CN108129633B

CN108129633B - Folding-resistant high-transparency mirror polyurethane resin and preparation method and application thereof

Info

Publication number: CN108129633B
Application number: CN201711340104.7A
Authority: CN
Inventors: 王传勇; 蒋红梅; 胡海波; 顾佳佳; 唐劲松
Original assignee: Shanghai Huafon Material Technology Research Institute LP; Shanghai Huafon New Material Research & Development Technology Co ltd
Current assignee: Shanghai Huafon Material Technology Research Institute LP; Shanghai Huafon New Material Research & Development Technology Co ltd
Priority date: 2017-12-14
Filing date: 2017-12-14
Publication date: 2020-09-11
Anticipated expiration: 2037-12-14
Also published as: CN108129633A

Abstract

The invention discloses a folding-resistant high-transparency mirror surface polyurethane resin and a preparation method and application thereof, wherein the folding-resistant high-transparency mirror surface polyurethane resin is prepared from the following components in percentage by weight: 6-25% of polyester diol, 2-5% of chain extender, 10-15% of diisocyanate, 0.02-0.05% of antioxidant, 0.05-0.25% of end-capping agent and the balance of solvent, wherein the polyester diol is selected from more than one of poly-1, 4-butanediol adipate diol, poly-1, 6-hexanediol adipate diol, poly-neopentyl glycol adipate diol, poly-1, 4-butanediol adipate diol or poly-1, 6-hexanediol adipate diol. The folding-resistant high-transparency mirror-surface polyurethane resin obtained by the invention can be used for preparing vamps. The mirror-surface polyurethane resin prepared by the invention has excellent folding resistance at normal and low temperatures, the light transmittance of the adhesive film is high, and a leather sample has good surface smoothness and is not easy to precipitate.

Description

Folding-resistant high-transparency mirror polyurethane resin and preparation method and application thereof

Technical Field

The present invention relates to a polyurethane resin.

Background

The polyurethane synthetic leather is a composite material consisting of a polyurethane coating and a base material, the polyurethane coating is generally divided into a surface layer and a bonding layer, polyurethane resin of the bonding layer is used for bonding the surface layer and the base material together, and the surface layer mainly plays a role in reflecting the appearance and style of the synthetic leather and protecting the synthetic leather, so that the surface layer plays a vital role in the quality of the whole synthetic leather, and particularly in the field of mirror surface layers, higher requirements on hand feeling and physical properties are provided.

The mirror surface leather is mainly applied to shoes, and the common mirror surface shoe leather has poor folding resistance due to high resin modulus and strong crystallinity, which seriously influences the service life of the shoe leather. In addition, in order to seek good hand feeling, different performance and hand feeling requirements are usually achieved by adding the organic silicon, but the common organic silicon is easy to migrate to the surface layer to cause the phenomenon of precipitation and fogging. The phenomenon of fogging cannot be noticed within a short time due to precipitation, and an organic silicon aggregation layer can be obviously formed on the surface of the leather after a period of aggregation, so that the appearance and the use can be influenced, a large amount of finished leather is wasted, and huge losses are brought to a tannery and a resin factory.

At present, mirror resin on the market is various, but the folding resistance is poor, and fogging is easily separated out on the surface, so that the requirement for leather is difficult to meet.

Disclosure of Invention

The invention aims to provide a folding-resistant high-transparency mirror polyurethane resin and a preparation method and application thereof, so as to overcome the defects of the prior art.

The folding-resistant high-transparency mirror-surface polyurethane resin is prepared from the following raw materials:

polyester diol, a chain extender, diisocyanate, an antioxidant, a solvent and a blocking agent;

wherein:

the polyester diol is selected from more than one of poly adipic acid 1, 4-butanediol diol, poly adipic acid 1, 6-hexanediol diol, poly adipic acid neopentyl glycol ester diol, poly adipic acid glutaric acid 1, 4-butanediol diol or poly adipic acid glutaric acid 1, 6-hexanediol diol;

the number average molecular weight is 1000-;

preferred are the poly (1, 4-butanediol adipate glutarate diol) with a number average molecular weight of 1500; or a mixture of poly (1, 4-butylene adipate) glycol having a number average molecular weight of 1000-3500 and a number average molecular weight of 2000; or a mixture of 1, 4-butanediol polyglutamate diol having a number average molecular weight of 2000-;

the chain extender is selected from ethylene glycol, 1, 4-butanediol, 1, 6-hexanediol and neopentyl glycol, and 1, 4-butanediol is preferred;

the diisocyanate is selected from toluene diisocyanate or 4,4 '-diphenylmethane diisocyanate, preferably 4, 4' -diphenylmethane diisocyanate;

the antioxidant is hindered phenol antioxidant, preferably BHT;

the end-capping reagent is methanol or reactive organosilicon;

the solvent is at least one of dimethylformamide or butanone.

The reactive organosilicon is single-terminal amino reactive organosilicon, and the molecular structural formula is as follows:

n is 1; the number average molecular weight is 800-; the reactive silicone manufacturer is wacker chemistry.

The weight percentage of each component is as follows:

the preferable weight percentage is as follows:

preferably, the polyester diol is:

poly (1, 4-butanediol adipate diol): 1, 4-butanediol adipate glycol is 1-3: 1 (weight ratio);

preferably, the polyester diol is:

1, 4-butanediol polyglutamate diol: 1, 4-butanediol adipate glycol is 1-3: 1 (weight ratio);

when the polyester diol is poly adipic acid glutaric acid 1, 4-butanediol ester diol, the molar ratio of adipic acid to glutaric acid is 1: 3/7-7/3;

preferably, the polyester diol is:

poly (1, 4-butanediol adipate) diol (number average molecular weight 2000): poly (1, 4-butylene adipate glycol) (number average molecular weight 2000) to 3:1 (weight ratio);

poly (1, 4-butanediol adipate) diol (number average molecular weight 3500): poly (1, 4-butylene adipate) glycol (number average molecular weight 2000) 3:2 (weight ratio);

poly (1, 4-butanediol adipate) diol (number average molecular weight 1000): poly (1, 4-butylene adipate) glycol (number average molecular weight 2000) 1:1 (weight ratio);

poly (1, 4-butylene adipate glycol) (number average molecular weight 1500);

1, 4-butanediol polyglutamate diol (number average molecular weight 2000): poly (1, 4-butylene adipate) glycol (number average molecular weight 2000) 1:1 (weight ratio);

1, 4-butanediol polyglutamate diol (number average molecular weight 2500): poly (1, 4-butylene adipate glycol) (number average molecular weight 2000) to 3:1 (weight ratio);

poly (1, 4-butanediol adipate) diol (number average molecular weight 3000): poly (1, 4-butylene adipate glycol) (number average molecular weight 2000) to 3:1 (weight ratio);

poly (1, 4-butanediol adipate) diol (number average molecular weight 2000): poly (1, 4-butylene adipate) glycol (number average molecular weight 2000) 1:1 (weight ratio);

the preparation method of the folding-resistant high-transparency mirror polyurethane resin comprises the following steps:

(1) mixing an antioxidant, polyester diol, a chain extender and a partial solvent at 50-60 ℃, wherein the partial solvent accounts for 55-65% of the total mass of the solvent;

(2) then adding diisocyanate accounting for 85-95% of the total amount, heating to 70-80 ℃, and reacting for 4-6 hours;

(3) supplementing the rest of diisocyanate;

(4) adding the balance of solvent B;

(5) adding a blocking agent, blocking to terminate the reaction, and preserving the heat for 1-2 hours at the temperature of 45-75 ℃ to obtain the folding-resistant high-transparency mirror polyurethane resin with the mass solid content of 30-35% and the final viscosity of 80-140PaS/25 ℃.

The folding-resistant high-transparency mirror-surface polyurethane resin obtained by the invention can be used for preparing vamps.

The invention has the beneficial effects that:

the mirror-surface polyurethane resin prepared by the invention has excellent folding resistance at normal and low temperatures, the light transmittance of the adhesive film is high, and a leather sample has good surface smoothness and is not easy to precipitate.

Detailed Description

The invention will be further illustrated with reference to the following specific examples. In the examples, sample A is used as a control, the modified samples are B1-B8, respectively, for a total of 8 samples, and samples B1-B8 are compared with A.

Comparative example 1

This example prepares control A, where the polyester diol used was poly 1, 4-butylene adipate diol and the number average molecular weight of the polyester diol was 2000.

Comparative sample a used the following raw materials and weights:

name of raw materials	Weight (gram)	Percent (%)
			Antioxidant BHT	1.00	0.02％
Poly (1, 4-butylene adipate) glycol (number average molecular weight 2000)	616	15.3％
			1, 4-butanediol	142	3.5％
4, 4' -diphenylmethane diisocyanate	472	11.7％
			Dimethyl formamide	2380	59％
Butanone	420	10.4％
			Methanol	4	0.1％
Total mass	4035	100％

Comparative sample a was prepared as follows:

1) uniformly mixing antioxidant BHT, poly 1,4 butanediol adipate glycol, 1, 4-butanediol and dimethylformamide (60 percent of the total weight) at the temperature of 55 ℃;

2) then adding 4, 4' -diphenylmethane diisocyanate (90 percent of the total weight), heating to 70 ℃, and carrying out heat preservation reaction for 6 hours;

3) supplementing the rest of 4, 4' -diphenylmethane diisocyanate;

4) adding butanone and the balance dimethylformamide, and continuing stirring;

5) then, methanol was added and stirred at 70 ℃ for 1 hour to terminate the reaction, and the final viscosity was adjusted to 80 to 140PaS/25 ℃ to obtain sample a.

Example 1

The polyester diols used in this example were poly-adipic acid 1, 4-butanediol ester diol (A) and poly-adipic acid 1, 4-butanediol ester diol (B), the molar ratio of adipic acid to glutaric acid in (A) being 3:7, the number average molecular weight being 2000; (ii) has a number average molecular weight of 2000; wherein (A): (ii) (b) ═ 3:1 (by weight);

the molecular weight of the single-terminal amino silicone oil used in this example was 800.

Sample B1 was prepared in this example, where sample B1 used the following raw materials and weights:

name of raw materials	Weight (gram)	Percent (%)
			Antioxidant BHT	1.00	0.02％
Polyester diol (A)	441	11％
			Polyester diol (second)	147	3.7％
1, 4-butanediol	142.5	3.6％
			4, 4' -diphenylmethane diisocyanate	469.3	11.7％
Dimethyl formamide	2400	59.9％
			Butanone	400	10％
Single amino silicone oil (number average molecular weight 800)	4	0.1％
			Total mass	4004.8	100％

The procedure for sample B1 was as follows:

1) uniformly mixing antioxidant BHT, polyester dihydric alcohol (A), polyester dihydric alcohol (B), 1, 4-butanediol and dimethylformamide (60% of the total weight) at 55 ℃;

3) supplementing the rest of 4, 4' -diphenylmethane diisocyanate;

4) adding butanone and the balance dimethylformamide, and continuing stirring;

5) and adding the single-end amino silicone oil, stirring for 2 hours at 45 ℃ to terminate the end capping reaction, wherein the final viscosity is 80-140PaS/25 ℃, and obtaining a sample B1.

Example 2

The polyester diols used in this example were poly-adipic acid 1, 4-butanediol ester diol (A) and poly-adipic acid 1, 4-butanediol ester diol (B), the molar ratio of adipic acid to glutaric acid in (A) being 1:1, the number average molecular weight being 3500; (ii) has a number average molecular weight of 2000; wherein (A): (ii) (b) 3:2 (weight ratio);

the molecular weight of the single-terminal amino silicone oil used in this example was 1000.

Sample B2 was prepared in this example, where sample B2 used the following raw materials and weights:

name of raw materials	Weight (gram)	Percent (%)
			Antioxidant BHT	1.00	0.02％
Polyester diol (A)	338.4	8.4％
			Polyester diol (second)	225.6	5.6％
1, 4-butanediol	154	3.8％
			4, 4' -diphenylmethane diisocyanate	484.2	12.1％
Dimethyl formamide	2400	59.9％
			Butanone	400	10％
Single amino silicone oil (number average molecular weight 1000)	6	0.15％
			Total mass	4008.2	100％

The procedure for sample B2 was as follows:

1) uniformly mixing antioxidant BHT, polyester dihydric alcohol (A), polyester dihydric alcohol (B), 1, 4-butanediol and dimethylformamide (65% of the total weight) at 50 ℃;

2) then adding 4, 4' -diphenylmethane diisocyanate (85% of the total weight), heating to 75 ℃, and carrying out heat preservation reaction for 5 hours;

3) supplementing the rest of 4, 4' -diphenylmethane diisocyanate;

4) adding butanone and the balance dimethylformamide, and continuing stirring;

5) then, the terminal amino silicone oil was added, and the mixture was stirred at 50 ℃ for 1.5 hours to terminate the reaction, and the final viscosity was controlled at 80 to 140PaS/25 ℃ to obtain sample B2.

Example 3

The polyester diols used in this example were poly-adipic acid 1, 4-butanediol ester diol (A) and poly-adipic acid 1, 4-butanediol ester diol (B), the molar ratio of adipic acid to glutaric acid in (A) being 7:3, the number average molecular weight being 1000; (ii) has a number average molecular weight of 2000; wherein (A): (ii) (1: 1 (by weight);

Sample B3 was prepared in this example, where sample B3 used the following raw materials and weights:

the procedure for sample B3 was as follows:

1) uniformly mixing antioxidant BHT, polyester dihydric alcohol (A), polyester dihydric alcohol (B), 1, 4-butanediol and dimethylformamide (55% of the total weight) at 60 ℃;

2) then adding 4, 4' -diphenylmethane diisocyanate (95% of the total weight), heating to 80 ℃, and carrying out heat preservation reaction for 4 hours;

3) supplementing the rest of 4, 4' -diphenylmethane diisocyanate;

4) adding butanone and the balance dimethylformamide, and continuing stirring;

5) then, the terminal amino silicone oil was added, and the mixture was stirred at 55 ℃ for 1.5 hours to terminate the reaction, and the final viscosity was controlled at 80 to 140PaS/25 ℃ to obtain sample B3.

Example 4

The polyester diol used in this example was poly adipic acid, glutaric acid, 1, 4-butanediol diol, wherein the molar ratio of adipic acid to glutaric acid was 1:1, and the number average molecular weight was 1500;

the molecular weight of the single-terminal amino silicone oil used in this example was 2000.

Sample B4 was prepared in this example, where sample B4 used the following raw materials and weights:

the procedure for sample B4 was as follows:

1) uniformly mixing antioxidant BHT, poly adipic acid glutaric acid 1, 4-butanediol ester diol, 1, 4-butanediol and dimethylformamide (60 percent of the total weight) at 58 ℃;

2) then adding 4, 4' -diphenylmethane diisocyanate (90 percent of the total weight), heating to 75 ℃, and carrying out heat preservation reaction for 5.5 hours;

3) supplementing the rest of 4, 4' -diphenylmethane diisocyanate;

4) adding butanone and the balance dimethylformamide, and continuing stirring;

5) and adding single-end amino silicone oil, stirring for 1 hour at 60 ℃ to terminate the end capping reaction, and controlling the final viscosity to be 80-140PaS/25 ℃ to obtain a sample B4.

Example 5

The polyester diols used in this example were polyglutamic acid 1, 4-butanediol diol (a) and polyhexamic acid 1, 4-butanediol diol (b), the number average molecular weight of (a) being 2000; (ii) has a number average molecular weight of 2000; wherein (A): (ii) (1: 1 (by weight);

the molecular weight of the single-terminal amino silicone oil used in this example was 1500.

Sample B5 was prepared in this example, where sample B5 used the following raw materials and weights:

name of raw materials	Weight (gram)	Percent (%)
			Antioxidant BHT	1.00	0.02％
Polyester diol (A)	294	7.3％
			Polyester diol (second)	294	7.3％
1, 4-butanediol	142.5	3.6％
			4, 4' -diphenylmethane diisocyanate	469.3	11.7％
Dimethyl formamide	2400	59.9％
			Butanone	400	10％
Single amino silicone oil (number average molecular weight 1500)	6	0.15％
			Total mass	4006.8	100％

The procedure for sample B5 was as follows:

1) uniformly mixing antioxidant BHT, polyester dihydric alcohol (A), polyester dihydric alcohol (B), 1, 4-butanediol and dimethylformamide (65% of the total weight) at 55 ℃;

2) then adding 4, 4' -diphenylmethane diisocyanate (the total weight is 95%), heating to 70 ℃, and carrying out heat preservation reaction for 6 hours;

3) supplementing the rest of 4, 4' -diphenylmethane diisocyanate;

4) adding butanone and the balance dimethylformamide, and continuing stirring;

5) and adding single-end amino silicone oil, stirring for 1 hour at 65 ℃ to terminate the end capping reaction, and controlling the final viscosity to be 80-140PaS/25 ℃ to obtain a sample B5.

Example 6

The polyester diols used in this example were polyglutamic acid 1, 4-butanediol diol (A) and polyhexamic acid 1, 4-butanediol diol (B), the number average molecular weight of (A) being 2500; (ii) has a number average molecular weight of 2000; wherein (A): (ii) (b) ═ 3:1 (by weight);

Sample B6 was prepared in this example, where sample B6 used the following raw materials and weights:

name of raw materials	Weight (gram)	Percent (%)
			Antioxidant BHT	1.00	0.02％
Polyester diol (A)	432	10.8％
			Polyester diol (second)	144	3.6％
1, 4-butanediol	149	3.7％
			4, 4' -diphenylmethane diisocyanate	475.1	11.9％
Dimethyl formamide	2400	59.9％
			Butanone	400	10％
Single amino silicone oil (number average molecular weight 1000)	4	0.1％
			Total mass	4005.1	100％

The procedure for sample B6 was as follows:

1) uniformly mixing antioxidant BHT, polyester dihydric alcohol (A), polyester dihydric alcohol (B), 1, 4-butanediol and dimethylformamide (58% of the total weight) at 50 ℃;

2) then adding 4, 4' -diphenylmethane diisocyanate (85% of the total weight), heating to 80 ℃, and reacting for 4.5 hours in a heat preservation manner;

3) supplementing the rest of 4, 4' -diphenylmethane diisocyanate;

4) adding butanone and the balance dimethylformamide, and continuing stirring;

5) and adding single-end amino silicone oil, stirring for 1 hour at 70 ℃ to terminate the end capping reaction, and controlling the final viscosity to be 80-140PaS/25 ℃ to obtain a sample B6.

Example 7

The polyester diols used in this example were poly-adipic acid 1, 4-butanediol ester diol (A) and poly-adipic acid 1, 4-butanediol ester diol (B), the molar ratio of adipic acid to glutaric acid in (A) being 3:7, the number average molecular weight being 3000; (ii) has a number average molecular weight of 2000; wherein (A): (ii) (b) ═ 3:1 (by weight);

Sample B7 was prepared in this example, where sample B7 used the following raw materials and weights:

name of raw materials	Weight (gram)	Percent (%)
			Antioxidant BHT	1.00	0.02％
Polyester diol (A)	423	10.6％
			Polyester diol (second)	141	3.5％
1, 4-butanediol	154.5	3.9％
			4, 4' -diphenylmethane diisocyanate	482	12％
Dimethyl formamide	2400	59.9％
			Butanone	400	10％
Single amino silicone oil (number average molecular weight 2000)	6	0.15％
			Total mass	4007.5	100％

The procedure for sample B7 was as follows:

1) uniformly mixing antioxidant BHT, polyester dihydric alcohol (A), polyester dihydric alcohol (B), 1, 4-butanediol and dimethylformamide (60% of the total weight) at 60 ℃;

3) supplementing the rest of 4, 4' -diphenylmethane diisocyanate;

4) adding butanone and the balance dimethylformamide, and continuing stirring;

5) and adding the single-end amino silicone oil, stirring for 1 hour at 75 ℃ to terminate the end capping reaction, and controlling the final viscosity to be 80-140PaS/25 ℃ to obtain a sample B7.

Example 8

The polyester diols used in this example were poly-adipic acid 1, 4-butanediol ester diol (A) and poly-adipic acid 1, 4-butanediol ester diol (B), the molar ratio of adipic acid to glutaric acid in (A) being 7:3, the number average molecular weight being 2000; (ii) has a number average molecular weight of 2000; wherein (A): (ii) (1: 1 (by weight);

the molecular weight of the single-terminal amino silicone oil used in this example was 2300.

Sample B8 was prepared in this example, where sample B8 used the following raw materials and weights:

name of raw materials	Weight (gram)	Percent (%)
			Antioxidant BHT	1.00	0.02％
Polyester diol (A)	300	7.5％
			Polyester diol (second)	300	7.5％
1, 4-butanediol	139	3.5％
			4, 4' -diphenylmethane diisocyanate	461	11.5％
Dimethyl formamide	2400	59.8％
			Butanone	400	10％
Single amino silicone oil (number average molecular weight 2300)	10	0.25％
			Total mass	4011	100％

The procedure for sample B8 was as follows:

2) then adding 4, 4' -diphenylmethane diisocyanate (95% of the total weight), heating to 70 ℃, and carrying out heat preservation reaction for 6 hours;

3) supplementing the rest of 4, 4' -diphenylmethane diisocyanate;

4) adding butanone and the balance dimethylformamide, and continuing stirring;

5) then, the terminal amino silicone oil was added, and the mixture was stirred at 45 ℃ for 1.5 hours to terminate the reaction, and the final viscosity was controlled at 80 to 140PaS/25 ℃ to obtain sample B8.

Example 9

Application examples are as follows:

the resin application comprises film preparation and leather making, wherein raw materials used in the leather making comprise the synthesized resin, solvent, color chips and functional auxiliary agent, wherein:

the synthetic resin had 1 control A, 8 example B1-B8;

solvents include dimethylformamide and butanone;

color chips are black, such as pigment SP-1698 (mirror black) from Boston;

the functional assistant is organic silicon, such as BYK-L9565 of Bick chemical company;

the raw materials comprise the following components in percentage by mass:

the film preparation and leather making application of the polyurethane mirror resin comprises the following steps:

the preparation method of the mirror film comprises the following steps: coating the sample resin on mirror surface release paper according to the coating thickness of 0.15mm, baking for 10-15min at 130 ℃, and taking out from the release paper to obtain the mirror surface adhesive film.

The preparation method of the mirror surface leather comprises the following steps: 100 parts of resin, 70 parts of dimethylformamide, 30 parts of butanone, 0.05 part of flatting agent BYK-L9565 (wherein samples B1-B8 do not need to be added), 6 parts of black sheet SP-1698 are sequentially put into a sampling cup, uniformly stirred and mixed through a dispersing agent, the mixed solution is coated on mirror surface release paper according to the coating thickness of 0.15mm, baked for 3-5min at the temperature of 130 ℃, then a layer of solvent adhesive JF-HSY-AD45P2 (Shanghai Huafeng materials science and technology Limited company) with the thickness of 0.15mm is directly coated on the mirror surface adhesive film, and then the mirror surface adhesive JF-HSY-AD45P2 (Shanghai Huafeng materials science and technology Limited company) with₂The shoe leather microfiber substrate (Shanghai Huafeng microfiber materials Co., Ltd.) is rolled back and forth 3-5 times by a rolling rod, is placed into a 135 ℃ oven for baking for 5-8 minutes, and is released from release paper, so that the mirror leather can be obtained.

The normal temperature folding endurance test method comprises the following steps: and (3) sequentially cutting a plurality of sample pieces on the prepared mirror leather sample by using a folding-resistant cutting sample mold (45 × 70mm), wherein the number of the warp-wise sample piece and the weft-wise sample piece is half of that of each sample piece, and the name, the warp-wise direction, the temperature condition and the folding-resistant times of the sample pieces are marked on the back of each sample piece. And respectively mounting the cut sample wafers on a normal-temperature folding endurance testing machine (Taiwan high-speed railway, equipment model GT-7071-B) according to set conditions for testing, and recording folding endurance results according to the testing conditions.

The low-temperature folding endurance test method comprises the following steps: and (3) sequentially cutting a plurality of sample pieces on the prepared mirror leather sample by using a folding-resistant cutting sample mold (45 × 70mm), wherein the number of the warp-direction sample pieces and the weft-direction sample pieces is half of that of the warp-direction sample pieces, and the back surfaces of the sample pieces are marked with the name of the leather sample, the warp-direction sample pieces, the weft-direction sample pieces, the temperature condition (-20 ℃) and the folding-resistant times. And respectively mounting the cut sample wafers on a low-temperature folding endurance testing machine (Taiwan Honda, equipment model HT-8043) to test according to set conditions, and recording folding endurance results according to test conditions.

The light transmittance test method comprises the following steps: the mirror surface adhesive film was prepared into a test piece, and a light transmittance test was performed on a light transmittance meter (model DR81, julian electronics technologies ltd., east china) using organic glass as a control sample. According to the test conditions, the light transmittance results were recorded.

The friction coefficient test method comprises the following steps: cutting two mirror surface adhesive films, fixing one mirror surface adhesive film on a horizontal test plate by using a double-sided adhesive tape, fixing the other mirror surface adhesive film on a special slide block, then placing the center of a first sample on the test plate according to a specific operation instruction, and enabling the test directions of the two samples to be parallel to the sliding direction and the force measuring system to be just not stressed. The slide block slides over the sample for a certain distance at a test speed specified by the standard (GB10006), and the coefficient of a friction coefficient meter (model MXD-02, Vinan Languan electromechanical technology, Inc.) is read and recorded.

Leather sample precipitation test method: and (3) sequentially cutting a plurality of sample pieces on the prepared mirror leather sample by using a sample cutting mold (180X 180mm), wherein the back surfaces of the sample pieces are marked with the names of the leather samples and are placed in an oven for a day. Respectively hanging the cut sample wafers in a high-temperature high-humidity tester (Shanghai Jia Ben test equipment Co., Ltd., equipment model GDW-010C) to test according to set conditions (temperature is 70 ℃ and humidity is 95%), and recording leather sample precipitation results according to test conditions.

Physical property measurements for comparative example 1 and examples 1-8 are shown in the following table:

the above table shows that the mirror-surface polyurethane resin prepared by the invention has excellent folding resistance at normal and low temperatures, the light transmittance of the adhesive film is high, and the leather sample has good surface smoothness and is not easy to precipitate.

Claims

1. The folding-resistant high-transparency mirror polyurethane resin is characterized by being prepared from the following components in percentage by weight:

the end-capping reagent is reactive organosilicon, the reactive organosilicon is single-end amino silicone oil, and the number average molecular weight of the reactive organosilicon is 800, 1000, 1500, 2000 or 2300.

2. The folding-resistant high-transparency mirror-surface polyurethane resin according to claim 1, wherein the weight percentages of the components are as follows:

3. the folding-resistant highly transparent mirror polyurethane resin as claimed in claim 1 or 2, wherein the polyester diol has a number average molecular weight of 1000-3500.

4. The folding-resistant highly transparent mirror-like polyurethane resin according to claim 1 or 2, wherein said polyester diol is 1, 4-butanediol adipate diol having a number average molecular weight of 1500; or a mixture of poly (1, 4-butylene adipate) glycol having a number average molecular weight of 1000-3500 and a number average molecular weight of 2000; or a mixture of 1, 4-butanediol polyglutamate diol having a number average molecular weight of 2000-.

5. The folding-resistant highly transparent mirror-like polyurethane resin according to claim 1 or 2, wherein said chain extender is selected from the group consisting of ethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, and neopentyl glycol;

the diisocyanate is selected from toluene diisocyanate or 4, 4' -diphenylmethane diisocyanate.

6. The folding-resistant highly transparent mirror surface polyurethane resin according to claim 1 or 2, wherein said antioxidant is a hindered phenol-based antioxidant.

7. The folding-resistant highly transparent mirror-like polyurethane resin according to claim 1 or 2, wherein said polyester diol is:

poly (1, 4-butanediol adipate diol): 1-3: 1 weight ratio of poly (1, 4-butanediol adipate),

1, 4-butanediol polyglutamate diol: 1-3: 1 weight ratio of poly (1, 4-butanediol adipate),

Wherein the molar ratio of adipic acid to glutaric acid in the poly adipic acid glutaric acid 1, 4-butanediol ester diol is 1: 3/7-7/3;

1, 4-butanediol adipate glutarate diol with a number average molecular weight of 2000: the weight ratio of poly (1, 4-butylene adipate) glycol with the number average molecular weight of 2000 is 3:1,

1, 4-butanediol adipate glutarate diol with a number average molecular weight of 3500: the weight ratio of poly (1, 4-butylene adipate) glycol with the number average molecular weight of 2000 is 3:2,

1, 4-butanediol adipate glutarate diol with a number average molecular weight of 1000: the weight ratio of poly (1, 4-butylene adipate) glycol with the number average molecular weight of 2000 is 1:1,

1, 4-butanediol adipate glutarate diol with a number average molecular weight of 1500;

1, 4-butanediol polyglutamate diol having a number average molecular weight of 2000: the weight ratio of poly (1, 4-butylene adipate) glycol with the number average molecular weight of 2000 is 1:1,

1, 4-butanediol polyglutamate diol having a number average molecular weight of 2500: the weight ratio of poly (1, 4-butylene adipate) glycol with the number average molecular weight of 2000 is 3:1,

1, 4-butanediol adipate glutarate diol with a number average molecular weight of 3000: the weight ratio of 1, 4-butanediol adipate diol having a number-average molecular weight of 2000 is 3:1 or

1, 4-butanediol adipate glutarate diol with a number average molecular weight of 2000: the weight ratio of 1, 4-butanediol adipate diol having a number average molecular weight of 2000 was 1: 1.

8. The method for preparing the folding-resistant high-transparency mirror-surface polyurethane resin according to any one of claims 1 to 7, comprising the steps of:

(1) mixing an antioxidant, polyester diol, a chain extender and a partial solvent, wherein the partial solvent accounts for 55-65% of the total mass of the solvent;

(2) then adding diisocyanate accounting for 85-95% of the total amount, and heating for reaction;

(3) supplementing the rest of diisocyanate;

(4) adding the rest solvent;

(5) adding an end-capping reagent, terminating the end-capping reaction, and preserving the temperature to obtain the folding-resistant high-transparency mirror-surface polyurethane resin.

9. The method according to claim 8, wherein in the step (1), the antioxidant, the polyester diol, the chain extender and the partial solvent are mixed at 50 to 60 ℃; in the step (2), the temperature is raised to 70-80 ℃ and the reaction is carried out for 4-6 hours; in the step (5), the temperature is kept for 1 to 2 hours at the temperature of between 45 and 75 ℃.

10. The use of the folding-resistant high-transparency mirror-surface polyurethane resin according to any one of claims 1 to 7 for manufacturing a shoe upper.