CN117164803A - Polyurethane surface layer resin with good binding force with organosilicon treating agent, preparation method and PU leather composite material prepared by using polyurethane surface layer resin - Google Patents

Abstract

The application relates to the technical field of polyurethane surface layer resin, in particular to polyurethane surface layer resin with good binding force with an organosilicon treating agent, a preparation method and a PU leather composite material prepared by using the polyurethane surface layer resin. A polyurethane surface layer resin with good binding force with organosilicon treating agent is mainly prepared from polyalcohol, chain extender, dihydroxyvinyl silicone oil, diisocyanate, catalyst, organic solvent, auxiliary agent and terminator; the polyol is at least one of polyether polyol and polycarbonate polyol with molecular weight of 1000-3000 matched with maleic anhydride modified polyester polyol; the maleic anhydride modified polyester polyol is mainly prepared from maleic anhydride, adipic acid and low-polarity dihydric alcohol, wherein the mass of the maleic anhydride is 5-25wt% of that of the adipic acid. The polyurethane surface layer resin prepared by the application has good bonding force with the surface formed by the organosilicon treating agent, is not easy to fall off, and has the excellent performances of wear resistance, folding resistance, stain resistance and smoothness.

Description

Polyurethane surface layer resin with good binding force with organosilicon treating agent, preparation method and PU leather composite material prepared by using polyurethane surface layer resin

Technical Field

The application relates to the technical field of polyurethane surface layer resin, in particular to polyurethane surface layer resin with good binding force with an organosilicon treating agent, a preparation method and a PU leather composite material prepared by using the polyurethane surface layer resin.

Background

Polyurethane resin is easy to absorb dust on the surface due to the characteristic of high polarity, and soft leather has poor smoothness, so that the application of the polyurethane resin in the field of soft furniture leather is limited due to the defects. In order to achieve better slip performance, softness is often sacrificed to improve hardness, or more slip-type organosilicon auxiliary agents are added. The surface energy of the organosilicon auxiliary agent is lower, the smoothness of the surface can be well improved, but the compatibility of the organosilicon and the polyurethane resin is relatively poor, and the organosilicon can be gradually separated out along with the time, so that the problems of leather surface fogging and the like are caused, and the use effect is affected.

In order to solve the problems, the latest treatment method in the industry is to roll coat a thin layer of vinyl silicon and hydrogen-containing silicone oil on the surface of the synthetic leather, and to carry out addition polymerization under the action of a catalyst to form an organosilicon polymer, so that the synthetic leather prepared by the method has smooth surface, high softness and good weather resistance, and the problems of fogging or later-stage smoothness reduction cannot occur. However, the solution is not high in bonding fastness due to the polarity difference of the organic silicon and the polyurethane, and the problem that the organic silicon layer falls off easily occurs, so the application provides the polyurethane surface layer resin with good bonding force with the organic silicon treating agent and the preparation method thereof.

Disclosure of Invention

In order to solve the technical problems, the application provides polyurethane surface layer resin with good binding force with an organosilicon treating agent, a preparation method and a PU leather composite material prepared by using the polyurethane surface layer resin.

In a first aspect, the polyurethane surface layer resin with good binding force with the organosilicon treating agent is realized by the following technical scheme:

the polyurethane surface layer resin with good binding force with the organosilicon treating agent is mainly prepared from polyalcohol, a chain extender, vinyl silicone oil with active groups at two ends, diisocyanate, a catalyst, an organic solvent, an auxiliary agent and a terminator;

the diisocyanate is at least one of diisocyanates with molecular weight less than 300 g/mol;

the polyol is at least one of polyether polyol and polycarbonate polyol with molecular weight of 1000-3000 matched with maleic anhydride modified polyester polyol;

the chain extender is at least one of saturated glycol, diamine and alcohol amine with the molecular weight of 76-200 g/mol and the double bond-containing glycol with the molecular weight of 61-200 g/mol;

the maleic anhydride modified polyester polyol is mainly prepared from maleic anhydride, adipic acid and low-polarity dihydric alcohol, wherein the mass of the maleic anhydride is 5-25wt% of that of the adipic acid;

The low-polarity dihydric alcohol is at least one dihydric alcohol with a molecular weight of 76-200 g/mol and a side group; the dihydric alcohol containing the side group is at least one of poly 1,3 propylene glycol, 1,5 pentanediol, 1,2 propanediol and neopentyl glycol;

the mass of the catalyst is equal to 10ppm-500ppm of the total mass of diisocyanate, polyol and chain extender; the catalyst is organic tin;

the molar ratio of the polyol to the chain extender is controlled at 1: (0.01-0.3);

the organic solvent comprises at least one of acetone, butanone, DMF and toluene;

the terminator is a dihydroxy small molecule;

the vinyl silicone oil with active groups at two ends is at least one of dihydroxyvinyl silicone oil and vinyl amino-terminated silicone oil;

the auxiliary agent comprises at least one of polymerization inhibitor, flatting agent, slipping agent, dispersing agent, adhesion promoter, coupling agent, defoaming agent, thickening agent, antioxidant, anti-ultraviolet agent, color paste and functional filler.

In the prior art, polyurethane resin with good binding force with an organosilicon treating agent does not appear, and a conventional polyurethane surface layer resin is subjected to surface treatment by adopting a reactive organosilicon treating agent, so that the problems of easy separation of a surface layer and an organosilicon treating layer and poor binding force are caused. The application carries out corresponding structural design on polyurethane surface layer resin, and introduces double bonds into a soft section and/or a hard section, so that hydrogen-containing silicone oil can also carry out addition polymerization with the double bonds; in the prepared polyurethane resin, hydroxyl end capping is adopted, and under the action of a catalyst, hydrogen-containing silicone oil reacts with hydroxyl; in addition, the polyurethane molecule contains vinyl silicone oil, and has good compatibility with an organosilicon layer; so that the polyurethane surface layer resin and the organic silicon resin have chemical bond connection and combination with similar physical polarity; the polyurethane surface layer resin and the organic silicon resin form a whole connected by chemical bonds in multiple aspects, so that the combination firmness of the reactive organic silicon treating agent and the polyurethane surface layer resin is effectively improved, and the problem that the organic silicon resin is separated from the polyurethane surface layer is solved.

The polyurethane surface layer resin formed by the application has good bonding force with the surface formed by the organosilicon treating agent, is not easy to fall off, and has lasting wear resistance, folding resistance, dirt resistance and slipping performance.

Preferably, the organotin includes, but is not limited to, at least one of dibutyltin dibutyrate, dimethyltin dibutyrate, dioctyltin dibutyrate, dibutyltin diacetate, dimethyltin dilaurate, stannous octoate, iso Xin Ku dibutyltin dithioacetate, isooctyl tin dithioacetate, iso Xin Ku dioctyltin dithioacetate, dibutyltin dioctyl dicaprylate, dimethyltin dioctyldecanoate, dioctyltin dioctyldecanoate, dimethyltin dilaurate, and dimethyltin dioleate.

Preferably, the preparation method of the maleic anhydride modified polyester polyol comprises the following steps: firstly, maleic anhydride, adipic acid and low-polarity dihydric alcohol are put into a reaction kettle, the temperature is increased to react, the kettle temperature in the first stage is increased to 130-135 ℃, and the temperature is maintained for 3h; then heating to 225-230 ℃ at constant speed within 4 hours, and preserving heat for 3.0 hours; then controlling the temperature at the top of the distillation tower to be between 101 and 103 ℃, sampling to measure the acid value along with the reaction, adding tetrabutyl titanate and vacuumizing after the acid value reaches 30mgKOH/g, gradually vacuumizing the kettle from normal pressure to about-0.098 MPa (25 torr) relative to vacuum within 4 hours, sampling and detecting, and finally breaking the reaction kettle by nitrogen and cooling to 108 to 110 ℃ when the hydroxyl value of the product in the kettle reaches 17 to 224mgKOH/g, unloading and packaging to obtain the maleic anhydride polyol with the molecular weight of 500 to 6500.

The preparation method of the maleic anhydride modified polyester polyol is relatively simple, has low operation difficulty, is convenient for realizing industrial production and manufacture, and can ensure the quality of the prepared maleic anhydride modified polyester polyol.

Preferably, the polyol is a polyester polyol modified with maleic anhydride having a molecular weight of 2000, polytetrahydrofuran ether glycol having a molecular weight of 3000, polycarbonate glycol having a molecular weight of 2000 in a molar ratio of (2-4): (1-4): (1-4).

The good mechanical property and weather resistance of the polyurethane surface layer can be ensured by the optimized design of the polyol.

Preferably, the chain extender is at least one of 3-allyloxy-1, 2-propanediol, 1, 4-butenediol, 1, 5-hexadiene-3, 4-diol, and at least one of 1, 4-butanediol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol, 1, 4-butanediamine, 1, 5-pentanediamine, 1, 6-hexanediamine, isophorone diamine, 4' -diaminodicyclohexylmethane, and hexamethylenediamine.

By introducing double bonds into the chain extender, the hydrogen-containing silicone oil in the surface treatment agent can also undergo addition polymerization on the double bonds in the chain extender, so that the bonding firmness of the surface treatment agent and the surface layer resin can be improved.

Preferably, the chain extender is prepared from 1, 5-hexadiene-3, 4-diol, 1, 6-hexanediol and isophorone diamine in a molar ratio (1-3): (4-8): (4-8).

By optimizing the composition ratio of the chain extender, not only the bonding firmness of the surface treatment agent and the polyurethane surface layer resin can be improved, but also the mechanical property of the prepared polyurethane surface layer resin can be optimized and improved.

Preferably, the diisocyanate is composed of MDI, HMDI in a molar ratio of (6-8): of (2-4).

The heat resistance, yellowing resistance and wear resistance of polyurethane surface layer resin can be improved by adjusting and combining the molar ratio of MDI and HMDI, and the polyurethane surface layer resin has good mechanical property and flexibility.

In a second aspect, the preparation method of the polyurethane surface layer resin with good binding force with the organosilicon treating agent is realized by the following technical scheme:

a preparation method of polyurethane surface layer resin with good binding force with organosilicon treating agent comprises the following steps:

s1, preparing maleic anhydride modified polyester polyol;

s2, uniformly mixing the maleic anhydride modified polyester polyol prepared in the S1 with other polyols, a chain extender, dihydroxyvinyl silicone oil, diisocyanate, a catalyst, an organic solvent and an auxiliary agent, and heating and reacting to obtain 3-20 x 10 ⁴ And (3) after cps/25 ℃, terminating the reaction by using a terminator to obtain the finished polyurethane surface layer resin.

The preparation method of the polyurethane surface layer resin with good binding force with the organosilicon treating agent is relatively simple, has low operation difficulty, is convenient for realizing industrial production and manufacturing, and has good market prospect.

In a third aspect, the application provides a PU leather composite material prepared by polyurethane surface layer resin with good binding force with organosilicon treating agent, which is realized by the following technical scheme:

the PU leather composite material prepared by using polyurethane surface layer resin with good binding force with an organosilicon treating agent comprises microfiber cloth, wherein the surface of the microfiber cloth is compounded with a PU surface layer; the PU surface layer is made of the polyurethane surface layer resin with good binding force with the organosilicon treating agent; the surface of the PU surface layer facing away from the microfiber cloth is rich in a folding-resistant smooth layer; the folding-resistant slipping layer is prepared from organic silicon resin or a reactive organic silicon treating agent which has good binding force with polyurethane resin;

the reactive organosilicon treating agent mainly comprises vinyl silicone oil, hydrogen-containing silicone oil and a catalyst;

the organic silicon resin with good binding force with polyurethane resin is prepared from a component A, a component B and a platinum catalyst; the component A is mainly prepared from polyalcohol, chain extender, diisocyanate, organic solvent, catalyst, auxiliary agent and vinyl silicone oil, wherein the polyalcohol in the component A is at least one of maleic anhydride modified polyester polyalcohol, polyether with molecular weight of 1000-3000 or polycarbonate polyalcohol; the maleic anhydride modified polyester polyol in the folding-resistant smooth layer is the same as the maleic anhydride modified polyester polyol adopted in the PU surface layer; the component B is hydrogen-containing silicone oil; the molar ratio of the vinyl in the component A to the active hydrogen in the hydrogen-containing silicone oil in the component B is 1 (1.1-1.3).

The folding-resistant smooth layer prepared by the method can be a commercially available reactive organic silicon treating agent or organic silicon resin with good binding force with polyurethane resin, and the PU surface layer and the folding-resistant smooth layer in the PU leather composite material prepared by adopting the two surface treating agents have good binding force, namely are not easy to fall off and peel off, have long service life and have good functions of wear resistance, stain resistance and smoothness. Compared with the commercially available reactive organic silicon treating agent, the PU leather composite material prepared by adopting the organic silicon resin with good binding force with the polyurethane resin has better binding stability, and is suitable for high-end leather materials or personalized products customized by private persons. The PU leather composite material prepared by the commercially available reactive organosilicon treating agent is suitable for industrial production, has relatively low production cost, and is applied to the fields of case leather, shoe leather and the like.

Preferably, the chain extender in the component A is one or a mixture of more than two of diol, diamine or alcohol amine with the molecular weight of 61-200 g/mol; the diisocyanate in the component A is one or a mixture of more than two diisocyanates with molecular weight less than 300 g/mol; the vinyl silicone oil in the component A is one or a mixture of more than two vinyl silicone oils with the vinyl content of 0.09-20wt%; the hydrogen content of the hydrogen-containing silicone oil in the component B is 0.03% -1.60%; the auxiliary agent in the component A comprises one or a mixture of more than two of an antioxidant, matting powder and light stabilizer.

Preferably, the preparation method of the PU leather composite material prepared by using the polyurethane surface layer resin with good binding force with the organosilicon treating agent comprises the following steps:

s1, preparing polyurethane surface layer resin with good binding force with an organosilicon treating agent;

meanwhile, preparing the folding-resistant and slipping-resistant layer organic silicon resin;

s2, coating polyurethane surface layer resin with good binding force with the organosilicon treating agent, which is prepared in the step S1, on the surface of the microfiber cloth, and drying for 5-10min at 150-170 ℃ after the polyurethane surface layer resin is roll-coated on the microfiber cloth to obtain a PU surface layer;

and S3, coating the folding-resistant and slipping-resistant layer organic silicon resin prepared in the step S1 on the surface of the PU surface layer, and baking at 150-170 ℃ for 5-10min after the organic silicon resin is roll-coated on the PU surface layer to obtain the finished PU leather composite material.

The preparation method of the PU leather composite material is relatively simple, has low operation difficulty and is convenient for realizing industrial production and manufacturing.

In summary, the application has the following advantages:

1. the polyurethane surface layer resin formed by the application has good bonding force with the surface formed by the organosilicon treating agent, is not easy to fall off, and has lasting wear resistance, folding resistance, dirt resistance and slipping performance.

2. The preparation method is relatively simple, has low operation difficulty and is convenient for realizing industrial production and manufacture.

Description of the embodiments

The present application will be described in further detail with reference to comparative examples and examples.

Preparation example 1: the maleic anhydride modified polyester polyol was prepared from 14g of maleic anhydride, 146g of adipic acid, 142g of neopentyl glycol, 0.02g of tetrabutyl titanate, and 0.03g of antioxidant 1010.

The preparation method of the maleic anhydride modified polyester polyol comprises the following steps:

s1, putting maleic anhydride, adipic acid, neopentyl glycol and an antioxidant 1010 into a reaction kettle, heating to react, and keeping the temperature at 135 ℃ for 3.0h in the first stage kettle; then the temperature is increased to 230 ℃ at a constant speed within 4.0h, and the temperature is kept for 3.0h;

s2, controlling the temperature at the top of the distillation tower to be between 101 and 103 ℃, sampling to measure the acid value along with the progress of the reaction, adding tetrabutyl titanate and vacuumizing after the acid value reaches 30mgKOH/g, gradually vacuumizing the kettle from normal pressure to about-0.098 MPa (25 torr) in 4 hours, sampling and detecting, and obtaining qualified products when the hydroxyl value of the products in the kettle reaches 56.0mgKOH/g, breaking the vacuum of the reaction kettle by nitrogen, cooling to 110 ℃, unloading and packaging to obtain the maleic anhydride polyol with the molecular weight of 2000.

A silicone resin having excellent bonding force with polyurethane surface layer resin is prepared from 100g of maleic anhydride modified polyester polyol with molecular weight of 2000, 76g of MDI, 0.001g of stannous octoate, 0.1g of triphenyl phosphite, 7g of ethylene glycol and 400g of toluene.

The preparation method of the organic silicon resin with excellent bonding force with polyurethane surface layer resin comprises the following steps:

s1, adding 100g of maleic anhydride polyol, 7g of ethylene glycol, 0.1g of antioxidant and 400g of toluene into a reactor, heating to 45 ℃, and stirring for 25min; 41g of MDI is added, the kettle temperature is controlled at 75 ℃ for reaction for 1 hour, catalyst is added for continuous reaction, and when the viscosity reaches 5.0X103 mPa.s/25 ℃; adding the rest MDI to react for 40min, and discharging to obtain the maleic anhydride polyurethane resin with 31% of solid content.

S2, preparing a material A from 15g of maleic anhydride polyurethane resin with 31% of solid content and 100g of vinyl silicone oil (provided by Jia Yi materials Co., ltd.) with 0.098% of vinyl content;

when the silicone resin is used, 0.001g of platinum catalyst and 21.6g of hydrogen-containing silicone oil B material (supplied by Jiangxi Xinjia Jiu materials Co., ltd.) with the hydrogen content of 0.03% are added into the material A prepared in the step S2 at the stirring speed of 320rpm, and the mixture is continuously and uniformly mixed at the stirring speed of 320rpm, so that the silicone resin with good bonding force with polyurethane is obtained.

Preparation 2 differs from preparation 1 in that: the maleic anhydride-modified polyester polyol was a molecular weight 1500 maleic anhydride-modified polyester polyol prepared from 28g of maleic anhydride, 146g of adipic acid, 182g of 3-methyl-1, 5-pentanediol, 0.02g of tetrabutyl titanate, and 0.03g of antioxidant 1010.

A silicone resin having excellent bonding force with polyurethane surface layer resin is prepared from 100g of maleic anhydride modified polyester polyol with molecular weight of 1500, 50g of polytetrahydrofuran glycol with molecular weight of 2000, 58.7g of TDI, 67.9g of MDI, 0.001g of stannous octoate, 0.02g of triphenyl phosphite, 15g of ethanolamine and 500g of toluene.

The preparation method of the organic silicon resin with excellent bonding force with polyurethane surface layer resin comprises the following steps:

s1, adding maleic anhydride polyester polyol, polytetrahydrofuran glycol, an antioxidant, ethanolamine and toluene into a reactor, heating to 45 ℃, and stirring for 25min; adding TDI completely, reacting at 85deg.C for 2 hr, adding catalyst, and reacting until the viscosity reaches 1.2X10 ⁴ mPa.s/25 ℃; adding MDI to react for 60min, and discharging to obtain the maleic anhydride modified polyurethane resin with the solid content of 36.8%.

S2, preparing a material A from 20g of maleic anhydride polyurethane resin and 100g of vinyl silicone oil (provided by new polymer materials Inc. in Jiande City) with 10% of vinyl content;

when in use, the material A prepared in the step S2 is added with 0.001g of platinum catalyst and 31.6g of hydrogen-containing silicone oil B material with hydrogen content of 1.60 percent (Japanese SHIN-ETSU KF99 hydrogen-containing silicone oil, CAS: 7223-15) at a stirring speed of 320rpm, and the mixture is continuously and uniformly mixed at the stirring speed of 320rpm, so that the silicone resin with good bonding force with polyurethane is obtained.

The difference between preparation example 3 and preparation example 1 is that: the maleic anhydride-modified polyester polyol was a molecular weight 3000 maleic anhydride-modified polyester polyol prepared from 36g of maleic anhydride, 146g of adipic acid, 152g of 2-methyl-1, 3-propanediol, 0.02g of tetrabutyl titanate, 0.03g of antioxidant 1076.

A silicone resin having excellent bonding force with polyurethane surface layer resin is prepared from 150g of maleic anhydride modified polyester polyol with a molecular weight of 3000, 90g of polypropylene oxide glycol with a molecular weight of 3000, 154.3g of IPDI, 0.003g of dibutyl tin dilaurate, 20g of 1, 4-butanediol, 420g of toluene and 0.03g of antioxidant 1024.

The preparation method of the organic silicon resin with excellent bonding force with polyurethane surface layer resin comprises the following steps:

s1, charging 150g of maleic anhydride polyester polyol, 90g of polypropylene oxide glycol (molecular weight 3000), 20g of 1,4 butanediol, 0.03g of antioxidant and 420g of toluene into a reactor, heating to 45 ℃, and stirring for 25min; adding EPDI67.1g, controlling the kettle temperature at 95 ℃ for 2 hours, adding a catalyst, and continuing the reaction until the viscosity reaches 9000 mPa.s/25 ℃; adding 87.2g of IPDI for reaction for 60min, and discharging to obtain maleic anhydride polyurethane resin with the solid content of 50%;

S2, preparing a material A from 25g of maleic anhydride polyurethane resin with the solid content of 50 percent and 100g of vinyl silicone oil with the vinyl content of 8 percent (provided by Jiangxi Xin Jia Yi materials Co., ltd.);

when the polyurethane surface layer resin is used, 0.001g of platinum catalyst and 103.9g of hydrogen-containing silicone oil B material (supplied by Jiangxi Xinjia material Co., ltd.) with the hydrogen content of 0.45% are added into the material A prepared in the step S2 at the stirring speed of 320rpm, and the mixture is uniformly mixed to obtain the organic silicon resin with excellent bonding force with the polyurethane surface layer resin.

The difference between preparation example 4 and preparation example 1 is that: the maleic anhydride-modified polyester polyol was a molecular weight 1000 maleic anhydride-modified polyester polyol prepared from 30g of maleic anhydride, 146g of adipic acid, 120g of 1,2 propylene glycol, 0.02g of tetrabutyl titanate, 0.03g of antioxidant 1076.

A silicone resin having excellent bonding force with polyurethane surface layer resin is prepared from 200g of maleic anhydride modified polyester polyol with molecular weight of 1000, 100g of polycarbonate diol with molecular weight of 2000, 127g of MDI, 104g of 4, 4-dicyclohexylmethane diisocyanate, 0.003g of dibutyl tin dilaurate, 10g of neopentyl glycol, 10g of ethylene glycol, 560g of toluene and 0.03g of triphenyl phosphite.

The preparation method of the organic silicon resin with excellent bonding force with polyurethane surface layer resin comprises the following steps:

s1, adding 200g of maleic anhydride polyester polyol and 100g of polycarbonate diol into a reactor; 10g of ethylene glycol and 10g of neopentyl glycol; 0.03g of antioxidant, 560g of toluene, heating to 45 ℃ and stirring for 25min; 127g of MDI is put into the reactor, the reactor temperature is controlled at 75 ℃ for reaction for 1 hour, and the catalyst is put into the reactor for reaction until the viscosity is 1.1X104 mPa.s/25 ℃; 104g of 4, 4-dicyclohexylmethane diisocyanate is added, and the mixture is reacted for 60 minutes to be discharged, so that the maleic anhydride polyurethane resin with the solid content of 49.6% is obtained;

s2, when 20g of maleic anhydride polyurethane resin with the solid content of 49.6% and 100g of vinyl silicone oil with the vinyl content of 3% (provided by Sanguis new materials Co., ltd., guangzhou) are prepared into a material A, and when the material A is used, the material A prepared in the S2 is uniformly mixed with 0.001g of platinum catalyst and 8.24g of hydrogen-containing silicone oil B with the hydrogen content of 1.60% (provided by Jiangxi Xinjia material Co., ltd.), so as to obtain the organic silicon resin with excellent bonding force with polyurethane surface layer resin.

The difference between preparation example 5 and preparation example 1 is that: 100g of vinyl silicone oil with the vinyl content of 0.098% is prepared into a material A, and the material A is uniformly mixed with 0.001g of platinum catalyst and 16.3g of hydrogen-containing silicone oil B with the hydrogen content of 0.03% to obtain the reactive organosilicon treating agent. When in use, the coating is rolled on the surface of the synthetic leather, and then baked at 160 ℃ for 8 min.

The difference between preparation example 6 and preparation example 2 is that: 100g of vinyl silicone oil with 10% vinyl content is prepared into a material A; when in use, the reaction type organosilicon treating agent is obtained by uniformly mixing 0.001g of platinum catalyst and 31.46g of hydrogen-containing silicone oil (material B) with the hydrogen content of 1.60 percent.

The difference between preparation 7 and preparation 3 is: 100g of vinyl silicone oil with 8% vinyl content is prepared into a material A; when in use, the reaction type organosilicon treating agent is obtained by uniformly mixing 0.001g of platinum catalyst and 102.56g of hydrogen-containing silicone oil (material B) with the hydrogen content of 0.45 percent.

The difference between preparation 8 and preparation 4 is: 100g of vinyl silicone oil with 3% vinyl content is prepared into a material A; when in use, the reaction type organosilicon treating agent is obtained by uniformly mixing 0.001g of platinum catalyst and 7.98g of hydrogen-containing silicone oil (material B) with the hydrogen content of 1.59 percent.

Examples

The polyurethane surface layer resin with good binding force with the organosilicon treating agent is mainly prepared from polyalcohol, a chain extender, vinyl silicone oil with active groups at two ends, diisocyanate, a catalyst, an organic solvent, an auxiliary agent and a terminator. The diisocyanate is at least one of diisocyanates with molecular weight less than 300g/mol, and preferably, the diisocyanate is composed of MDI and HMDI in a molar ratio of (6-8): 2-4.

The polyol is at least one of polyether polyol and polycarbonate polyol with molecular weight of 1000-3000 and modified polyester polyol of maleic anhydride. The maleic anhydride modified polyester polyol is mainly prepared from maleic anhydride, adipic acid and low-polarity dihydric alcohol, wherein the mass of the maleic anhydride is 5-25wt% of the mass of the adipic acid. The low-polarity dihydric alcohol is at least one of glycol with the molecular weight of 76-200 g/mol and dihydric alcohol with side group. The dihydric alcohol containing side group is at least one of poly (1, 3-propylene glycol), 1, 5-pentanediol, 1, 2-propylene glycol and neopentyl glycol.

The preparation method of the maleic anhydride modified polyester polyol comprises the following steps:

firstly, maleic anhydride, adipic acid and low-polarity dihydric alcohol are put into a reaction kettle, the temperature is increased to react, the kettle temperature in the first stage is increased to 130-135 ℃, and the temperature is maintained for 3h; then heating to 225-230 ℃ at constant speed within 4 hours, and preserving heat for 3.0 hours; then controlling the temperature at the top of the distillation tower to be between 101 and 103 ℃, sampling to measure the acid value along with the reaction, adding tetrabutyl titanate and vacuumizing after the acid value reaches 30mgKOH/g, gradually vacuumizing the kettle from normal pressure to about-0.098 MPa (25 torr) relative to vacuum within 4 hours, sampling and detecting, and finally breaking the reaction kettle by nitrogen and cooling to 108 to 110 ℃ when the hydroxyl value of the product in the kettle reaches 17 to 224mgKOH/g, unloading and packaging to obtain the maleic anhydride polyol with the molecular weight of 500 to 6500.

Preferably, the polyol is a polyester polyol modified with maleic anhydride having a molecular weight of 2000, polytetrahydrofuran ether glycol having a molecular weight of 3000, polycarbonate glycol having a molecular weight of 2000 in a molar ratio of (2-4): (1-4): (1-4).

The chain extender is at least one of saturated glycol, diamine and alcohol amine with the molecular weight of 76-200 g/mol and the double bond-containing glycol with the molecular weight of 61-200 g/mol.

Preferably, the chain extender is at least one of 3-allyloxy-1, 2-propanediol, 1, 4-butenediol, 1, 5-hexadiene-3, 4-diol, 1, 4-butanediol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol, 1, 4-butanediamine, 1, 5-pentanediamine, 1, 6-hexanediamine, isophorone diamine, 4' -diaminodicyclohexylmethane, hexamethylenediamine.

Further preferably, the chain extender is a mixture of 1, 5-hexadiene-3, 4-diol, 1, 6-hexanediol, isophorone diamine in a molar ratio (1-3): (4-8): (4-8).

The mass of the catalyst is equal to 10ppm to 500ppm of the total mass of diisocyanate, polyol and chain extender. The catalyst is organic tin, and dibutyl tin dilaurate or stannous octoate is adopted in the application.

The molar ratio of polyol to chain extender is controlled at 1: (0.01-0.3).

The organic solvent comprises at least one of acetone, butanone, DMF and toluene.

The terminating agent is a dihydroxyl small molecule, preferably ethylene glycol.

The vinyl silicone oil with active groups at the two ends is at least one of dihydroxyvinyl silicone oil and vinyl amino-terminated silicone oil.

The auxiliary agent comprises at least one of polymerization inhibitor, flatting agent, slipping agent, dispersing agent, adhesion promoter, coupling agent, defoamer, thickener, antioxidant, anti-ultraviolet agent, color paste and functional filler.

A preparation method of polyurethane surface layer resin with good binding force with organosilicon treating agent comprises the following steps:

s1, preparing maleic anhydride modified polyester polyol;

s2, uniformly mixing the maleic anhydride modified polyester polyol prepared in the S1 with other polyols, a chain extender, dihydroxyvinyl silicone oil, diisocyanate, a catalyst, an organic solvent and an auxiliary agent, and heating and reacting to obtain 3-20 x 10 ⁴ And (3) after cps/25 ℃, terminating the reaction by using a terminator to obtain the finished polyurethane surface layer resin.

A PU leather composite material prepared by polyurethane surface layer resin with good binding force with organosilicon treating agent comprises microfiber cloth, wherein the surface of the microfiber cloth is compounded with a PU surface layer. The PU surface layer is made of the polyurethane surface layer resin with good binding force with the organosilicon treating agent. The PU surface layer is rich in a folding-resistant and slipping layer on the surface facing away from the microfiber cloth, and the folding-resistant and slipping layer is prepared from organic silicon resin or a reactive organic silicon treating agent which has good binding force with polyurethane resin.

The reactive organosilicon treating agent mainly comprises vinyl silicone oil, hydrogen-containing silicone oil and a catalyst.

The organic silicon resin with good binding force with polyurethane resin is prepared from an A component, a B component and a platinum catalyst. The component A is mainly prepared from polyol, a chain extender, diisocyanate, an organic solvent, a catalyst, an auxiliary agent and vinyl silicone oil, wherein the polyol in the component A is at least one of maleic anhydride modified polyester polyol, polyether with molecular weight of 1000-3000 or polycarbonate polyol. The maleic anhydride modified polyester polyol in the fold-resistant and smooth layer is the same as the maleic anhydride modified polyester polyol used in the PU surface layer.

The component B is hydrogen-containing silicone oil, and the molar ratio of vinyl in the component A to active hydrogen in the component B is 1 (1.1-1.3).

The chain extender in the component A is one or a mixture of more than two of diol, diamine or alcohol amine with the molecular weight of 61-200 g/mol. The diisocyanate in the component A is one or a mixture of more than two diisocyanates with molecular weight less than 300 g/mol. The vinyl silicone oil in the component A is one or a mixture of more than two vinyl silicone oils with the vinyl content of 0.09-20wt%. The auxiliary agent in the component A comprises one or a mixture of more than two of an antioxidant, matting powder and light stabilizer. The hydrogen content of the hydrogen-containing silicone oil in the component B is 0.03-1.60%.

The preparation method of the PU leather composite material prepared by using the polyurethane surface layer resin with good binding force with the organosilicon treating agent comprises the following steps:

s1, preparing polyurethane surface layer resin with good binding force with an organosilicon treating agent;

meanwhile, preparing the folding-resistant and slipping-resistant layer organic silicon resin;

s2, coating polyurethane surface layer resin with good binding force with the organosilicon treating agent, which is prepared in the step S1, on the surface of the microfiber cloth, and drying for 5-10min at 150-170 ℃ after the polyurethane surface layer resin is roll-coated on the microfiber cloth to obtain a PU surface layer;

and S3, coating the folding-resistant and slipping-resistant layer organic silicon resin prepared in the step S1 on the surface of the PU surface layer, and baking at 150-170 ℃ for 5-10min after the organic silicon resin is roll-coated on the PU surface layer to obtain the finished PU leather composite material.

Example 1: a polyurethane surface layer resin with good binding force with an organosilicon treating agent is prepared from 1mol of MDI (tobacco smoke, 0.25mol of HMDI (tobacco smoke, 0.1mol of homemade maleic anhydride modified polyester polyol with a molecular weight of 2000, 0.05mol of polyether polyol-polytetrahydrofuran glycol with a molecular weight of 3000 (from the dawn group), 0.05mol of polycarbonate glycol with a molecular weight of 2000 (from Tosoh in Japan, model: NIPPOLLAN 964, hydroxyl value 56.0+ -3; main component 1.6-HDO content 50%), 0.5mol of 1, 4-butanediol, 0.5mol of 1, 6-hexanediol, 0.06mol of dihydroxyvinyl silicone oil (Anhui Ai Yaoda silicone oil Co., ltd., hydroxyl end-capped methyl vinyl silicone oil IOTA V, hydroxyl content of more than or equal to 6.0%, vinyl content of 6.5-7.5m o1%), 200g of DMF, 600g of ethylene glycol, 0.28g of stannous octoate, 2g of 1010, and 0.168 g of antioxidant.

The maleic anhydride-modified polyester polyol having a molecular weight of 2000 was prepared from 14g of maleic anhydride, 146g of adipic acid, 142g of neopentyl glycol, 0.02g of tetrabutyl titanate and 0.03g of antioxidant 1010.

The preparation method of the maleic anhydride modified polyester polyol with the molecular weight of 2000 comprises the following steps:

s1, putting maleic anhydride, adipic acid, neopentyl glycol and an antioxidant 1010 into a reaction kettle, heating to react, and keeping the temperature for 3 hours when the temperature of the kettle rises to 135 ℃ in the first stage; then heating to 230 ℃ at constant speed in 4 hours, and preserving heat for 3.0 hours;

s2, controlling the temperature at the top of the distillation tower to be between 101 and 103 ℃, sampling to measure the acid value along with the progress of the reaction, adding tetrabutyl titanate and vacuumizing after the acid value reaches 30mgKOH/g, gradually vacuumizing the kettle from normal pressure to about-0.098 MPa (25 torr) in 4 hours, sampling and detecting, and obtaining qualified products when the hydroxyl value of the products in the kettle reaches 56.0mgKOH/g, breaking the vacuum of the reaction kettle by nitrogen, cooling to 110 ℃, unloading and packaging to obtain the maleic anhydride polyol with the molecular weight of 2000.

A preparation method of polyurethane surface layer resin with good binding force with organosilicon treating agent comprises the following steps:

s1, preparation of maleic anhydride modified polyester polyol: see above for a process for preparing a maleic anhydride modified polyester polyol having a molecular weight of 2000;

S2, uniformly mixing the maleic anhydride modified polyester polyol prepared in the S1 with accurate metering with polytetrahydrofuran glycol, polycarbonate glycol, 1, 4-butanediol, hydroxyl-terminated methyl vinyl silicone oil IOTA 1203V, MDI, HMDI, stannous octoate, DMF, toluene, antioxidant 1010 and antioxidant 168, reacting for 3.60 hours at 80 ℃, gradually adding 1, 6-hexanediol into a reaction kettle, and heating and reacting to obtain 12-16 x 10 ⁴ And (3) after the temperature of cps/25 ℃, using ethylene glycol to perform 30min termination reaction to obtain the finished polyurethane surface layer resin.

The preparation method of the PU leather composite material prepared by using the polyurethane surface layer resin with good binding force with the organosilicon treating agent comprises the following steps:

s1, preparing polyurethane surface layer resin with good binding force with an organosilicon treating agent, wherein the preparation method of the polyurethane surface layer resin with good binding force with the organosilicon treating agent is disclosed;

meanwhile, the preparation of the organic silicon resin with good binding force with polyurethane resin is carried out, see preparation example 1;

s2, coating the polyurethane surface layer resin with good binding force with the organosilicon treating agent, which is prepared in the S1, on the surface of microfiber cloth (provided by Hexin colali microfiber skin (Jiaxing) limited company), and drying at 160 ℃ for 8min after the polyurethane surface layer resin is roll-coated on the microfiber cloth to obtain a PU surface layer;

And S3, coating the organic silicon resin with good binding force with polyurethane resin, which is prepared in the step S1, on the surface of the PU surface layer, and drying at 150 ℃ for 10min after the organic silicon resin is roll-coated on the PU surface layer, so as to obtain the finished PU leather composite material.

Example 2 differs from example 1 in that: dihydroxyvinyl silicone oil (manufactured by Anhui Ai Yaoda silicone oil Co., ltd., hydroxyl-terminated methyl vinyl silicone oil containing 8.5-9.0 mO1%) was used.

Example 3 differs from example 1 in that: dihydroxyvinyl silicone oil (manufactured by Anhui Ai Yaoda silicone oil Co., ltd., hydroxyl-terminated methyl vinyl silicone oil containing vinyl content of 5.0-6.0 mO1%) was used.

Example 4 differs from example 1 in that: the silicone resin having good bonding force with the polyurethane resin in preparation example 2 was used.

Example 5 differs from example 1 in that: the silicone resin having good bonding force with the polyurethane resin in preparation example 3 was used.

Example 6 differs from example 1 in that: the silicone resin having good bonding strength with polyurethane resin in preparation example 4 was used.

Example 7 differs from example 1 in that: the folding-resistant smooth layer is prepared from a reactive organosilicon treating agent. The reactive silicone treatment in preparation example 5 was used.

Example 8 differs from example 1 in that: the folding-resistant smooth layer is prepared from a reactive organosilicon treating agent. The reactive silicone treatment in preparation example 6 was used.

Example 9 differs from example 1 in that: the folding-resistant smooth layer is prepared from a reactive organosilicon treating agent. The reactive silicone treatment in preparation example 7 was used.

Example 10 differs from example 1 in that: the folding-resistant smooth layer is prepared from a reactive organosilicon treating agent. The reactive silicone treatment in preparation example 8 was used.

Example 11 differs from example 1 in that: a polyurethane top layer resin having good bonding force with a silicone treatment is prepared from 1mol of MDI, 0.25mol of HMDI, 0.06mol of maleic anhydride modified polyester polyol having a molecular weight of 2000, 0.08mol of polyether polyol-polytetrahydrofuran diol having a molecular weight of 3000, 0.08mol of polycarbonate diol having a molecular weight of 2000, 0.2mol of 1, 5-hexadiene-3, 4-diol, 0.4mol of 1, 4-butanediol, 0.4mol of 1, 6-hexanediol, 0.06mol of dihydroxyvinyl silicone oil, 240g of DMF, 640g of toluene, 2g of ethylene glycol, 0.32g of dibutyltin dilaurate, 2g of antioxidant 1010, and 0.5g of antioxidant 168.

Example 12 differs from example 1 in that: a polyurethane top layer resin having good bonding force with a silicone treatment agent is prepared from 1mol of MDI, 0.25mol of HMDI, 0.12mol of maleic anhydride modified polyester polyol having a molecular weight of 2000, 0.08mol of polyether polyol-polytetrahydrofuran diol having a molecular weight of 3000, 0.2mol of 1, 5-hexadiene-3, 4-diol, 0.4mol of 1, 4-butanediol, 0.4mol of 1, 6-hexanediol, 0.06mol of dihydroxyvinyl silicone oil, 200g of DMF, 660g of toluene, 2g of ethylene glycol, 0.30g of stannous octoate, 2g of antioxidant 1010, and 0.5g of antioxidant 168.

Example 13 differs from example 1 in that: a polyurethane top layer resin having good bonding strength with a silicone treatment is prepared from 1mol of MDI, 0.25mol of HMDI, 0.06mol of a maleic anhydride modified polyester polyol having a molecular weight of 2000, 0.08mol of a polyether polyol-polytetrahydrofuran diol having a molecular weight of 3000, 0.08mol of a polycarbonate diol having a molecular weight of 2000, 0.2mol of 1, 5-hexadiene-3, 4-diol, 0.4mol of 1, 4-butanediol, 0.4mol of 1, 6-hexanediol, 0.06mol of a bisaminovinylsilicone oil, 200g of DMF, 650g of toluene, 2.0g of ethylene glycol, 0.30g of dibutyltin dilaurate, 2g of antioxidant 1010, and 0.5g of antioxidant 168.

Example 14 differs from example 1 in that: a polyurethane top layer resin having good bonding strength with a silicone treatment is prepared from 1mol of MDI, 0.25mol of HMDI, 0.08mol of a maleic anhydride modified polyester polyol having a molecular weight of 2000, 0.06mol of a polyether polyol-polytetrahydrofuran diol having a molecular weight of 3000, 0.06mol of a polycarbonate diol having a molecular weight of 2000, 0.1mol of 1, 5-hexadiene-3, 4-diol, 0.45mol of 1, 4-butanediol, 0.45mol of 1, 6-hexanediol, 0.06mol of a bisaminovinylsilicone oil, 240g of DMF, 620g of toluene, 2.0g of ethylene glycol, 0.32g of dibutyltin dilaurate, 2g of antioxidant 1010, and 0.5g of antioxidant 168.

Example 16 differs from example 1 in that: a polyurethane top layer resin having good bonding force with a silicone treatment is prepared from 1mol of MDI, 0.25mol of HMDI, 0.08mol of maleic anhydride modified polyester polyol having a molecular weight of 2000, 0.06mol of polyether polyol-polytetrahydrofuran diol having a molecular weight of 3000, 0.06mol of polycarbonate diol having a molecular weight of 2000, 0.3mol of 1, 5-hexadiene-3, 4-diol, 035mol of 1, 4-butanediol, 0.35mol of 1, 6-hexanediol, 0.06mol of bisaminovinylsilicone oil, 200g of DMF, 650g of toluene, 2.0g of ethylene glycol, 0.28g of dibutyltin dilaurate, 2g of antioxidant 1010, and 0.5g of antioxidant 168.

Example 16 differs from example 1 in that: a polyurethane top layer resin having good bonding strength with a silicone treatment is prepared from 1mol of MDI, 0.25mol of HMDI, 0.08mol of maleic anhydride modified polyester polyol having a molecular weight of 2000, 0.06mol of polyether polyol-polytetrahydrofuran diol having a molecular weight of 3000, 0.06mol of polycarbonate diol having a molecular weight of 2000, 0.3mol of 1, 5-hexadiene-3, 4-diol, 03mol of 1, 4-butanediol, 0.30mol of 1, 6-hexanediol, 0.1mol of isophorone diamine, 0.06mol of bisaminovinyl silicone oil, 200g of DMF, 650g of toluene, 2.0g of ethylene glycol, 0.28g of dibutyl tin dilaurate, 2g of antioxidant 1010, 0.5g of antioxidant 168. Example 17 differs from example 1 in that: the molecular weight 2000 maleic anhydride modified polyester polyol was replaced with a molecular weight 3000 maleic anhydride modified polyester polyol.

The molecular weight 3000 maleic anhydride modified polyester polyol was a molecular weight 3000 maleic anhydride modified polyester polyol prepared from 36g maleic anhydride, 146g adipic acid, 152g 2-methyl-1, 3 propanediol, 0.02g tetrabutyl titanate, 0.03g antioxidant 1076.

The preparation method of the maleic anhydride modified polyester polyol with the molecular weight of 3000 comprises the following steps:

S1, putting maleic anhydride, adipic acid, 2-methyl-1, 3-propanediol and an antioxidant 1076 into a reaction kettle, heating to react, and keeping the temperature for 3h at the temperature of 135 ℃ in the first stage kettle; then heating to 230 ℃ at constant speed in 4 hours, and preserving heat for 3.0 hours;

s2, controlling the temperature at the top of the distillation tower to be between 101 and 103 ℃, sampling to measure the acid value along with the reaction, adding tetrabutyl titanate and vacuumizing after the acid value reaches 30mgKOH/g, gradually vacuumizing the pressure in the kettle from normal pressure to about-0.098 MPa (25 torr) within 4 hours, sampling and detecting, and when the hydroxyl value of the product in the kettle reaches 37.4+/-2.0 mgKOH/g, obtaining the qualified product, breaking the vacuum of the reaction kettle by using nitrogen, cooling to 110 ℃, unloading and packaging to obtain the maleic anhydride polyol with the molecular weight of 3000.

Example 18 differs from example 1 in that: the maleic anhydride modified polyester polyol having a molecular weight of 2000 was replaced with a maleic anhydride modified polyester polyol having a molecular weight of 1000.

The molecular weight 1000 maleic anhydride-modified polyester polyol was a molecular weight 1000 maleic anhydride-modified polyester polyol prepared from 30g of maleic anhydride, 146g of adipic acid, 120g of 1,2 propylene glycol, 0.02g of tetrabutyl titanate, 0.03g of antioxidant 1076.

The preparation method of the maleic anhydride modified polyester polyol with the molecular weight of 1000 comprises the following steps:

s1, putting maleic anhydride, adipic acid, 1, 2-propylene glycol and an antioxidant 1076 into a reaction kettle, heating to react, and keeping the temperature for 3h when the temperature of the kettle is raised to 135 ℃ in the first stage; then heating to 230 ℃ at constant speed in 4 hours, and preserving heat for 3.0 hours;

s2, controlling the temperature at the top of the distillation tower to be between 101 and 103 ℃, sampling to measure the acid value along with the reaction, adding tetrabutyl titanate and vacuumizing after the acid value reaches 30mgKOH/g, gradually vacuumizing the pressure in the kettle to about-0.098 MPa (25 torr) from normal pressure within 4.0h, sampling and detecting, judging the product is qualified when the hydroxyl value of the product in the kettle reaches 112+/-3 mgKOH/g, breaking the vacuum of the reaction kettle by nitrogen, cooling to 110 ℃, unloading and packaging to obtain the maleic anhydride polyol with the molecular weight of 1000.

Comparative example 1 differs from example 1 in that: no dihydroxyvinyl silicone oil is contained and conventional polyester polyols are used. The method comprises the following steps: a polyurethane top layer resin having good bonding force with a silicone treatment agent is prepared from 1mol of MDI, 0.25mol of HMDI, 0.12mol of a polyester polyol-polyhexamethylene adipate glycol having a molecular weight of 2000 (CAS: 25212-06-0), 0.052mol of a polyether polyol-polytetrahydrofuran glycol having a molecular weight of 3000, 0.054mol of a polycarbonate diol having a molecular weight of 2000, 0.522mol of 1, 4-butanediol, 0.53mol of 1, 6-hexanediol, 200g of DMF, 600g of toluene, 2g of ethylene glycol, 0.28g of stannous octoate, 2g of an antioxidant 1010, and 0.5g of an antioxidant 168. And the folding-resistant smooth layer adopts the organic silicon resin with good binding force with polyurethane resin in preparation example 5.

Comparative example 2 differs from comparative example 1 in that: the silicone resin having good bonding force with the polyurethane resin in preparation example 6 was used.

Comparative example 3 differs from comparative example 1 in that: the silicone resin having good bonding strength with polyurethane resin in preparation example 7 was used.

Comparative example 4 differs from comparative example 1 in that: the silicone resin having good bonding force with the polyurethane resin in preparation example 8 was used.

(1) The method for testing the folding endurance comprises the following steps: after being placed in an environment with 80 ℃ and 75% humidity for 400 hours, the steel plate is placed in an environment with minus 20 ℃ and is bent until cracking, and the bending times (ten thousands times) are recorded.

(2) The method for testing the hemming wear resistance comprises the following steps:

1. test purpose: and detecting the abrasion resistance degree of the sample under the action of a certain external force.

2. The device comprises: PK-237 double-hammer electric friction decoloring tester

3. The operation steps are as follows:

3-1 sampling, namely measuring 185mm 55mm samples and cutting;

3-2 clamping the sample, namely folding the sample in half and fixing the folded sample at the middle position of the fixer;

3-3, replacing the friction cloth on the friction head of the equipment, and putting down the friction head to enable the sample edge to be positioned in the middle of the friction head;

3-4, starting the test:

3-4-1 switching on a power switch of the power-on instrument;

3-4-2, setting test times on the control panel according to the test requirements;

Zeroing the 3-4-3 equipment;

3-4-4, starting the test, reaching the set test times, automatically stopping the machine or stopping the machine by pressing a stop key when the test sample is damaged in the test process;

3-5, judging the result: taking down the test sample, and judging the test result;

4. notice matters

4-1, in the sample clamping process, the folded edges of the sample are required to be just overlapped with the center line of the fixer;

4-2 the friction cloth must be changed one by one;

4-3, when the result is judged, the judgment needs to be carried out under the condition of sufficient light, and when necessary, the judgment needs to be carried out under the condition of lamplight.

(3) And (3) testing the stain resistance grade: stain resistance rating was tested according to GMW 3402.

Table 1 shows the test parameters of PU leather materials in preparation examples 1 to 8

	-20 ℃ folding endurance (ten thousand times)	Hemming wear-resistant (times)	Dirt resistance grade
				Example 1	More than 10 ten thousand times	More than 10 ten thousand times	Grade 8 or more
Example 2	More than 10 ten thousand times	More than 10 ten thousand times	Grade 8 or more
				Example 3	More than 10 ten thousand times	More than 10 ten thousand times	Grade 8 or more
Example 4	More than 10 ten thousand times	More than 10 ten thousand times	Grade 8 or more
				Comparative example 1	3 ten thousand times	5 ten thousand (5)	Grade 8 or more
Comparative example 2	6 ten thousand times	7 ten thousand (7)	Grade 8 or more
				Comparative example 3	7 ten thousand times	8 ten thousand (ten thousand)	Grade 8 or more
Comparative example 4	7 ten thousand times	7 ten thousand (7)	Grade 8 or more

Remarks: the PU leather materials for testing can be obtained by spin-coating the organic silicon resin with excellent bonding force with polyurethane surface layer resin on the surface of synthetic leather (provided by Zhejiang Hexin New material Co., ltd., model 5BVF-AM9-38LS-FOJ 9-136) and baking at 160 ℃ for 8 minutes.

As can be seen by combining preparation examples 1-8 and combining Table 1, the silicone resin surface treatment layer prepared by the method has excellent bonding force with the polyurethane surface layer resin, is not easy to fall off or peel off, has relatively durable service life, and can have good folding resistance, wear resistance, antifouling and slip effects.

Table 2 is a table of the test parameters for the PU leather composites of examples 1-18 and comparative examples 1-4

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As can be seen from the combination of examples 1 to 18 and comparative examples 1 to 4 and the combination of Table 2, the PU surface layer formed by the polyurethane surface layer resin prepared in the application has good bonding force with the surface treatment layer formed by the conventional organosilicon treating agent (preparation examples 5 to 8) on the market, is not easy to fall off, and endows the polyurethane surface layer resin with overall durable wear resistance, folding resistance, dirt resistance and smooth performance. The PU leather composite material prepared by the commercially available reactive organosilicon treating agent is suitable for industrial production, has relatively low production cost, and is applied to the fields of case leather, shoe leather and the like.

It can be seen from the combination of examples 1 to 18 and comparative examples 1 to 4 and the combination of tables 1 to 2 that the PU surface layer formed from the polyurethane surface layer resin prepared in the present application has excellent bonding force with the surface treatment layer formed from the silicone treatment agent prepared in the present application (preparation examples 1 to 4), long service life, good weather resistance, and gives the whole more durable abrasion resistance, folding resistance, stain resistance, and smooth property.

To test the difference in the folding endurance of the commercially available conventional silicone treatment agents (preparation examples 5 to 8) and the silicone resins excellent in the bonding force with the polyurethane topcoat resin (preparation examples 1 to 4), the folding endurance was further tested for example 1 and example 7, and the folding endurance test was performed for the folding endurance number Q _MAX The number of times of fracture resistance of the PU leather composite material was observed. As is evident from the test, the number of folding times Q of example 1 _MAX Cracking was observed up to 35 ten thousand times, and the number of folding endurance Q of example 7 _MAX The cracking is observed for 20 ten thousand times, so that the PU surface layer formed by the polyurethane surface layer resin prepared by the application has more excellent bonding force with the surface treatment layer formed by the organosilicon treating agent (preparation examples 1-4) prepared by the application, but the overall production cost is relatively high, and the polyurethane surface layer resin is suitable for high-end leather materials or personal customized personalized products.

The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.

Claims (10)

1. A polyurethane surface layer resin with good binding force with an organosilicon treating agent is characterized in that: the chain extender is mainly prepared from polyalcohol, chain extender, vinyl silicone oil with active groups at two ends, diisocyanate, catalyst, organic solvent, auxiliary agent and terminator;

The diisocyanate is at least one of diisocyanates with molecular weight less than 300 g/mol;

the polyol is at least one of polyether polyol and polycarbonate polyol with molecular weight of 1000-3000 matched with maleic anhydride modified polyester polyol;

the chain extender is at least one of saturated glycol, diamine and alcohol amine with the molecular weight of 76-200 g/mol and the double bond-containing glycol with the molecular weight of 61-200 g/mol;

the maleic anhydride modified polyester polyol is mainly prepared from maleic anhydride, adipic acid and low-polarity dihydric alcohol, wherein the mass of the maleic anhydride is 5-25wt% of that of the adipic acid;

the low-polarity dihydric alcohol is at least one of glycol with a molecular weight of 76-200 g/mol and dihydric alcohol containing a side group; the dihydric alcohol containing the side group is at least one of poly 1,3 propylene glycol, 1,5 pentanediol, 1,2 propanediol and neopentyl glycol;

the mass of the catalyst is equal to 10ppm-500ppm of the total mass of diisocyanate, polyol and chain extender; the catalyst is organic tin;

the molar ratio of the polyol to the chain extender is controlled at 1: (0.01-0.3);

the organic solvent comprises at least one of acetone, butanone, DMF and toluene;

The terminator is a dihydroxy small molecule;

the vinyl silicone oil with active groups at two ends is at least one of dihydroxyvinyl silicone oil and vinyl amino-terminated silicone oil;

the auxiliary agent comprises at least one of polymerization inhibitor, flatting agent, slipping agent, dispersing agent, adhesion promoter, coupling agent, defoaming agent, thickening agent, antioxidant, anti-ultraviolet agent, color paste and functional filler.

2. The polyurethane surface layer resin with good binding force with organosilicon treating agent as set forth in claim 1, wherein: the preparation method of the maleic anhydride modified polyester polyol comprises the following steps: firstly, maleic anhydride, adipic acid and low-polarity dihydric alcohol are put into a reaction kettle, the temperature is increased to react, the kettle temperature in the first stage is increased to 130-135 ℃, and the temperature is maintained for 3h; then heating to 225-230 ℃ at constant speed within 4 hours, and preserving heat for 3.0 hours; then controlling the temperature at the top of the distillation tower to be between 101 and 103 ℃, sampling to measure the acid value along with the reaction, adding tetrabutyl titanate and vacuumizing after the acid value reaches 30mgKOH/g, gradually vacuumizing the kettle from normal pressure to about-0.098 MPa (25 torr) relative to vacuum within 4 hours, sampling and detecting, and finally breaking the reaction kettle by nitrogen and cooling to 108 to 110 ℃ when the hydroxyl value of the product in the kettle reaches 17 to 224mgKOH/g, unloading and packaging to obtain the maleic anhydride polyol with the molecular weight of 500 to 6500.

3. The polyurethane surface layer resin with good binding force with organosilicon treating agent as set forth in claim 2, wherein: the polyol is prepared from maleic anhydride modified polyester polyol with a molecular weight of 2000, polytetrahydrofuran ether glycol with a molecular weight of 3000 and polycarbonate glycol with a molecular weight of 2000 in a molar ratio of (2-4): (1-4): (1-4).

4. The polyurethane surface layer resin with good binding force with organosilicon treating agent as set forth in claim 1, wherein: the chain extender is at least one of 3-allyloxy-1, 2-propylene glycol, 1, 4-butylene glycol, 1, 5-hexadiene-3, 4-diol, 1, 4-butanediol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol, 1, 4-butanediamine, 1, 5-pentanediamine, 1, 6-hexanediamine, isophorone diamine, 4' -diamino dicyclohexylmethane and hexamethylenediamine.

5. The polyurethane surface layer resin with good binding force with organosilicon treating agent according to claim 4, which is characterized in that: the chain extender is prepared from 1, 5-hexadiene-3, 4-diol, 1, 6-hexanediol and isophorone diamine according to the molar ratio of (1-3): (4-8): (4-8).

6. The polyurethane surface layer resin with good binding force with organosilicon treating agent as set forth in claim 1, wherein: the diisocyanate consists of MDI and HMDI in the molar ratio of (6-8) to (2-4).

7. A method for preparing a polyurethane surface layer resin with good binding force with an organosilicon treating agent according to any one of claims 1-6, which is characterized in that: the method comprises the following steps:

s1, preparing maleic anhydride modified polyester polyol;

s2, the maleic anhydride modified polyester polyol prepared in the S1 is mixed with the rest polyol, the chain extender and the dihydroxyethylAlkenyl silicone oil, diisocyanate, catalyst, organic solvent and assistant are mixed evenly and heated to react to 3-20 x 10 ⁴ And (3) after cps/25 ℃, terminating the reaction by using a terminator to obtain the finished polyurethane surface layer resin.

8. A PU leather composite prepared using the polyurethane topcoat resin of any one of claims 1-6 having good adhesion to silicone treatment, characterized in that: the PU leather composite material comprises microfiber cloth, wherein a PU surface layer is compounded on the surface of the microfiber cloth; the PU surface layer is made of the polyurethane surface layer resin with good binding force with the organosilicon treating agent in any one of claims 1-8; the surface of the PU surface layer, which is back to the microfiber cloth, is compounded with a folding-resistant smooth layer; the folding-resistant slipping layer is prepared from organic silicon resin or a reactive organic silicon treating agent which has good binding force with polyurethane resin; the reactive organosilicon treating agent mainly comprises vinyl silicone oil, hydrogen-containing silicone oil and a catalyst; the organic silicon resin with good binding force with polyurethane resin is prepared from a component A, a component B and a platinum catalyst; the component A is mainly prepared from polyalcohol, chain extender, diisocyanate, organic solvent, catalyst, auxiliary agent and vinyl silicone oil, wherein the polyalcohol in the component A is at least one of maleic anhydride modified polyester polyalcohol, polyether with molecular weight of 1000-3000 or polycarbonate polyalcohol; the maleic anhydride modified polyester polyol in the folding-resistant smooth layer is the same as the maleic anhydride modified polyester polyol adopted in the PU surface layer; the component B is hydrogen-containing silicone oil; the molar ratio of the vinyl in the component A to the active hydrogen in the hydrogen-containing silicone oil in the component B is 1 (1.1-1.3).

9. The PU leather composite material according to claim 8, which is prepared by using polyurethane surface layer resin having good binding force with organosilicon treating agent, wherein the PU leather composite material is characterized in that: the chain extender in the component A is one or a mixture of more than two of diol, diamine or alcohol amine with the molecular weight of 61-200 g/mol; the diisocyanate in the component A is one or a mixture of more than two diisocyanates with molecular weight less than 300 g/mol; the vinyl silicone oil in the component A is one or a mixture of more than two vinyl silicone oils with the vinyl content of 0.09-20wt%; the hydrogen content of the hydrogen-containing silicone oil in the component B is 0.03% -1.60%; the auxiliary agent in the component A comprises one or a mixture of more than two of an antioxidant, matting powder and light stabilizer.

10. The PU leather composite material according to claim 8, which is prepared by using polyurethane surface layer resin having good binding force with organosilicon treating agent, wherein the PU leather composite material is characterized in that: the preparation method comprises the following steps:

s1, preparing polyurethane surface layer resin with good binding force with an organosilicon treating agent;

meanwhile, preparing the folding-resistant and slipping-resistant layer organic silicon resin;

s2, coating polyurethane surface layer resin with good binding force with the organosilicon treating agent, which is prepared in the step S1, on the surface of the microfiber cloth, and drying for 5-10min at 150-170 ℃ after the polyurethane surface layer resin is roll-coated on the microfiber cloth to obtain a PU surface layer;

And S3, coating the folding-resistant and slipping-resistant layer organic silicon resin prepared in the step S1 on the surface of the PU surface layer, and baking at 150-170 ℃ for 5-10min after the organic silicon resin is roll-coated on the PU surface layer to obtain the finished PU leather composite material.