with polyurethane resin and acrylic resin.

The hydrogen-containing silicone oil is vinyl silicone oil which is used as a basic polymer and contains active Si-H bonds, and can be used as a cross-linking agent to promote the cross-linking of the side chain fluorine-containing vinyl silicone resin and vinyl polysilazane. Under the action of a platinum catalyst, one coordination bond of a platinum atom is broken to coordinate with the fluorine-containing vinyl silicone resin on the side chain, the other coordination bond is broken to coordinate with the vinyl polysilazane, the two basic resin sites are close to each other, and then the hydrogen-containing silicone oil is respectively connected and bridged with the fluorine-containing vinyl silicone resin and the vinyl polysilazane, so that the cross-linking of the fluorine-containing vinyl silicone resin and the vinyl polysilazane is realized, and the structural strength of a surface layer is greatly improved. In addition, active Si-H bonds in the hydrogen-containing silicone oil are easy to react with-Si-NH-Si-, and can be added with vinyl groups to increase crosslinking points. Finally, the hydrogen-containing silicone oil also has good hydrophobicity, and the hydrophobicity of the surface of the synthetic leather can be improved.

The surface layer is modified by a material mainly containing organic silicon resin, so that the cost is greatly reduced compared with that of full-silicon synthetic leather, and the wear resistance and the mechanical property are improved.

The organic solvent is used for dissolving the components. The inhibitor is used in combination with platinum catalysis, and is used as an addition type silicone rubber storage stabilizer to inhibit the progress of hydrosilylation reaction and ensure the vinyl content capable of generating crosslinking with hydrogen-containing silicone oil.

Further, the surface layer resin consists of 25-30 parts of silicon modified polyurethane resin and the balance of base resin.

By adopting the technical scheme, experiments show that the synthetic leather obtained by using the silicon modified polyurethane resin and the residual basic resin in the proportion has better mechanical strength performance.

Further, the base resin is prepared from the following components in parts by weight of 1: (0.2-0.3) polyurethane resin and thermosetting acrylic resin.

By adopting the technical scheme, the polyurethane resin has high mechanical strength, good elasticity and good weather resistance; the thermosetting acrylic resin is an insoluble and infusible acrylic polymer which takes an acrylate monomer as a basic component and is crosslinked into a network structure, and has very excellent mechanical property and chemical resistance. The thermosetting acrylic resin reacts with functional groups in the polyurethane resin to form a net structure, so that the integral mechanism strength of the synthetic leather is further improved, and meanwhile, carboxyl hydroxyl in the acrylic resin and Si-NH-Si bonds are easy to react, so that the synthetic leather is well combined with a base material.

Further, the accelerant is polydimethylsiloxane which contains silicon atoms connected with 3 hydrogen atoms, the hydrogen atoms are positioned at terminal positions or side chains, and the content of the hydrogen atoms is 0.3-1.6%.

By adopting the technical scheme, the Si-H bond directly connected with hydrogen in the polydimethylsiloxane is very active and can react with the-Si-NH-Si-main chain of the vinyl polysilazane to form a three-dimensional crosslinking structure, so that the crosslinking is further promoted, the crosslinking degree is improved, and the integral mechanical property of the synthetic leather is improved.

Furthermore, the adhesive is at least one of gamma- (methacryloyloxy) propyl trimethoxy silane, 2- (3, 4-epoxy cyclohexyl) ethyl triethoxy silane and tris (2-hydroxyethyl) isocyanuric acid triacrylate.

By adopting the technical scheme, the monomers in the adhesive can be polymerized to realize self-adhesion, and on the other hand, the adhesive can be chemically reacted with polar functional groups (such as hydroxyl, isocyanate and amino) of the surface layer, so that the polar groups are increased, the surface polarity is increased, the surface tension is increased, the problem of low surface tension of the organic silicon material is solved, and the adhesion performance with other base materials is improved.

Further, the filler is at least one of aluminum hydroxide, aluminum oxide, magnesium hydroxide, zinc borate, aluminum silicate, calcium carbonate, magnesium carbonate, glass beads, white carbon black, silicone resin micro powder, silicon dioxide, calcium carbonate and magnesium oxide with the particle size of 800-1250 meshes.

By adopting the technical scheme, the filler is used as an additive, and the filler plays a role mainly by occupying volume, so that molecular chains of the matrix material can not occupy all space any more, chain segments are fixed to a certain degree, the movement of the molecular chains is limited to a certain degree, the glass transition temperature is increased, and the heat resistance, the elastic modulus, the rigidity and the impact strength are improved.

Further, the bonding layer is foamed solvent-free polyurethane.

By adopting the technical scheme, the solvent-free polyurethane does not contain components which can be volatilized in the atmosphere, and can not negatively influence the environment and human production. The adhesive layer can be used for realizing the adhesion of the base cloth and the surface layer, and simultaneously, the soft and good-elasticity hand feeling is provided, and the better mechanical property can be provided for the whole synthetic leather.

In order to achieve the second object, the invention provides the following technical scheme: a preparation method of semi-silicon synthetic leather comprises the following steps:

preparing a surface layer: weighing surface layer resin, dimethyl formamide, butanone and pigment, and stirring at the temperature of 30-50 ℃ and the stirring speed of 800-1500r/min for 30min for later use;

preparation of the surface layer: weighing and mixing side chain fluorine-containing vinyl silicone resin, vinyl polysilazane, hydrogen-containing silicone oil, an organic solvent, an adhesive, an inhibitor and a filler, mixing at the temperature of 30-50 ℃ and under the stirring condition of 800-;

s1: coating the surface layer on release paper by 0.2 +/-0.02 mm, and drying at 70-130 ℃;

s2: coating a bonding layer with the thickness of 0.4 +/-0.05 mm on the surface layer, compounding the bonding layer with the base cloth, drying and curing at the temperature of 70-120 ℃ to realize the molding of the surface layer, the bonding layer and the base cloth;

s3: printing the surface layer on the surface layer by using a 80-200 mesh screen roller or a rolling way, and drying at the temperature of 130-150 ℃ for 1-3 min.

By adopting the technical scheme, the synthetic leather which is uniform and has good bonding between layers is obtained.

In conclusion, the invention has the following beneficial effects:

1. in the invention, the surface layer resin is preferably formed by adopting the silicon modified polyurethane resin, and the surface layer which is mainly prepared from the organic silicon resin (side chain fluorine-containing vinyl silicon resin and vinyl polysilazane) is matched to form the semi-silicon synthetic leather, so that the semi-silicon synthetic leather has comprehensive mechanical property, wear resistance, easy cleaning, stain resistance and cost.

2. In the invention, the side chain fluorine-containing vinyl silicone resin, vinyl polysilazane, hydrogen-containing silicone oil and platinum catalyst are preferably adopted, the side chain fluorine-containing vinyl silicone resin takes a-Si-O-bond as a main chain, is soft and smooth, is anti-fouling and is easy to clean, the side chain contains vinyl, fluorine atoms are introduced into the side chain, and the fluorine atoms of the side chain enable the surface of the synthetic leather to be smoother and are less prone to be stained, so that the synthetic leather with excellent performance in the aspects of easy cleaning and anti-fouling is obtained; the-Si-NH-Si-contains polar groups, nitrogen atoms can easily form intramolecular hydrogen bonds, the molecular bonding strength is improved, and the-Si-NH-Si-reacts with polar functional groups in the surface layer, so that the wear resistance of the surface layer can be greatly improved; the matching of the hydrogen-containing silicone oil and the platinum catalyst can promote the crosslinking of the side chain fluorine-containing vinyl silicone resin and vinyl polysilazane, and improve the overall mechanical strength of the synthetic leather.

3. The invention preferably adopts polyurethane resin and thermosetting acrylic resin to form the base resin, the thermosetting acrylic resin reacts with functional groups in the polyurethane resin to form a net structure, the integral mechanism strength of the synthetic leather is further improved, and meanwhile, carboxyl hydroxyl in the acrylic resin and Si-NH-Si bonds are easy to react, so that the good combination with the base material is brought.

4. In the invention, polydimethylsiloxane is preferably adopted as an accelerant to react with the-Si-NH-Si-main chain of vinyl polysilazane to form a three-dimensional crosslinking structure, so that the crosslinking is further promoted, and the crosslinking degree is improved, thereby improving the overall mechanical property of the synthetic leather.

Detailed Description