阅读说明：本技术 高水压耐水洗的纺织涂层用聚氨酯底胶树脂及其制备方法 (High-water-pressure washing-resistant polyurethane primer resin for textile coating and preparation method thereof ) 是由 陈元昌 舒科进 于 2021-01-15 设计创作，主要内容包括：本发明提供了高水压耐水洗的纺织涂层用聚氨酯底胶树脂和制备方法,该底胶树脂以下的组分构成：已二酸与新戊二醇共聚二元醇,聚碳酸酯二元醇,1、4－丁二醇,三羟甲基丙烷,甲苯二异氰酸酯,4、4－二苯基甲烷二异氰酸酯、乙二醇。本发明利用其新戊二醇的侧链甲基具有良好的拒水性能,从而可大力提升产品的抗水压性能,并结合采用聚碳酸酯多元醇来增加产品的耐水解性能,可提高产品洗前水压与洗后水压,也适用于高丹尼数(如600D牛津布等)的布料上,以满足产品户外环境条件下使用需求,又可提高底胶树脂对基材的附着力,并减轻涂布制备产品易吸水易膨润的问题,且聚酯多元醇的附着力较好,对水洗后水压有较大帮助和提升。(The invention provides a high-water-pressure washing-resistant polyurethane primer resin for a textile coating and a preparation method thereof, wherein the primer resin comprises the following components: adipic acid and neopentyl glycol copolymerized dihydric alcohol, polycarbonate dihydric alcohol, 1, 4-butanediol, trimethylolpropane, toluene diisocyanate, 4-diphenylmethane diisocyanate and ethylene glycol. According to the invention, the side chain methyl of neopentyl glycol has good water repellency, so that the water pressure resistance of a product can be greatly improved, and polycarbonate polyol is adopted to improve the hydrolysis resistance of the product, so that the water pressure of the product before washing and the water pressure of the product after washing can be improved, and the polyester polyol is also suitable for cloth with high denier (such as 600D oxford cloth) to meet the use requirement of the product under the outdoor environment condition, the adhesive force of primer resin to a base material can be improved, the problem that the product prepared by coating is easy to absorb water and swell is solved, and the polyester polyol has good adhesive force, so that the water pressure after washing is greatly helped and improved.)

1. High water pressure is resistant polyurethane primer resin for textile coating who washes, its characterized in that: the high-water-pressure washing-resistant polyurethane primer resin for the textile coating comprises the following components in percentage by weight:

antioxidant: 0.01 to 0.3%, copolymerized diol: 24-44%, polycarbonate diol: 5-10%, toluene diisocyanate: 2-8%, ethylene glycol 0.05-0.5%, 4-diphenylmethane diisocyanate: 2-8%, chain extender 1.5-4.5%, and malic acid: 0.05 to 0.5%, dimethylformamide: 20-30% and toluene: 20-30%.

2. The high water pressure wash-resistant polyurethane primer resin for textile coatings according to claim 1, characterized in that: the copolymerized dihydric alcohol is copolymerized dihydric alcohol of adipic acid and neopentyl glycol, the molecular weight of the copolymerized dihydric alcohol is 1000-4000, and the number of hydroxyl groups is 2.

3. The high water pressure wash-resistant polyurethane primer resin for textile coatings according to claim 1, characterized in that: the antioxidant is one or two of JPP-100 and 2, 6-di-tert-butyl-4-methylphenol.

4. The high water pressure wash-resistant polyurethane primer resin for textile coatings according to claim 1, characterized in that: the chain extender is one or two of 1, 4-butanediol, neopentyl glycol, 1.6 hexanediol and trimethylolpropane.

5. The high water pressure wash-resistant polyurethane primer resin for textile coatings according to claim 1, characterized in that: the high-water-pressure washing-resistant polyurethane primer resin for the textile coating comprises the following components in percentage by weight:

JPP-100: 0.01 to 0.3%, adipic acid and neopentyl glycol copolymerized diol: 24-44%, polycarbonate diol: 5-10%, 1, 4-butanediol: 1.5-4.5%, trimethylolpropane: 0.05-1%, toluene diisocyanate: 2-8%, 4-diphenylmethane diisocyanate: 2-8% of ethylene glycol: 0.05-0.5%, malic acid: 0.05 to 0.5%, dimethylformamide: 20-30% and toluene: 20-30%.

6. The method of preparing a high water pressure wash resistant polyurethane primer resin for textile coatings as claimed in claim 1, wherein: the preparation method comprises the following steps:

the first step is as follows: putting 42-58% of dimethylformamide, an antioxidant, adipic acid and neopentyl glycol copolymerized dihydric alcohol, polycarbonate dihydric alcohol, 1, 4-butanediol and trimethylolpropane into a reaction kettle, stirring for 10-30 min, and keeping the temperature to 60-80 ℃;

the second step is that: adding all toluene diisocyanate, and reacting for 1-2.5 h at the temperature of 80-98 ℃;

the third step: adding 25-45% of dimethylformamide and 60-70% of methylbenzene into a reaction kettle, stirring for 5-15 min, and cooling to 60-80 ℃;

the fourth step: adding 42-58% of 4, 4-diphenylmethane diisocyanate, and reacting for 20-40 min after keeping the temperature to 70-90 ℃;

the fifth step: adding 5-15% of 4, 4-diphenylmethane diisocyanate every 20-40 min to correct the viscosity to the required value;

and a sixth step: adding ethylene glycol, terminating the reaction by using excessive hydroxyl of the ethylene glycol, adding malic acid, 5-25% of dimethylformamide and 20-40% of toluene, fully stirring for 20-40 min, discharging and subpackaging to obtain the polyurethane primer resin with the solid content of 50 +/-2%, the viscosity of 60000-90000 CPS/25 ℃ and the 100% elastic modulus of 1-2 Mpa.

7. The method for preparing the polyurethane primer resin for the high water pressure washing-resistant textile coating according to claim 6, wherein the polyurethane primer resin comprises the following components: the preparation method comprises the following steps:

the first step is as follows: putting 45-55% of dimethylformamide, JPP-100, adipic acid and neopentyl glycol copolymerized dihydric alcohol, polycarbonate dihydric alcohol, 1, 4-butanediol and trimethylolpropane into a reaction kettle, stirring for 15-25 min, and keeping the temperature to 65-75 ℃;

the second step is that: adding all toluene diisocyanate, and keeping the temperature to 85-95 ℃ to react for 1-2 h;

the third step: adding 30-40% of total amount of dimethylformamide and 65-75% of total amount of toluene into a reaction kettle, stirring for 8-13 min, and cooling to 65-75 ℃;

the fourth step: adding 45-55% of 4, 4-diphenylmethane diisocyanate, keeping the temperature to 75-85 ℃, and reacting for 25-35 min;

the fifth step: adding 5-15% of 4, 4-diphenylmethane diisocyanate every 25-35 min to correct the viscosity to the required value;

and a sixth step: adding ethylene glycol, terminating the reaction by using excessive hydroxyl of the ethylene glycol, adding malic acid, 10-20% of dimethylformamide and 25-35% of toluene, fully stirring for 25-35 min, discharging and subpackaging to obtain the polyurethane primer resin with the solid content of 50 +/-2%, the viscosity of 60000-90000 CPS/25 ℃ and the 100% elastic modulus of 1-2 Mpa.

Technical Field

Embodiments disclosed herein relate generally to the field of chemical engineering, and more particularly, to a high-water-pressure water-fast polyurethane primer resin for textile coatings and a method for preparing the same.

Background

The fabric coating is the composition of fabric and high molecular polymer, the performance of the composite fabric is obviously changed, the original function of the fabric is maintained, the function of the covering layer is increased, the fabric coating technology provides more possibilities for manufacturing functional fabrics in the textile industry, the application of the fabric is greatly widened, and the application field is wider and wider. The fabric coating is a textile after-finishing technology which is developed most rapidly and widely in recent years, and the fabric finished by the coating has special performances of water resistance, air permeability, moisture permeability, stain resistance, flame retardance, antistatic property and the like, and plays an important role in three pillar products of textiles, namely clothes materials, industrial cloth and interior decoration.

Most of the high water pressure resistant coating adhesives/emulsions for textiles in the market at present are solvent-based coating adhesives which have good performances, but harmful substances such as toluene, DMF and the like can be discharged in the using process, so that the environment is polluted and the human body is damaged. The water-based polyurethane emulsion for the water pressure resistance of the textile has the advantages of low temperature resistance, good solvent resistance, good elasticity and flexibility, but poor water resistance, poor washing fastness, low mechanical strength and poor abrasion resistance. The water pressure effect of the existing polyurethane product for the textile coating on some high-denier (such as 600D oxford cloth) fabrics is not ideal, and particularly, the water pressure after washing is very low, so that the requirement of a customer cannot be met.

Disclosure of Invention

Aiming at the problems in the prior art, the invention aims to provide a high-water-pressure water-washing-resistant polyurethane primer resin for a textile coating and a preparation method thereof, which can effectively solve the problems in the prior art.

The technical scheme of the invention is as follows:

the polyurethane primer resin for the high-water-pressure water-washing-resistant textile coating comprises the following components in percentage by weight:

antioxidant: 0.01 to 0.3%, copolymerized diol: 24-44%, polycarbonate diol: 5-10%, toluene diisocyanate: 2-8%, ethylene glycol 0.05-0.5%, 4-diphenylmethane diisocyanate: 2-8%, chain extender 1.5-4.5%, and malic acid: 0.05 to 0.5%, dimethylformamide: 20-30% and toluene: 20-30%.

Preferably, the copolymerized diol is copolymerized diol of adipic acid and neopentyl glycol, the molecular weight of the copolymerized diol is 1000-4000, and the number of hydroxyl groups is 2.

Preferably, the antioxidant is one or two of JPP-100 and 2, 6-di-tert-butyl-4-methylphenol.

Preferably, the chain extender is one or two of 1, 4-butanediol, neopentyl glycol, 1, 6 hexanediol and trimethylolpropane.

Preferably, the high-water-pressure washing-resistant polyurethane primer resin for the textile coating comprises the following components in percentage by weight:

JPP-100: 0.01 to 0.3%, adipic acid and neopentyl glycol copolymerized diol: 24-44%, polycarbonate diol: 5-10%, 1, 4-butanediol: 1.5-4.5%, trimethylolpropane: 0.05-1%, toluene diisocyanate: 2-8%, 4-diphenylmethane diisocyanate: 2-8% of ethylene glycol: 0.05-0.5%, malic acid: 0.05 to 0.5%, dimethylformamide: 20-30% and toluene: 20-30%.

Further, the present invention also provides: the preparation method of the polyurethane primer resin for the textile coating with high water pressure and washing resistance comprises the following steps:

the first step is as follows: putting 42-58% of dimethylformamide, an antioxidant, adipic acid and neopentyl glycol copolymerized dihydric alcohol, polycarbonate dihydric alcohol, 1, 4-butanediol and trimethylolpropane into a reaction kettle, stirring for 10-30 min, and keeping the temperature to 60-80 ℃;

the second step is that: adding all toluene diisocyanate, and reacting for 1-2.5 h at the temperature of 80-98 ℃;

the third step: adding 25-45% of dimethylformamide and 60-70% of methylbenzene into a reaction kettle, stirring for 5-15 min, and cooling to 60-80 ℃;

the fourth step: adding 42-58% of 4, 4-diphenylmethane diisocyanate, and reacting for 20-40 min after keeping the temperature to 70-90 ℃;

the fifth step: adding 5-15% of 4, 4-diphenylmethane diisocyanate every 20-40 min to correct the viscosity to the required value;

and a sixth step: adding ethylene glycol, terminating the reaction by using excessive hydroxyl of the ethylene glycol, adding malic acid, 5-25% of dimethylformamide and 20-40% of toluene, fully stirring for 20-40 min, discharging and subpackaging to obtain the polyurethane primer resin with the solid content of 50 +/-2%, the viscosity of 60000-90000 CPS/25 ℃ and the 100% elastic modulus of 1-2 Mpa.

Preferably, the preparation method of the high-water-pressure washing-resistant polyurethane primer resin for the textile coating comprises the following steps:

the first step is as follows: putting 45-55% of dimethylformamide, JPP-100, adipic acid and neopentyl glycol copolymerized dihydric alcohol, polycarbonate dihydric alcohol, 1, 4-butanediol and trimethylolpropane into a reaction kettle, stirring for 15-25 min, and keeping the temperature to 65-75 ℃;

the second step is that: adding all toluene diisocyanate, and keeping the temperature to 85-95 ℃ to react for 1-2 h;

the third step: adding 30-40% of dimethylformamide and 65-75% of methylbenzene into a reaction kettle, stirring for 8-13 min, and cooling to 65-75 ℃;

the fourth step: adding 45-55% of 4, 4-diphenylmethane diisocyanate, keeping the temperature to 75-85 ℃, and reacting for 25-35 min;

the fifth step: adding 5-15% of 4, 4-diphenylmethane diisocyanate every 25-35 min to correct the viscosity to the required value;

and a sixth step: adding ethylene glycol, terminating the reaction by using excessive hydroxyl of the ethylene glycol, adding malic acid, 10-20% of dimethylformamide and 25-35% of toluene, fully stirring for 25-35 min, discharging and subpackaging to obtain the polyurethane primer resin with the solid content of 50 +/-2%, the viscosity of 60000-90000 CPS/25 ℃ and the 100% elastic modulus of 1-2 Mpa.

The invention has the advantages that:

(1) according to the invention, the side chain methyl of neopentyl glycol has good water repellency, so that the water pressure resistance of a product can be greatly improved, and polycarbonate polyol is adopted to improve the hydrolysis resistance of the product, so that the water pressure of the product before washing and the water pressure of the product after washing can be improved, and the polyester polyol is also suitable for cloth with high denier (such as 600D oxford cloth) to meet the use requirement of the product under the outdoor environment condition, the adhesive force of primer resin to a base material can be improved, and the problem that the product prepared by coating is easy to hydrolyze and age is solved.

(2) During the reaction process, the mixed block polymerization mode of the polyol copolymerized by adipic acid and neopentyl glycol and polycarbonate diol is adopted. The two polyols are complementary in performance, the adipic acid and neopentyl glycol polyol has lower crystallinity, better flexibility, good water repellency and good adhesion property with base cloth, and the polycarbonate mixed polymerization side can provide higher crystallinity, tensile strength of a film and excellent hydrolysis resistance and acid and salt resistance.

(3) The invention adopts excessive glycol as a stopping agent for end capping, can lead the tail end of a molecular chain to have a small amount of hydroxyl, and is beneficial to curing and crosslinking of various bridging agents used in the subsequent processing. The crosslinking density and the curing fastness of the product are improved.

It should be understood that the statements herein reciting aspects are not intended to limit the critical or essential features of any embodiment of the invention, nor are they intended to limit the scope of the invention. Other features of the present invention will become apparent from the following description.

Detailed Description

Example 1

The polyurethane primer resin for the high-water-pressure water-washing-resistant textile coating comprises the following components in percentage by weight:

JPP-100: 0.01%, adipic acid copolymerized with neopentyl glycol: 44%, polycarbonate diol: 5%, 1, 4-butanediol: 1.5%, trimethylolpropane: 0.05%, toluene diisocyanate: 2%, 4-diphenylmethane diisocyanate: 2%, ethylene glycol: 0.05%, malic acid: 0.05%, dimethylformamide: 20%, toluene: 25.34 percent.

The preparation method of the polyurethane primer resin for the high-water-pressure washing-resistant textile coating comprises the following steps:

the first step is as follows: putting 45% of dimethylformamide, JPP-100, adipic acid and neopentyl glycol copolymerized dihydric alcohol, polycarbonate dihydric alcohol, 1, 4-butanediol and trimethylolpropane into a reaction kettle, stirring for 15min, and keeping the temperature to 65 ℃;

the second step is that: adding all toluene diisocyanate and keeping the temperature to 85 ℃ to react for 2 hours;

the third step: adding 40% of dimethylformamide and 65% of toluene, stirring for 8min, and cooling to 65 ℃;

the fourth step: adding 45% of 4, 4-diphenylmethane diisocyanate, keeping the temperature to 75 ℃ and reacting for 35 min;

the fifth step: adding 15% 4, 4-diphenylmethane diisocyanate every 35min to correct the viscosity to the required value;

and a sixth step: adding ethylene glycol, terminating the reaction by using excessive hydroxyl of the ethylene glycol, adding malic acid, 15% of dimethylformamide and 35% of toluene, fully stirring for 25min, discharging and subpackaging to obtain the polyurethane primer resin with the solid content of 50 +/-2%, the viscosity of 60000-90000 CPS/25 ℃ and the 100% elastic modulus of 1-2 Mpa.

Example 2

The polyurethane primer resin for the high-water-pressure water-washing-resistant textile coating comprises the following components in percentage by weight:

JPP-100: 0.3%, adipic acid copolymerized with neopentyl glycol: 24%, polycarbonate diol: 10%, 1, 4-butanediol: 3%, trimethylolpropane: 1%, toluene diisocyanate: 8%, 4-diphenylmethane diisocyanate: 8%, ethylene glycol: 0.5%, malic acid: 0.5%, dimethylformamide: 24.7%, toluene: 20 percent.

The preparation method of the polyurethane primer resin for the high-water-pressure washing-resistant textile coating comprises the following steps:

the first step is as follows: putting 55% of dimethylformamide, JPP-100, adipic acid and neopentyl glycol copolymerized dihydric alcohol, polycarbonate dihydric alcohol, 1, 4-butanediol and trimethylolpropane into a reaction kettle, stirring for 25min, and keeping the temperature to 75 ℃;

the second step is that: adding all toluene diisocyanate and keeping the temperature to 95 ℃ to react for 1 h;

the third step: adding 30% of dimethylformamide and 75% of toluene, stirring for 13min, and cooling to 75 ℃;

the fourth step: adding 55% of 4, 4-diphenylmethane diisocyanate, keeping the temperature to 85 ℃, and reacting for 25 min;

the fifth step: adding 5% 4, 4-diphenylmethane diisocyanate every 25min to correct the viscosity to the required value;

and a sixth step: adding ethylene glycol, terminating the reaction by using excessive hydroxyl of the ethylene glycol, adding malic acid, 15% of dimethylformamide and 25% of toluene, fully stirring for 35min, discharging and subpackaging to obtain the polyurethane primer resin with the solid content of 50 +/-2%, the viscosity of 60000-90000 CPS/25 ℃ and the 100% elastic modulus of 1-2 Mpa.

Example 3

The polyurethane primer resin for the high-water-pressure water-washing-resistant textile coating comprises the following components in percentage by weight:

JPP-100: 0.01%, adipic acid copolymerized with neopentyl glycol: 30.19%, polycarbonate diol: 7.5%, 1, 4-butanediol: 2.4%, trimethylolpropane: 0.1%, toluene diisocyanate: 4.9%, 4-diphenylmethane diisocyanate: 4.7%, ethylene glycol: 0.1%, malic acid: 0.1%, dimethylformamide: 25%, toluene: 25 percent.

The preparation method of the polyurethane primer resin for the high-water-pressure washing-resistant textile coating comprises the following steps:

the first step is as follows: putting 50% of dimethylformamide, JPP-100, adipic acid and neopentyl glycol copolymerized dihydric alcohol, polycarbonate dihydric alcohol, 1, 4-butanediol and trimethylolpropane into a reaction kettle, stirring for 20min, and keeping the temperature to 70 ℃;

the second step is that: adding all toluene diisocyanate and keeping the temperature to 90 ℃ to react for 1.5 h;

the third step: adding 35% of dimethylformamide and 70% of toluene, stirring for 10min, and cooling to 70 ℃;

the fourth step: adding 50% of 4, 4-diphenylmethane diisocyanate, keeping the temperature to 80 ℃, and reacting for 30 min;

the fifth step: adding 10% 4, 4-diphenylmethane diisocyanate every 30min to correct the viscosity to the required value;

and a sixth step: adding ethylene glycol, terminating the reaction by using excessive hydroxyl of the ethylene glycol, adding malic acid, 15% of dimethylformamide and 30% of toluene, fully stirring for 30min, discharging and subpackaging to obtain the polyurethane primer resin with the solid content of 50 +/-2%, the viscosity of 60000-90000 CPS/25 ℃ and the 100% elastic modulus of 1-2 Mpa.

Example 4

The polyurethane primer resin for the high-water-pressure water-washing-resistant textile coating comprises the following components in percentage by weight:

JPP-100: 0.01%, adipic acid copolymerized with neopentyl glycol: 33.49%, polycarbonate diol: 8.5%, 1, 4-butanediol: 2%, trimethylolpropane: 0.3%, toluene diisocyanate: 5.5%, 4-diphenylmethane diisocyanate: 5.1%, ethylene glycol: 0.3%, malic acid: 0.3%, dimethylformamide: 23.5%, toluene: 26 percent.

The preparation method of the polyurethane primer resin for the high-water-pressure washing-resistant textile coating comprises the following steps:

the first step is as follows: putting 48% of dimethylformamide, JPP-100, adipic acid and neopentyl glycol copolymerized dihydric alcohol, polycarbonate dihydric alcohol, 1, 4-butanediol and trimethylolpropane into a reaction kettle, stirring for 18min, and keeping the temperature to 72 ℃;

the second step is that: adding all toluene diisocyanate and keeping the temperature to 88 ℃ to react for 1.8 h;

the third step: adding 37% of dimethylformamide and 67% of toluene, stirring for 12min, and cooling to 72 ℃;

the fourth step: adding 52% of 4, 4-diphenylmethane diisocyanate, keeping the temperature to 78 ℃ and reacting for 32 min;

the fifth step: adding 12% 4, 4-diphenylmethane diisocyanate every 28min to correct the viscosity to the required value;

and a sixth step: adding ethylene glycol, terminating the reaction by using excessive hydroxyl of the ethylene glycol, adding malic acid, 15% of dimethylformamide and 32% of toluene, fully stirring for 32min, discharging and subpackaging to obtain the polyurethane primer resin with the solid content of 50 +/-2%, the viscosity of 60000-90000 CPS/25 ℃ and the 100% elastic modulus of 1-2 Mpa.

The polyurethane primer resins of examples 1-4 obtained above are each 100 parts, and are respectively matched with 3-5% of amino resin as a bridging agent, 1-3% of an acidic catalyst or 5-10% of an isocyanate bridging agent (about 13% of isocyanate content), and a proper amount of a diluent. Respectively coating the mixture on a calendered 300D oxford fabric and a calendered 600D oxford fabric, and then coating a proper and same surface adhesive. The textile coating product with high water pressure and water washing resistance can be obtained. The textile coating product was subjected to ISO6330 under the same water washing standard: 20126N × 5, water pressure detection standard: the water washing experiment carried out by AATCC 127-:

TABLE 1 comparison of Water pressure before and after washing of textiles coated in the various examples (Water pressure/mmH 2O)

The water pressure before washing of 300D oxford cloth coated by commercial polyurethane primer resin and 600D oxford cloth is 8000mmH2O and 6000mmH2O respectively, and the water pressure after washing is 2000mmH2O and 1500mmH2O respectively. Therefore, the water pressure before and after washing of 300D oxford fabric can be obviously improved by the polyurethane primer resin prepared by the method and the proportion, the water pressure before and after washing of 600D oxford fabric is also improved, and particularly the improvement effect of the polyurethane primer resin prepared in the embodiment 3 is obvious.

In order to make the objects, technical solutions and advantages of the embodiments of the present disclosure more clear, the technical solutions in the embodiments of the present disclosure are clearly and completely described, and it is obvious that the described embodiments are a part of the embodiments of the present disclosure, but not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.

The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.