阅读说明：本技术 改性有机硅树脂及其在聚氨酯无溶剂装饰革、家具革、汽车革方面的应用 (Modified organic silicon resin and application thereof in polyurethane solvent-free decorative leather, furniture leather and automobile leather ) 是由 张宇辉 曹文奎 于 2020-12-31 设计创作，主要内容包括：本发明涉及一种有机硅树脂,特别涉及一种改性有机硅树脂及其在聚氨酯无溶剂装饰革、家具革、汽车革方面的应用。一种改性有机硅树脂,该树脂包括以下以重量份计的原料：有机硅树脂30-60,聚醚多元醇10-20,气相白炭黑10-30,液态硅胶10-40,铂金催化剂0.01-0.5,抑制剂0.1-1,乙烯基双封头10-40,高含氢硅油5-20,抗涂鸦助剂0.5-2,手感剂1-5。相比于纯硅胶皮革,本产品实现了耐刮性能提升80%,皮革手感饱满且成本下降50%的优势,产品性能超过无溶剂皮革及纯硅胶皮革。(The invention relates to an organic silicon resin, in particular to a modified organic silicon resin and application thereof in solvent-free polyurethane decorative leather, furniture leather and automobile leather. A modified organic silicon resin comprises the following raw materials in parts by weight: 30-60 parts of organic silicon resin, 10-20 parts of polyether polyol, 10-30 parts of fumed silica, 10-40 parts of liquid silica gel, 0.01-0.5 part of platinum catalyst, 0.1-1 part of inhibitor, 10-40 parts of vinyl double end socket, 5-20 parts of high hydrogen silicone oil, 0.5-2 parts of anti-doodling auxiliary agent and 1-5 parts of hand feeling agent. Compared with pure silica gel leather, the product has the advantages of improving the scratch resistance by 80%, enabling the leather to have full hand feeling and reducing the cost by 50%, and enabling the product performance to exceed that of solvent-free leather and pure silica gel leather.)

1. The modified organic silicon resin is characterized by comprising the following raw materials in parts by weight:

30-60 parts of organic silicon resin,

10-20 parts of polyether polyol,

10-30 parts of gas-phase white carbon black,

10-40 parts of liquid silica gel,

0.01 to 0.5 percent of platinum catalyst,

0.1-1 parts of inhibitor,

10-40 parts of vinyl double-end socket,

5 to 20 portions of high hydrogen-containing silicone oil,

0.5 to 2 portions of anti-doodling auxiliary agent,

1-5 of hand feeling agent.

2. A method for preparing a modified silicone resin according to claim 1, comprising the steps of:

a. fully mixing the vinyl double-end socket, the fumed silica, the organic silicon resin, the liquid silica gel and the hand feeling agent, heating to 180 +/-10 ℃, fully vacuumizing and stirring for more than 4 hours to prepare a material A;

b. fully stirring the high hydrogen-containing silicone oil, the platinum catalyst and the anti-doodling auxiliary agent for more than 2 hours to prepare a material B;

c. stirring polyether polyol and an inhibitor to prepare a material C;

d. a, B, C are respectively mixed and fully stirred according to the weight ratio of 100:10-20:10-20, and a proper amount of toner is added according to the design requirement for color matching, so as to obtain the modified organic silicon resin.

3. Use of the modified silicone resin of claim 1 in solvent-free polyurethane decorative leather, furniture leather, and automobile leather.

4. An organic silicon polyurethane solvent-free leather is characterized in that: the modified silicone resin comprises a modified silicone resin layer (1), a water-based polyurethane resin layer (2), a solvent-free foaming adhesive layer (3) and a base cloth or a microfiber cloth (4) from top to bottom in sequence, wherein the modified silicone resin layer is formed by coating the modified silicone resin slurry as claimed in claim 1.

5. A preparation method of organic silicon polyurethane solvent-free leather is characterized by comprising the following steps:

s1, preparing modified organic silicon resin slurry, covering the modified organic silicon resin slurry on release paper, and baking the release paper in an oven at the temperature of 110-130 ℃ for 3-5min to obtain a modified organic silicon resin layer;

s2, preparing aqueous polyurethane resin slurry, coating the aqueous polyurethane resin slurry on the modified organic silicon resin layer, and drying and curing at the temperature of 110-130 ℃ for 8-10min to form an aqueous polyurethane resin layer;

s3, preparing solvent-free polyurethane resin slurry, coating the solvent-free polyurethane resin slurry on a water-based polyurethane resin layer to form a solvent-free foaming bonding layer, drying at the temperature of 100-120 ℃ to enable the solvent-free foaming bonding layer to be compounded with base cloth or microfiber cloth, and then drying at the temperature of 120-140 ℃ for 15-20min to obtain semi-finished leather;

s4, separating the release paper from the semi-finished leather, curing at 35 +/-2 ℃ for more than 12 hours, and post-treating the organic silicon resin to obtain the finished leather.

6. The method for preparing polyurethane solvent-free decorative leather according to claim 5, wherein the method comprises the following steps: in step S1, the thickness of the coating of the modified organic silicon resin slurry is controlled to be 0.1-0.15 mm.

Technical Field

The invention relates to an organic silicon resin, in particular to a modified organic silicon resin and application thereof in polyurethane solvent-free leather.

Background

The conventional leathers are mainly genuine leather, PVC leathers (subbase + polyvinyl chloride) and oily PU leathers (subbase + polyurethane).

In the years, the scratch resistance of solvent-free water-based PU leather (substrate, solvent-free resin and water-based resin) on the market reaches more than 20 ten thousand times, the manufacturing process is environment-friendly, solvent-free and harmless to personnel, the performance-price ratio is higher, but special functions are not provided, and the environment-friendly scratch resistance is better and has little difference with the traditional leather.

In addition, synthetic leather consisting of organic silicon leather (substrate and silicon resin or silicon rubber) is also available in the market, generally called as organic silicon leather, and organic silicon leather products have excellent weather resistance (hydrolysis resistance, UV resistance and salt mist resistance), flame resistance, antifouling property, easy management, waterproofness, skin friendliness, no stimulation, mildew resistance, antibacterial property, safety, environmental protection and other properties, but leather is stiff in hand feeling, and poor in scratch resistance and tearing resistance due to the fact that a large amount of organic silicon materials are used. In addition, the silica gel is expensive, and the prepared leather cannot be widely accepted by the market.

Disclosure of Invention

The invention aims to provide a modified organic silicon resin which can be stably combined with an intermediate layer formed by solvent-free polyurethane resin, so that the prepared polyurethane solvent-free decorative leather has the advantages of full silica gel leather.

The invention also provides the modified organic silicon resin and application thereof in polyurethane solvent-free leather.

The technical scheme adopted by the invention for solving the technical problems is as follows:

a modified organic silicon resin comprises the following raw materials in parts by weight:

30-60 parts of organic silicon resin,

10-20 parts of polyether polyol,

10-30 parts of gas-phase white carbon black,

10-40 parts of liquid silica gel,

0.01 to 0.5 percent of platinum catalyst,

0.1-1 parts of inhibitor,

10-40 parts of vinyl double-end socket,

5 to 20 portions of high hydrogen-containing silicone oil,

0.5 to 2 portions of anti-doodling auxiliary agent,

1-5 of hand feeling agent.

In the formula, polyether is used for modifying silicon resin, and platinum is used for catalyzing organic silicon to prepare the modified organic silicon resin.

A preparation method of the modified organic silicon resin comprises the following steps:

a. fully mixing the vinyl double-end socket, the fumed silica, the organic silicon resin, the liquid silica gel and the hand feeling agent, heating to 180 +/-10 ℃, fully vacuumizing and stirring for more than 4 hours to prepare a material A;

b. fully stirring the high hydrogen-containing silicone oil, the platinum catalyst and the anti-doodling auxiliary agent for more than 2 hours to prepare a material B;

c. stirring polyether polyol and an inhibitor to prepare a material C;

d. a, B, C are mixed and fully stirred according to the proportion of 100:10-20:10-20 respectively, and a proper amount of toner is added according to the design requirement for color matching to obtain the modified organic silicon resin.

The application of the modified organic silicon resin in solvent-free polyurethane decorative leather, furniture leather and automobile leather.

The organic silicon polyurethane solvent-free leather sequentially comprises a modified organic silicon resin layer, a water-based polyurethane resin layer, a solvent-free foaming bonding layer and base cloth or microfiber cloth from top to bottom, wherein the modified organic silicon resin layer is formed by coating the modified organic silicon resin slurry. The aqueous polyurethane resin layer and the solvent-free foaming adhesive layer are conventional techniques and conventional choices in the field, are not important for the research of the present invention, and will not be described herein.

The invention relates to application of modified organic silicon resin in solvent-free polyurethane decorative leather, furniture leather and automobile leather. The application of the modified organic silicon resin in the aspect of solvent-free leather realizes the effective perfect combination of the functions of silica gel and solvent-free polyurethane, greatly improves the performance and the efficacy of the leather, reduces the cost of the leather product, and is beneficial to popularization and application.

A preparation method of organic silicon polyurethane solvent-free leather comprises the following steps:

s1, preparing modified organic silicon resin slurry, covering the modified organic silicon resin slurry on release paper, and baking the release paper in an oven at the temperature of 110-130 ℃ for 3-5min to obtain a modified organic silicon resin layer;

s2, preparing aqueous polyurethane resin slurry, coating the aqueous polyurethane resin slurry on the modified organic silicon resin layer, and drying and curing at the temperature of 110-130 ℃ for 8-10min to form an aqueous polyurethane resin layer;

s3, preparing solvent-free polyurethane resin slurry, coating the solvent-free polyurethane resin slurry on a water-based polyurethane resin layer to form a solvent-free foaming bonding layer, drying at the temperature of 100-120 ℃ to enable the solvent-free foaming bonding layer to be compounded with base cloth or microfiber cloth, and then drying at the temperature of 120-140 ℃ for 15-20min to obtain semi-finished leather;

s4, separating the release paper from the semi-finished leather, curing at 35 +/-2 ℃ for more than 12 hours, and post-treating the organic silicon resin to obtain the finished leather.

The invention has the beneficial effects that:

the modified organic silicon resin provided by the invention is used in polyurethane solvent-free leather, can exert the advantages of environment-friendly solvent-free leather, low VOC (volatile organic compound) emission, scratch resistance, full hand feeling and the like, and can exert the functions of organic silicon (such as antifouling, smoothness, high and low temperature resistance, weather resistance, antibacterial and mildew resistance, ultraviolet resistance and flame retardance) on the surface of the leather. Compared with pure silica gel leather, the product has the advantages of improving the scratch resistance by 80%, enabling the leather to have full hand feeling and reducing the cost by 50%, and enabling the product performance to exceed that of solvent-free leather and pure silica gel leather.

Drawings

FIG. 1 is a schematic cross-sectional view of a silicone polyurethane solventless leather product of the present invention, in which a modified silicone resin layer (1), an aqueous polyurethane resin layer (2), a solventless foaming adhesive layer (3) and a base fabric (4);

FIG. 2 is a photograph of a silicone polyurethane solventless leather product of the present invention.

Detailed Description

The technical solution of the present invention will be further specifically described below by way of specific examples. It is to be understood that the practice of the invention is not limited to the following examples, and that any variations and/or modifications may be made thereto without departing from the scope of the invention.

In the present invention, all parts and percentages are by weight, unless otherwise specified, and the equipment and materials used are commercially available or commonly used in the art. The methods in the following examples are conventional in the art unless otherwise specified.

The reagents used in the following examples, unless otherwise specified, were purchased from conventional biochemical reagent stores.

The common equipment used in the following examples is shown in Table 1.

TABLE 1

The sources of reagents used in the following examples are shown in table 2.

TABLE 2

Name of article	Model number	Manufacturer of the product
			Silicone resin	LX-7080	Novel Shandong Shengyu material
Polyether polyols	X6033	Asahi Chuan chemistry
			Fumed silica	HB152D	Yichang Hui Fu
Liquid silica gel	KDS4A58	Dongguan Keduo
			Platinum catalyst	D4B21	Dongguan Dongcheng Cheng
Inhibitors	A65	Beijing Bailingwei science and technology
			Vinyl double seal head	F02	JIANGXI HUAER RUNZHI NEW MATERIAL Co.,Ltd.
High hydrogen-containing silicone oil	F03	JIANGXI HUAER RUNZHI NEW MATERIAL Co.,Ltd.
			Anti-graffiti adjuvants	3822F3	Sirocco chemical Co., Guangzhou city
Hand feeling agent	9988	Changzhou LangYing oil chemical Co Ltd

The core of the invention is to provide a modified organic silicon resin, which comprises the following raw materials in parts by weight: 30-60 parts of organic silicon resin, 10-20 parts of polyether polyol, 10-30 parts of fumed silica and liquid silica gel

10 to 40 portions of platinum catalyst, 0.01 to 0.5 portion of inhibitor, 10 to 40 portions of vinyl double-end socket, 5 to 20 portions of high hydrogen silicone oil, 0.5 to 2 portions of anti-graffiti auxiliary agent and 1 to 5 portions of hand feeling agent.

The second core of the invention is to provide a preparation method of the modified organic silicon resin, which comprises the following steps:

a. fully mixing the vinyl double-end socket, the fumed silica, the organic silicon resin, the liquid silica gel and the hand feeling agent, heating to 180 +/-10 ℃, fully vacuumizing and stirring for more than 4 hours to prepare a material A;

b. fully stirring the high hydrogen-containing silicone oil, the platinum catalyst and the anti-doodling auxiliary agent for more than 2 hours to prepare a material B;

c. stirring polyether polyol and an inhibitor to prepare a material C;

d. a, B, C are respectively mixed and fully stirred according to the weight ratio of 100:10-20:10-20, and a proper amount of toner is added according to the design requirement for color matching, so as to obtain the modified organic silicon resin.

The third core of the invention is to provide the application of the modified organic silicon resin in polyurethane solvent-free decorative leather, furniture leather and automobile leather.

The fourth core of the invention is to provide the organic silicon polyurethane solvent-free leather which has the structure shown in figure 1 and sequentially comprises a modified organic silicon resin layer 1, a water-based polyurethane resin layer 2, a solvent-free foaming adhesive layer 3 and a base fabric 4 from top to bottom, wherein the modified organic silicon resin layer is formed by coating the modified organic silicon resin slurry. The base cloth 4 may be replaced with a microfiber cloth.

The core of the invention is to provide a preparation method of organic silicon polyurethane solvent-free leather, which comprises the following specific steps:

s1, preparing modified organic silicon resin slurry, covering the modified organic silicon resin slurry on release paper, and baking the release paper in an oven at the temperature of 110-130 ℃ for 3-5min to obtain a modified organic silicon resin layer;

the thickness of the coating of the modified organic silicon resin slurry is controlled to be 0.1-0.15 mm;

the modified organic silicon resin is prepared by the embodiment;

s2, preparing aqueous polyurethane resin slurry, coating the aqueous polyurethane resin slurry on the modified organic silicon resin layer, and drying and curing at the temperature of 110-130 ℃ for 8-10min to form an aqueous polyurethane resin layer;

s3, preparing solvent-free polyurethane resin slurry, coating the solvent-free polyurethane resin slurry on a water-based polyurethane resin layer to form a solvent-free foaming bonding layer, drying at the temperature of 100-120 ℃ to enable the solvent-free foaming bonding layer to be compounded with base cloth or microfiber cloth, and then drying at the temperature of 120-140 ℃ for 15-20min to obtain semi-finished leather;

s4, separating the release paper from the semi-finished leather, curing at 35 +/-2 ℃ for more than 12 hours, and post-treating the organic silicon resin to obtain the finished leather.

Aqueous polyurethane resin slurry, solvent-free polyurethane resin slurry are conventional choices.

Firstly, preparing modified organic silicon resin

1. The raw material formulation of the modified silicone resin is shown in table 3.

TABLE 3 formulation of modified Silicone resin (unit: kg)

Raw materials	Example 1	Example 2	Example 3
				Silicone resin	30	60	40
Polyether polyols	20	20	10
				Fumed silica	15	20	30
Liquid silica gel	20	40	10
				Platinum catalyst	0.5	0.5	0.5
Inhibitors	0.5	0.9	1
				Vinyl double seal head	30	40	10
High hydrogen-containing silicone oil	20	5	10
				Anti-graffiti adjuvants	1	1	2
Hand feeling agent	2	3	5

2. Preparation process

a. And (3) fully mixing the vinyl double-end socket, the fumed silica, the organic silicon resin, the liquid silica gel and the hand feeling agent, heating to 180 ℃, fully vacuumizing and stirring for more than 4 hours to obtain the material A.

b. And fully stirring the high-hydrogen silicone oil, the platinum catalyst and the anti-doodling auxiliary agent for more than 2 hours to prepare a material B.

c. And stirring the polyether polyol and the inhibitor to obtain a material C.

Second, leather product production process

A preparation method of organic silicon polyurethane solvent-free leather comprises the following specific steps:

s1, mixing A, B, C three groups of the raw materials according to the weight ratio of 100:10:10, stirring fully, adding toner for color mixing, and preparing an M1 material;

s2, fully stirring the aqueous polyurethane resin slurry, and adding color paste to obtain an intermediate layer material M2;

s3, putting the solvent-free polyurethane resin slurry into a casting tank for later use to prepare M3;

s4, the concrete process of the product production refers to the content of the fifth core of the invention, and the process flow is as follows: a leather production line adopting a three-coating four-drying method

The aqueous polyurethane resin layer and the solvent-free foaming adhesive layer are conventional techniques and conventional choices in the field, are not important for the research of the present invention, and will not be described herein.

Test results

The photo of the leather produced by the process is shown in figure 2, and the market is commonly called semi-silica gel leather. Through detection, the detection result of the organic silicon polyurethane solvent-free leather product prepared by the method is as follows:

a. the leather comprises the following components:

40-45% of fiber fabric, 50-55% of solvent-free polyether, polycarbon, 10-15% of organic silicon polymer, no PVC (polyvinyl chloride) and low VOCs (volatile organic compounds) emission; can be recovered, meets the RoHs environmental protection, REACH, 65 standards of California of America, and has no toxicity, formaldehyde and lead; contains no plasticizer/phthalate/heavy metal/BPA, is harmless to air and water, and has no odor. b. Color fastness of leather:

dry wiping color fastness is 4 grade, wet wiping is 3 grade;

perspiration fastness AATCC15 grade 4.

c. Leather stain resistance:

ink CFFA-141, grade 5; indigo transfer (no knowledge of translation accuracy) CFFA-141, grade 5,

cooking oil CFFA-141, grade 5; coffee/chocolate CFFA-141, grade 5,

blood stain/urine/iodine CFFA-141, grade 5; mustard sauce/red wine CFFA-141, grade 5,

lipstick CFFA-141, grade 5; ball-point pen, oil marker pen, Mark pen CFFA-141, grade 5.

d. Physical properties of leather:

martindale is wear resistant for 20 ten thousand times and is not broken;

TABOR H18500 g weight more than 10000 turns;

bending resistance is carried out for 50 ten thousand times at normal temperature; hydrolysis resistance: ASTM D3609-02,7 weeks; soaking 10% of NaoH at normal temperature; the physical properties were not significantly changed after 72 hours.

e. And (3) leather flame retardance:

the united states standard flame retardant, california 117, the british standard flame retardant, B1,

does not promote the growth of the mould, does not contain antibacterial additive/bactericide/or flame retardant,

cytotoxicity test: the ISO 10993-5 GLP-test passes,

skin allergy test: ISO10993-10 GLP-irritation was negligible.

The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.