阅读说明：本技术 一种负离子水性聚氨酯合成革及其制备方法 (Anion waterborne polyurethane synthetic leather and preparation method thereof ) 是由 倪伶俐 李浩扬 李桂军 张锋 冯会生 于 2021-08-18 设计创作，主要内容包括：本发明属于合成革技术领域,公开了一种负离子水性聚氨酯合成革及其制备方法,包括以下步骤：S1.将10-60 wt%碳酸钙、30-80 wt%电气石矿物和5-20 wt%丙烯酸树脂按比例加入到球磨机中,研磨10min；S2.向S1中加入20-100份丙烯酸改性的水性聚氨酯树脂中,同时加入1-6份自由基引发剂,搅拌混合均匀,经压缩空气发泡。通过利用丙烯酸树脂改性碳酸钙和电气石,不但可以有效提升粉体与树脂间的相容性,而且让矿物粉体与丙烯酸改性的水性聚氨酯乳液通过共价键连接,赋予该发泡层一定的机械强度,提升合成革的机械性能；使用有机硅和磷酸酯双改性的水性聚氨酯乳液作为面层原料,赋予制备出来的合成革表面具有耐污渍性能,同时还兼具阻燃性。(The invention belongs to the technical field of synthetic leather, and discloses anion waterborne polyurethane synthetic leather and a preparation method thereof, wherein the preparation method comprises the following steps: s1, adding 10-60 wt% of calcium carbonate, 30-80 wt% of tourmaline mineral and 5-20 wt% of acrylic resin into a ball mill in proportion, and grinding for 10 min; s2, adding 20-100 parts of acrylic acid modified waterborne polyurethane resin into S1, simultaneously adding 1-6 parts of free radical initiator, stirring and mixing uniformly, and foaming by compressed air. By using the acrylic resin modified calcium carbonate and the tourmaline, the compatibility between the powder and the resin can be effectively improved, and the mineral powder is connected with the acrylic acid modified waterborne polyurethane emulsion through a covalent bond, so that the foaming layer is endowed with certain mechanical strength, and the mechanical property of the synthetic leather is improved; the organic silicon and phosphate ester double-modified waterborne polyurethane emulsion is used as a surface layer raw material, so that the prepared synthetic leather surface has stain resistance and flame retardance.)

1. A negative ion waterborne polyurethane synthetic leather and a preparation method thereof are characterized in that: the method comprises the following steps:

s1, adding 10-60 wt% of calcium carbonate, 30-80 wt% of tourmaline mineral and 5-20 wt% of acrylic resin into a ball mill in proportion, and grinding for 10 min;

s2, adding 20-100 parts of acrylic acid modified waterborne polyurethane resin into S1, simultaneously adding 1-6 parts of free radical initiator, stirring and mixing uniformly, and foaming by compressed air;

and S3, coating the slurry after the foaming in the S2 mode on the surface of base cloth through a two-roll calender, drying the base cloth in an oven at the temperature of 110-130 ℃, and attaching a 5-20 mu m waterborne polyurethane surface layer on the surface of the base cloth to obtain the negative ion waterborne polyurethane synthetic leather.

2. The anion waterborne polyurethane synthetic leather and the preparation method thereof according to claim 1, wherein the anion waterborne polyurethane synthetic leather is characterized in that: the mineral granularity of the tourmaline is more than or equal to 200 meshes.

3. The anion waterborne polyurethane synthetic leather and the preparation method thereof according to claim 1, wherein the anion waterborne polyurethane synthetic leather is characterized in that: the acrylic resin is any one of 2-acrylic acid, 2-furan acrylic acid, 2-carboxyethyl acrylate, 2- (trifluoromethyl) acrylic acid, 4-pyridine acrylic acid, 2-benzyl acrylic acid and 3, 3-dimethyl acrylic acid.

4. The anion waterborne polyurethane synthetic leather and the preparation method thereof according to claim 1, wherein the anion waterborne polyurethane synthetic leather is characterized in that: the free radical initiator is any one of azobisisobutyronitrile, azobisisoheptonitrile and dimethyl azobisisobutyrate.

5. The anion waterborne polyurethane synthetic leather and the preparation method thereof according to claim 1, wherein the anion waterborne polyurethane synthetic leather is characterized in that: the water-based polyurethane surface layer is prepared from water-based polyurethane emulsion modified by organic silicon and phosphate.

Technical Field

The invention relates to the technical field of synthetic leather, in particular to anion waterborne polyurethane synthetic leather and a preparation method thereof.

Background

The polyurethane has the advantages of wide adjustable range of hardness, low temperature resistance, good flexibility, strong adhesive force and the like, and is widely applied to the fields of leather finishing, coatings, adhesives and the like. However, with the advent of environmental safety laws and regulations in various countries, many countries have limited the use of solvent-based polyurethanes.

The continuous phase of the waterborne polyurethane is water, so that the waterborne polyurethane is safe and easy to store and store, is convenient to use and low in cost, completely keeps the characteristics of the solvent type polyurethane, and is superior to the solvent type polyurethane in certain performance due to the coulomb force and hydrogen bond in the molecular chain of the waterborne polyurethane, so that the development and production of the waterborne polyurethane are paid attention by various countries in the world and are developed greatly. In the preparation of aqueous polyurethane, in order to obtain a stable polyurethane emulsion, a hydrophilic group is introduced into a prepolymer molecule of polyurethane, and the prepolymer molecule is emulsified in water.

Since Su Union reports the research result that the negative ions in the air can eliminate germs, the research enthusiasm of the negative ions is raised at home and abroad. At present, related products with a plurality of negative ions, such as negative ion floors, negative ion interior wall coatings, negative ion decorative paper, negative ion home decoration ecological plates and the like, exist in the market, but the products are used in the household environment, are difficult to be made into products which are easy to carry by people, and limit the technical development in the field of negative ions. In addition, related technical researches on the combination of the waterborne polyurethane and the negative ions are reported. Therefore, the anion waterborne polyurethane synthetic leather and the preparation method thereof are provided.

Disclosure of Invention

The invention aims to provide anion waterborne polyurethane synthetic leather and a preparation method thereof, which are used for further processing into products such as clothes, shoes, bags and the like which are convenient for people to carry about, and even further used for automotive interiors, provide better anion environment for people, guarantee the health of people and can effectively solve the problems provided in the background art.

In order to achieve the purpose, the invention adopts the technical scheme that:

a negative ion waterborne polyurethane synthetic leather and a preparation method thereof comprise the following steps:

s1, adding 10-60 wt% of calcium carbonate, 30-80 wt% of tourmaline mineral and 5-20 wt% of acrylic resin into a ball mill in proportion, and grinding for 10 min;

s2, adding 20-100 parts of acrylic acid modified waterborne polyurethane resin into S1, simultaneously adding 1-6 parts of free radical initiator, stirring and mixing uniformly, and foaming by compressed air;

s3, coating the slurry foamed in the step S2 on the surface of base cloth through a two-roll calender, drying the base cloth in an oven at the temperature of 110-130 ℃, and then attaching a 5-20 mu m waterborne polyurethane surface layer on the surface of the base cloth to obtain the negative ion waterborne polyurethane synthetic leather.

Further, the granularity of the tourmaline mineral is more than or equal to 200 meshes.

Preferably, the acrylic resin is any one of 2-acrylic acid, 2-furan acrylic acid, 2-carboxyethyl acrylate, 2- (trifluoromethyl) acrylic acid, 4-pyridine acrylic acid, 2-benzyl acrylic acid and 3, 3-dimethyl acrylic acid.

Further, the radical initiator is any one of azobisisobutyronitrile, azobisisoheptonitrile, and dimethyl azobisisobutyrate.

Preferably, the raw material of the water-based polyurethane surface layer is water-based polyurethane emulsion double-modified by organic silicon and phosphate.

Compared with the prior art, the invention has the following beneficial effects:

firstly, by using acrylic resin to modify calcium carbonate and tourmaline, the compatibility between powder and resin can be effectively improved, and mineral powder is connected with acrylic acid modified waterborne polyurethane emulsion through a covalent bond, so that a foaming layer is endowed with certain mechanical strength, and the mechanical property of the synthetic leather is improved; (ii) a

Secondly, the organic silicon and phosphate ester double-modified waterborne polyurethane emulsion is used as a surface layer raw material, so that the prepared synthetic leather surface has stain resistance and flame retardance;

thirdly, the use of a chemical foam stabilizer is avoided by utilizing the foam stabilizing effect of the mineral powder;

fourthly, the organic silicon and phosphate ester double-modified waterborne polyurethane emulsion is used as a surface layer raw material, and a large amount of calcium carbonate, tourmaline and other flame-retardant materials are added into a foaming layer, so that the synthetic leather has certain flame-retardant performance;

and fifthly, the adoption of the ball milling technology not only enables the grinding of the calcium carbonate and the tourmaline mineral powder to be finer, but also utilizes the heating and pressurizing effects generated in the ball milling process to better realize the surface modification of the powder by the acrylic resin.

Detailed Description

In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments.

The preparation methods of the acrylic acid modified aqueous polyurethane resin emulsion and the organic silicon and phosphate ester double modified aqueous polyurethane emulsion related to the following examples are as follows: acrylic acid modified aqueous polyurethane resin

In a three-neck round bottom flask equipped with a mechanical stirring paddle, a reflux condenser and a thermometer, uniformly stirring isophorone diisocyanate (IPDI, 32%), polyether polyol (PPG 2000, 5%) and polytetrahydrofuran polyol (PTMG 2000, 40%) at room temperature, adjusting the reaction temperature to (80 +/-1) DEG C, dropwise adding dibutyltin dilaurate (DBTDL, 0.6%) as a catalyst, and stirring for reacting for 2 hours; then adjusting the reaction temperature to (60 +/-1) DEG C, adding a certain amount of acrylic acid modifier (2-hydroxyethyl) methacrylate (HMA, 6.4%), stirring for reaction for 1 hour, adding a certain amount of 1, 4-butanediol (BDO, 4%), stirring for reaction for 0.5 hour, then adding metered 2, 2-dimethylolpropionic acid (DMPA, 5.5%), and continuing to react for 1 hour; during which time an appropriate amount of acetone was added for dilution. And then cooling to room temperature, adding a proper amount of acetone and a metered amount of triethylamine (TEA, 4.5%) for neutralization reaction, after neutralization is finished, adding a metered amount of ethylenediamine (EDA, 2%) for chain extension under high-speed stirring, adding water into the system for emulsification, and finally distilling under reduced pressure to remove the acetone to obtain the acrylic acid modified waterborne polyurethane emulsion (MAWPU).

Organosilicon and phosphate ester double-modified waterborne polyurethane emulsion

Adding metered amounts of isophorone diisocyanate (IPDI, 12%), hexamethylene diisocyanate (HDI, 20%), polytetrahydrofuran polyol (PTMG 2000, 25%), dihydroxy-terminated polysiloxane (hydroxy silicone oil, hydroxyl content 8-10%, 15%) and organic phosphate diol (OP 550, 10%) into a three-necked round-bottomed flask equipped with a mechanical stirring paddle, a reflux condenser and a thermometer, stirring uniformly at room temperature, adjusting the reaction temperature to (80 +/-1) ° C, dropwise adding a catalyst dibutyltin dilaurate (DBTDL, 1%), stirring for 2 hours, adding a certain amount of 1, 4-butanediol (BDO, 4%), stirring for 1 hour, then adding metered amounts of 2, 2-dimethylolpropionic acid (DMPA, 5%), and continuing the reaction for 1 hour; during which time an appropriate amount of acetone was added for dilution. Then cooling to room temperature, adding a proper amount of acetone and a measured amount of triethylamine (TEA, 5%) for neutralization reaction, after neutralization is finished, adding a measured amount of ethylenediamine (EDA, 3%) for chain extension under high-speed stirring, adding water into the system for emulsification, and finally carrying out reduced pressure distillation to remove acetone, thereby obtaining the organopolysiloxane and phosphate ester in-situ double-modified waterborne polyurethane emulsion;

example 1

Adding 60 wt% of calcium carbonate, 30 wt% of tourmaline mineral and 10 wt% of acrylic resin into a ball mill, grinding for 10min, adding 60 parts of calcium carbonate into 100 parts of vinyl modified waterborne polyurethane resin, adding 3 parts of free radical initiator, stirring and mixing uniformly, foaming by compressed air, coating the slurry on the surface of base cloth by a two-roller calender, drying in a 120 ℃ oven, and attaching a layer of waterborne polyurethane surface layer on the surface of the base cloth to obtain the anion waterborne polyurethane synthetic leather.

Example 2

Adding 40 wt% of calcium carbonate, 40 wt% of tourmaline mineral and 20 wt% of acrylic resin into a ball mill, grinding for 10min, adding 100 parts of calcium carbonate into 100 parts of vinyl modified waterborne polyurethane resin, simultaneously adding 6 parts of free radical initiator, stirring and mixing uniformly, foaming by compressed air, coating the slurry on the surface of base cloth by a two-roller calender, drying in a 120 ℃ oven, and then attaching a layer of waterborne polyurethane surface layer on the surface of the base cloth to obtain the anion waterborne polyurethane synthetic leather.

Example 3

Adding 15 wt% of calcium carbonate, 80 wt% of tourmaline mineral and 5 wt% of acrylic resin into a ball mill, grinding for 10min, adding 20 parts of calcium carbonate into 100 parts of vinyl modified waterborne polyurethane resin, simultaneously adding 1 part of free radical initiator, stirring and mixing uniformly, foaming by compressed air, coating the slurry on the surface of base cloth by a two-roller calender, drying in a 120 ℃ oven, and then attaching a layer of waterborne polyurethane surface layer on the surface of the base cloth to obtain the anion waterborne polyurethane synthetic leather.

Comparative example 1

Adding wood powder (20 parts), a foaming agent (4 parts), an aqueous color paste (1 part) and a thickening agent (1 part) into anionic aqueous polyurethane resin (100 parts), stirring and mixing uniformly, foaming the slurry to 1.5 times by a foaming machine, coating the slurry on the surface of base cloth treated and dried by 2% oxalic acid solution in a scraping way, drying the base cloth in a 120 ℃ drying oven, and attaching a layer of aqueous polyurethane surface layer on the surface of the base cloth to obtain the aqueous polyurethane synthetic leather.

The synthetic leathers prepared in examples 1 to 3 and comparative example were tested for their properties, and the specific test results are shown in table 1 below.

TABLE 1 Performance test results for different synthetic leather samples

The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.