CN106192443B - A kind of anion ecological artificial leather and preparation method thereof - Google Patents

A kind of anion ecological artificial leather and preparation method thereof Download PDF

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Publication number
CN106192443B
CN106192443B CN201610761521.8A CN201610761521A CN106192443B CN 106192443 B CN106192443 B CN 106192443B CN 201610761521 A CN201610761521 A CN 201610761521A CN 106192443 B CN106192443 B CN 106192443B
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polyvinyl chloride
slurry
layer
artificial leather
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CN106192443A (en
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顾跃进
朱建华
杨定书
吴进
朱明泉
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Nantong Zhonghao microfiber products Co. Ltd.
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Nantong Zhonghao Microfiber Products Co Ltd
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    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N3/06—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds with polyvinylchloride or its copolymerisation products
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    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
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    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
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    • D06N3/005—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers obtained by blowing or swelling agent
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    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0061—Organic fillers or organic fibrous fillers, e.g. ground leather waste, wood bark, cork powder, vegetable flour; Other organic compounding ingredients; Post-treatment with organic compounds
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    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
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    • D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
    • D06N3/0095—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by inversion technique; by transfer processes
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  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)

Abstract

The present invention relates to a kind of anion ecological artificial leather and preparation method thereof, the artificial leather includes polyvinyl chloride top, foaming layer and base cloth layer, and the polyvinyl chloride top is formed by polyvinyl chloride top slurry through 160~180 DEG C of drying；The base cloth layer is made of fabric, and the fabric is pre-processed by Anti-bacterial and Crease agent.Artificial leather mechanical property of the present invention, processing performance are excellent, have the characteristics that at low cost, volatile organic content is low, and acid and alkali-resistance is widely used in shoes, furniture, various interior/exterior decorations, aircraft, automobile, steamer decoration.

Description

A kind of anion ecological artificial leather and preparation method thereof
Technical field
The invention belongs to technical field of macromolecules, it is related to a kind of artificial leather and preparation method thereof, in particular to one kind Anion ecological artificial leather and preparation method thereof.
Background technique
Artificial leather is a kind of appearance, feel like leather and the plastic products that it can be replaced to use.China's artificial leather synthetic leather Industry is new industry after the founding of the state, starts to walk to develop in the fifties end, is to develop one of industry earlier in plastics industry.Through The construction of recent decades is crossed, artificial leather synthetic leather industry has had comparable economic scale；With domestic and international high-tech development With the application of advanced technologies equipment, trade management, technical level, product specification have the qualitative leap of essence, artificial leather Synthetic leather has evolved into one of industry important in current consumption Products Industry, and synchronize to march toward the world big with entire processing industry State's ranks are big producer, consumption big country in the world, one of foreign trade big country.
The artificial polyvinyl chloride leather (PVC artificial leather) occurred for 1948 is to coat polyvinyl chloride resin, plasticizer, steady on the fabric Determine paste made of the auxiliary agents such as agent, or laminating one layer of PVC film again, is then processed into through certain technical process.With people The development of fabricate-leather technology has the characteristics that the various performance materials close to natural leather by it, the big portion in life Point field is for replacing natural leather.Common artificial leather is made of base and surface layer, and base is common fabric, and surface layer is The PVC plastic bed of material, the shoes that such artificial leather is done, has a single function, because of nonventilated relationship, the growth of bacterium easy to breed.
Summary of the invention
The present invention provides a kind of anion ecological artificial leather, and mechanical property, processing performance are excellent, has at low cost, volatilization Property the low feature of content of organics, acid and alkali-resistance is widely used in shoes, furniture, various interior/exterior decorations, aircraft, automobile, steamer dress Decorations.
Specifically, the present invention provides a kind of anion ecological artificial leather, the artificial leather includes polyvinyl chloride top, foaming Layer and base cloth layer, the polyvinyl chloride top are formed by polyvinyl chloride top slurry through 160~180 DEG C of drying, the polychlorostyrene second Alkene surface layer slurry is made of the component of following parts by weight: 100-150 parts of PVC resin powder, 40-60 parts of triethyl citrate, and nanometer 15-30 parts of tourmaline powder, 2-5 parts of Bis(lauroyloxy)dioctyltin, 2-5 parts of nano zine oxide, 2-5 parts of barium stearate, trimerization phosphorus Sour sodium 1-3 parts, 10-15 parts of dioctyl azelate, 0.5-2 parts of white oil, 0.5-5 parts of dimethicone, dibenzyl sorbitol 0.5-2 parts, 0.5-3 parts of pigment, 0.1-3 parts of random copolymer of styrene and maleic anhydride, 0.5-3 parts of chitosan, titanium dioxide 0.5-2 parts；The base cloth layer is made of fabric, and the fabric is pre-processed by Anti-bacterial and Crease agent.
In a specific embodiment of the invention, the anion ecological artificial leather includes polyvinyl chloride top, hair Alveolar layer and base cloth layer, the polyvinyl chloride top are formed by polyvinyl chloride top slurry through 170 DEG C of drying, the polyvinyl chloride face Layer slurry is made of the component of following parts by weight: 130 parts of PVC resin powder, 50 parts of triethyl citrate, and nano-tourmaline powder 20 Part, 3 parts of Bis(lauroyloxy)dioctyltin, 4 parts of nano zine oxide, 3 parts of barium stearate, 2 parts of sodium tripolyphosphate, dioctyl azelate 12 parts, 1.5 parts of white oil, 3 parts of dimethicone, 1 part of dibenzyl sorbitol, 2 parts of pigment, styrene and maleic anhydride it is random .5 parts of copolymer 1,2 parts of chitosan, 1 part of titanium dioxide；The base cloth layer is made of fabric, and the fabric passes through Anti-bacterial and Crease Agent pretreatment.
In a specific embodiment of the invention, the anion ecological artificial leather includes polyvinyl chloride top, hair Alveolar layer and base cloth layer, the polyvinyl chloride top are formed by polyvinyl chloride top slurry through 160 DEG C of drying, the polyvinyl chloride face Layer slurry is made of the component of following parts by weight: 100 parts of PVC resin powder, 40 parts of triethyl citrate, and nano-tourmaline powder 30 Part, 2 parts of Bis(lauroyloxy)dioctyltin, 2 parts of nano zine oxide, 2 parts of barium stearate, 1 part of sodium tripolyphosphate, dioctyl azelate 10 parts, 0.5 part of white oil, 0.5 part of dimethicone, 0.5 part of dibenzyl sorbitol, 0.5 part of pigment, styrene and maleic anhydride 0.1 part of random copolymer, 0.5 part of chitosan, 0.5 part of titanium dioxide；The base cloth layer is made of fabric, and the fabric is by anti- The pretreatment of bacterium crease proofing agent.
In a specific embodiment of the invention, the Anti-bacterial and Crease agent is by poly- hydroxypropyl dimethyl chlorination 3-5 parts of ammonium, 3-5 parts of bamboo vinegar, 3-5 parts of tea polyphenols, 3-5 parts of Cocoamidopropyl betaine, 5-10 parts of sodium alginate, dihydroxy first 0.5-3 parts of base dihydroxy ethylene urea, 5-10 parts of isopropanol, 3-5 parts of aqueous polyurethane and 50-80 parts of deionized water mixing and At.
In a specific embodiment of the invention, the anion ecological artificial leather includes polyvinyl chloride top, hair Alveolar layer and base cloth layer, the polyvinyl chloride top are formed by polyvinyl chloride top slurry through 180 DEG C of drying, the polyvinyl chloride face Layer slurry is made of the component of following parts by weight: 150 parts of PVC resin powder, 60 parts of triethyl citrate, and nano-tourmaline powder 15 Part, 5 parts of Bis(lauroyloxy)dioctyltin, 5 parts of nano zine oxide, 5 parts of barium stearate, 3 parts of sodium tripolyphosphate, dioctyl azelate 15 parts, 2 parts of white oil, 5 parts of dimethicone, 2 parts of dibenzyl sorbitol, 3 parts of pigment, styrene and the random of maleic anhydride are total to 3 parts of polymers, 3 parts of chitosan, 2 parts of titanium dioxide；The base cloth layer is made of fabric, and the fabric is pre- by Anti-bacterial and Crease agent Processing.
In a specific embodiment of the invention, base cloth layer uses woven fabric cloth or woven fabric；PVC resin powder is S-5 Type generated by polyvinyl chloride by calcium carbide；The fabric is pre-processed by Anti-bacterial and Crease agent.
In a specific embodiment of the invention, the polyvinyl chloride top slurry is prepared by following methods:
1) PVC resin powder for taking formula ratio, under 80~85 DEG C, the heating stirring condition of 100~150r/min with formula Nano-tourmaline powder, lauric acid dioctyltin, nano zine oxide, the barium stearate of amount mix 5~10min；
2) triethyl citrate, dioctyl azelate, white oil, dimethicone, the dibenzylidene of formula ratio are sequentially added Sorbierite, sodium tripolyphosphate mix 30~40min under 50~60 DEG C, the heating stirring condition of 300~500r/min；
3) random copolymer, chitosan, titanium dioxide for sequentially adding pigment, styrene and maleic anhydride, 30~40 DEG C, Under the heating stirring condition of 1000~1500r/min mix 30~60min to get.
In a specific embodiment of the invention, step 1) in the preparation process of above-mentioned polyvinyl chloride top slurry Condition of heating and stirring is 80-85 DEG C, 120-130r/min；The condition of heating and stirring of step 2 is 50~60 DEG C, 400-450r/ min；The condition of heating and stirring of step 3) is 30-40 DEG C, 1400-1500r/min.
In a specific embodiment of the invention, the foaming layer between polyvinyl chloride top and base cloth layer, The foaming layer is formed by foam polyvinyl chloride slurry through 180~190 DEG C of drying, and the foam polyvinyl chloride slurry is by following heavy The component of amount part is made: 100 parts of polyvinyl chloride resin powder, 50~70 parts of triethyl citrate, and 0.5~2 part of foam stabilizer, foaming agent 1~3 part, 1-3 parts of poly hexamethylene biguanide, 10~20 parts of adipic acid propanediol polyester.
In a specific embodiment of the invention, the foam polyvinyl chloride slurry is prepared by following methods: By formula ratio polyvinyl chloride resin powder, triethyl citrate, foam stabilizer, foaming agent, poly hexamethylene biguanide, adipic acid propylene glycol Polyester is added in high speed disperser and is stirred, and air, mixing time are passed through into slurry from slurry bottom in whipping process It is 20~50 minutes, mixing speed is 1000~1500r/min.
Preferably, mixing time is 30-50 minutes, mixing speed 1400-1500r/min.
In a specific embodiment of the invention, antibacterial crease-resistant layer is coated on the polyvinyl chloride top, it is described anti- The anti-rennet of bacterium is by 20-30 parts of aqueous polyurethane, 1-2 parts of dimethicone, 3-5 parts of nano zine oxide, hydroxypropyl methyl cellulose 3-5 parts, 0.5-2 parts of triethanolamine, 0.5-2 parts of Boratex be made.
Another aspect of the present invention relates to the preparation methods of the anion ecological artificial leather, include the following steps:
(1) release paper and fabric are selected, fabric is pre-processed by Anti-bacterial and Crease agent, and prepares polyvinyl chloride top slurry Material；
(2) prepared polyvinyl chloride top slurry is coated uniformly in selected release paper, is dried through 160-180 DEG C Polyvinyl chloride top is formed after dry；
(3) foam polyvinyl chloride slurry is prepared, prepared foam polyvinyl chloride slurry is coated uniformly on polyvinyl chloride In surface layer, polyvinyl chloride foam layer is formed after 160-180 DEG C of drying；
(4) it is bonded fabric in polyvinyl chloride foam layer, is then dried through 170-190 DEG C；
(5) release paper is removed, with three printing machine roller coating, one layer of antibacterial crease-resistant layer in surface layer, is dried to get anion Ecological artificial leather.
Specifically, the preparation method of the anion ecological artificial leather, includes the following steps:
(1) release paper and fabric are selected, fabric is pre-processed by Anti-bacterial and Crease agent, prepares polyvinyl chloride top slurry Material :(a) the PVC resin powder for taking formula ratio, under 80~85 DEG C, the heating stirring condition of 100~150r/min with formula ratio Nano-tourmaline powder, lauric acid dioctyltin, nano zine oxide, barium stearate mix 5~10min；(b) formula is sequentially added Triethyl citrate, dioctyl azelate, white oil, dimethicone, dibenzyl sorbitol, the sodium tripolyphosphate of amount, 50 ~60 DEG C, mix 30~40min under the heating stirring condition of 300~500r/min；(c) pigment, styrene and horse are sequentially added The random copolymer, chitosan, titanium dioxide for carrying out acid anhydrides mix under 30~40 DEG C, the heating stirring condition of 1000~1500r/min Close 30~60min；
(2) prepared polyvinyl chloride top slurry is coated uniformly in selected release paper, is dried through 160-180 DEG C Polyvinyl chloride top is formed after dry；
(3) foam polyvinyl chloride slurry is prepared: by formula ratio polyvinyl chloride resin powder, triethyl citrate, foam stabilizer, hair Infusion, poly hexamethylene biguanide, adipic acid propanediol polyester are added in high speed disperser and are stirred, from slurry in whipping process Material bottom is passed through air into slurry, and mixing time is 20~50 minutes, and mixing speed is 1000~1500r/min；It will prepare Good foam polyvinyl chloride slurry is coated uniformly on polyvinyl chloride top, and polyvinyl chloride hair is formed after 160-180 DEG C of drying Alveolar layer；
(4) it is bonded fabric in polyvinyl chloride foam layer, is then dried through 170-190 DEG C；
(5) release paper is removed, with three printing machine roller coating, one layer of antibacterial crease-resistant layer in surface layer, is dried to get anion Ecological artificial leather；The antibacterial crease-resistant layer by 20-30 parts of aqueous polyurethane, 1-2 parts of dimethicone, 3-5 parts of nano zine oxide, 3-5 parts of hydroxypropyl methyl cellulose, 0.5-2 parts of triethanolamine, 0.5-2 parts of Boratex be made.
Parts by weight can be converted arbitrary unit of weight in the present invention.
Below with reference to the specific embodiment artificial leather that the present invention is further explained.
Specific embodiment
A kind of embodiment 1: preparation of anion ecological artificial leather
The anion ecological artificial leather includes polyvinyl chloride top, foaming layer and base cloth layer, the polyvinyl chloride top It is formed by polyvinyl chloride top slurry through 170 DEG C of drying, the polyvinyl chloride top slurry is made of the component of following parts by weight: 130 parts of PVC resin powder, 50 parts of triethyl citrate, 20 parts of nano-tourmaline powder, 3 parts of Bis(lauroyloxy)dioctyltin, nano oxygen 4 parts of zinc of change, 3 parts of barium stearate, 2 parts of sodium tripolyphosphate, 12 parts of dioctyl azelate, 1.5 parts of white oil, 3 parts of dimethicone, two 1 part of benzylidene sorbitol, 2 parts of pigment, 1.5 parts of random copolymer of styrene and maleic anhydride, 2 parts of chitosan, titanium dioxide 1 Part；The base cloth layer is made of fabric, and the fabric is pre-processed by Anti-bacterial and Crease agent；The Anti-bacterial and Crease agent By 4 parts of poly- Hydroxypropyldimonium Chloride, 4 parts of bamboo vinegar, 4 parts of tea polyphenols, 4 parts of Cocoamidopropyl betaine, sodium alginate 8 Part, 2 parts of hydroxymethyl-2 dihydroxy-ethylene urea, 8 parts of isopropanol, 4 parts of aqueous polyurethane and 65 parts of deionized water mix；
Preparation includes the following steps:
(1) release paper and fabric are selected, fabric is pre-processed by Anti-bacterial and Crease agent, prepares polyvinyl chloride top slurry Material :(a) the PVC resin powder for taking formula ratio, it is electrical with the nanometer of formula ratio under 83 DEG C, the heating stirring condition of 130r/min Mountain flour, lauric acid dioctyltin, nano zine oxide, barium stearate mixing 8min；(b) citric acid three of formula ratio is sequentially added Ethyl ester, dioctyl azelate, white oil, dimethicone, dibenzyl sorbitol, sodium tripolyphosphate, in 55 DEG C, 400r/min 35min is mixed under heating stirring condition；(c) sequentially add the random copolymer of pigment, styrene and maleic anhydride, chitosan, Titanium dioxide mixes 50min under 35 DEG C, the heating stirring condition of 1300r/min；
(2) prepared polyvinyl chloride top slurry is coated uniformly in selected release paper, after 170 DEG C of drying Form polyvinyl chloride top；
(3) foam polyvinyl chloride slurry is prepared: by 100 parts of polyvinyl chloride resin powder, 60 parts of triethyl citrate, foam stabilizer 1 part, 2 parts of foaming agent, 2 parts of poly hexamethylene biguanide, 15 parts of adipic acid propanediol polyester be added in high speed disperser and stirred It mixes, is passed through air into slurry from slurry bottom in whipping process, mixing time is 30 minutes, mixing speed 1300r/min； Prepared foam polyvinyl chloride slurry is coated uniformly on polyvinyl chloride top, forms polyvinyl chloride after 170 DEG C of drying Foaming layer；
(4) it is bonded fabric in polyvinyl chloride foam layer, is then dried through 180 DEG C；
(5) release paper is removed, release paper is removed, with three printing machine roller coating, one layer of antibacterial crease-resistant layer in surface layer, is dried, Up to anion ecological artificial leather；The antibacterial crease-resistant layer is by 25 parts of aqueous polyurethane, 1.5 parts of dimethicone, nano oxidized 4 parts of zinc, 4 parts of hydroxypropyl methyl cellulose, 1 part of triethanolamine, 1 part of Boratex be made.
A kind of preparation of the anion ecological artificial leather of embodiment 2
The anion ecological artificial leather includes polyvinyl chloride top, foaming layer and base cloth layer, the polyvinyl chloride top It is formed by polyvinyl chloride top slurry through 160 DEG C of drying, the polyvinyl chloride top slurry is made of the component of following parts by weight: 100 parts of PVC resin powder, 40 parts of triethyl citrate, 30 parts of nano-tourmaline powder, 2 parts of Bis(lauroyloxy)dioctyltin, nano oxygen 2 parts of zinc of change, 2 parts of barium stearate, 1 part of sodium tripolyphosphate, 10 parts of dioctyl azelate, 0.5 part of white oil, 0.5 part of dimethicone, 0.5 part of dibenzyl sorbitol, 0.5 part of pigment, 0.1 part of random copolymer of styrene and maleic anhydride, 0.5 part of chitosan, 0.5 part of titanium dioxide；The base cloth layer is made of fabric, and the fabric is pre-processed by Anti-bacterial and Crease agent；The antibacterial Crease proofing agent is by 3 parts of poly- Hydroxypropyldimonium Chloride, 3 parts of bamboo vinegar, 3 parts of tea polyphenols, Cocoamidopropyl betaine 3 Part, 5 parts of sodium alginate, 0.5 part of hydroxymethyl-2 dihydroxy-ethylene urea, 5 parts of isopropanol, 3 parts of aqueous polyurethane and deionized water 50 parts mix；
Preparation includes the following steps:
(1) release paper and fabric are selected, fabric is pre-processed by Anti-bacterial and Crease agent, prepares polyvinyl chloride top slurry Material :(a) the PVC resin powder for taking formula ratio, it is electrical with the nanometer of formula ratio under 80 DEG C, the heating stirring condition of 100r/min Mountain flour, lauric acid dioctyltin, nano zine oxide, barium stearate mixing 5min；(b) citric acid three of formula ratio is sequentially added Ethyl ester, dioctyl azelate, white oil, dimethicone, dibenzyl sorbitol, sodium tripolyphosphate, in 50 DEG C, 300r/min 30min is mixed under heating stirring condition；(c) sequentially add the random copolymer of pigment, styrene and maleic anhydride, chitosan, Titanium dioxide mixes 30min under 30 DEG C, the heating stirring condition of 1000r/min；
(2) prepared polyvinyl chloride top slurry is coated uniformly in selected release paper, after 160 DEG C of drying Form polyvinyl chloride top；
(3) prepare foam polyvinyl chloride slurry: by 100 parts of formula ratio polyvinyl chloride resin powder, 50 parts of triethyl citrate, 0.5 part of foam stabilizer, 1 part of foaming agent, 1 part of poly hexamethylene biguanide, 10 parts of adipic acid propanediol polyester be added to high speed disperser It is inside stirred, is passed through air into slurry from slurry bottom in whipping process, mixing time is 20 minutes, and mixing speed is 1000r/min；Prepared foam polyvinyl chloride slurry is coated uniformly on polyvinyl chloride top, the shape after 160 DEG C of drying At polyvinyl chloride foam layer；
(4) it is bonded fabric in polyvinyl chloride foam layer, is then dried through 170 DEG C；
(5) release paper is removed, foam leather is obtained；The antibacterial crease-resistant layer is by 20 parts of aqueous polyurethane, dimethyl-silicon Oil 1 part, 3 parts of nano zine oxide, 3 parts of hydroxypropyl methyl cellulose, 0.5 part of triethanolamine, 0.5 part of Boratex be made.
A kind of preparation of the anion ecological artificial leather of embodiment 3
The anion ecological artificial leather includes polyvinyl chloride top, foaming layer and base cloth layer, the polyvinyl chloride top It is formed by polyvinyl chloride top slurry through 180 DEG C of drying, the polyvinyl chloride top slurry is made of the component of following parts by weight: 150 parts of PVC resin powder, 60 parts of triethyl citrate, 15 parts of nano-tourmaline powder, 5 parts of Bis(lauroyloxy)dioctyltin, nano oxygen Change 5 parts of zinc, 5 parts of barium stearate, 3 parts of sodium tripolyphosphate, 15 parts of dioctyl azelate, 2 parts of white oil, 5 parts of dimethicone, two is sub- 2 parts of benzyl sorbitol, 3 parts of pigment, 3 parts of random copolymer of styrene and maleic anhydride, 3 parts of chitosan, 2 parts of titanium dioxide；Institute It states base cloth layer to be made of fabric, the fabric is pre-processed by Anti-bacterial and Crease agent；The Anti-bacterial and Crease agent is by gathering 5 parts of Hydroxypropyldimonium Chloride, 5 parts of bamboo vinegar, 5 parts of tea polyphenols, 5 parts of Cocoamidopropyl betaine, 10 parts of sodium alginate, 3 parts of hydroxymethyl-2 dihydroxy-ethylene urea, 10 parts of isopropanol, 5 parts of aqueous polyurethane and 80 parts of deionized water mix；
Preparation method includes the following steps:
(1) release paper and fabric are selected, fabric is pre-processed by Anti-bacterial and Crease agent, prepares polyvinyl chloride top slurry Material :(a) the PVC resin powder for taking formula ratio, it is electrical with the nanometer of formula ratio under 85 DEG C, the heating stirring condition of 150r/min Mountain flour, lauric acid dioctyltin, nano zine oxide, barium stearate mixing 10min；(b) citric acid of formula ratio is sequentially added Triethyl, dioctyl azelate, white oil, dimethicone, dibenzyl sorbitol, sodium tripolyphosphate, in 60 DEG C, 500r/min Heating stirring condition under mix 40min；(c) random copolymer, the shell for sequentially adding pigment, styrene and maleic anhydride are poly- Sugar, titanium dioxide mix 60min under 40 DEG C, the heating stirring condition of 1500r/min；
(2) prepared polyvinyl chloride top slurry is coated uniformly in selected release paper, after 180 DEG C of drying Form polyvinyl chloride top；
(3) prepare foam polyvinyl chloride slurry: by 100 parts of formula ratio polyvinyl chloride resin powder, 70 parts of triethyl citrate, 2 parts of foam stabilizer, 3 parts of foaming agent, 3 parts of poly hexamethylene biguanide, 20 parts of adipic acid propanediol polyester be added in high speed disperser It is stirred, is passed through air into slurry from slurry bottom in whipping process, mixing time is 50 minutes, and mixing speed is 1500r/min；Prepared foam polyvinyl chloride slurry is coated uniformly on polyvinyl chloride top, the shape after 180 DEG C of drying At polyvinyl chloride foam layer；
(4) it is bonded fabric in polyvinyl chloride foam layer, is then dried through 190 DEG C；
(5) release paper is removed, foam leather is obtained；The antibacterial crease-resistant layer is by 30 parts of aqueous polyurethane, dimethyl-silicon Oil 2 parts, 5 parts of nano zine oxide, 5 parts of hydroxypropyl methyl cellulose, 2 parts of triethanolamine, 2 parts of Boratex be made.
Comparative example 1:(replaces triethyl citrate with epoxy aliphatic acid methyl ester)
The anion ecological artificial leather includes polyvinyl chloride top, foaming layer and base cloth layer, the polyvinyl chloride top It is formed by polyvinyl chloride top slurry through 170 DEG C of drying, the polyvinyl chloride top slurry is made of the component of following parts by weight: 130 parts of PVC resin powder, 50 parts of epoxy aliphatic acid methyl ester, 20 parts of nano-tourmaline powder, 3 parts of Bis(lauroyloxy)dioctyltin, nanometer 4 parts of zinc oxide, 3 parts of barium stearate, 2 parts of sodium tripolyphosphate, 12 parts of dioctyl azelate, 1.5 parts of white oil, 3 parts of dimethicone, 1 part of dibenzyl sorbitol, 2 parts of pigment, 1.5 parts of random copolymer of styrene and maleic anhydride, 2 parts of chitosan, titanium dioxide 1 Part；Other are the same as embodiment 1.
Comparative example 2:(replaces nano zine oxide with nano-titanium dioxide)
The anion ecological artificial leather includes polyvinyl chloride top, foaming layer and base cloth layer, the polyvinyl chloride top It is formed by polyvinyl chloride top slurry through 170 DEG C of drying, the polyvinyl chloride top slurry is made of the component of following parts by weight: 130 parts of PVC resin powder, 50 parts of triethyl citrate, 20 parts of nano-tourmaline powder, 3 parts of Bis(lauroyloxy)dioctyltin, nanometer two 4 parts of titanium oxide, 3 parts of barium stearate, 2 parts of sodium tripolyphosphate, 12 parts of dioctyl azelate, 1.5 parts of white oil, 3 parts of dimethicone, 1 part of dibenzyl sorbitol, 2 parts of pigment, 1.5 parts of random copolymer of styrene and maleic anhydride, 2 parts of chitosan, titanium dioxide 1 Part；Other are the same as embodiment 1.
Comparative example 3 (omits triethanolamine)
The antibacterial crease-resistant layer is by 25 parts of aqueous polyurethane, 1.5 parts of dimethicone, 4 parts of nano zine oxide, hydroxypropyl first 4 parts of base cellulose, 1 part of Boratex be made；Other are the same as embodiment 1.
Comparative example 4(omits Boratex)
The antibacterial crease-resistant layer is by 25 parts of aqueous polyurethane, 1.5 parts of dimethicone, 4 parts of nano zine oxide, hydroxypropyl first 4 parts of base cellulose, 1 part of triethanolamine be made, other are the same as embodiment 1.
Comparative example 5(omits sodium alginate)
The Anti-bacterial and Crease agent is by 4 parts of poly- Hydroxypropyldimonium Chloride, 4 parts of bamboo vinegar, 4 parts of tea polyphenols, coconut palm 4 parts of oleamide propyl betaine, 2 parts of hydroxymethyl-2 dihydroxy-ethylene urea, 8 parts of isopropanol, 4 parts of aqueous polyurethane and deionization 65 parts of water mix；Other are the same as embodiment 1.
Embodiment 4: environmental-protecting performance test
Test the organic volatile amount (ginseng of the anion ecological artificial leather of 1-3 of the embodiment of the present invention and comparative example 1-5 preparation According to VDA277) ugC/g and its oder levels (VDA270), grade evaluation: 1 odorlessness；2 is odorous, but non interference；3 have Obvious smell, but still non interference；4 have interference smell；5 have strong interference smell；6 have insufferable smell.Knot Fruit is shown in Table 1.
The environmental-protecting performance of the anion ecological artificial leather of the present invention of table 1
Group Organic volatile amount ugC/g Oder levels (40 DEG C, for 24 hours)
Embodiment 1 2.7 1
Embodiment 2 2.6 1
Embodiment 3 2.5 1
Comparative example 1 4.3 2
Comparative example 2 4.5 2
Comparative example 3 5.2 2
Comparative example 4 5.0 3
Comparative example 5 3.5 1
Table 1 the result shows that, 1-3 of the embodiment of the present invention preparation artificial leather environmental-protecting performance it is excellent, release it is volatile Total amount of organic is lower, without any smell；Also show that comparative example 1(epoxy aliphatic acid methyl ester replaces lemon with the data in table 1 Triethylenetetraminehexaacetic acid ester), comparative example 2(with nano-titanium dioxide replace nano zine oxide), comparative example 3(omit triethanolamine), comparative example 4 (omit Boratex), comparative example 5(omit sodium alginate) volatile organic matter of release can obviously increase, and oder levels can also increase Add, illustrates that each component mutually cooperates in the present invention, plays a role jointly.
5 Mechanics Performance Testing of embodiment
Tearing strength (QB/T4043-2010), the peel strength (QB/T4043-2010), rub resistance of testing example 1-3 Color fastness (QB/T4043-2010), the results are shown in Table 2.
The mechanical property of 2 the present inventor's fabricate-leather of table
Table 2 statistics indicate that, the present inventor's fabricate-leather function admirable.
6 anti-microbial property test of embodiment
Sample to be tested is put into containing in certain density bacterium (staphylococcus aureus strain) culture solution, then examination Sample is placed on reciprocating oscillator, at (24 ± 1) DEG C, with the velocity fluctuation 18h of 150r/min, makes sample fabric by oscillation It after being come into full contact with bacterium solution, is cultivated in (37 ± 1) DEG C biochemical cultivation case for 24 hours, the clump count of measurement oscillation front and back bacterium passes through Method for counting colonies carrys out quantitative assessment antibacterial effect.
The calculating of succusion test anti-microbial property:
Wherein, A is that standard blank sample vibrates clump count after 18h to bacteriostasis rate (%)=(A-B)/A × 100%；B be to Test specimens vibrate clump count after 18h.Table 3 is the result that detection obtains.
The anti-microbial property of 3 the present inventor's fabricate-leather of table
Embodiment 1 Embodiment 2 Embodiment 3 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5
Bacteriostasis rate 99.93 99.95 99.96 95.35 94.68 94.31 95.73 97.38
It is in table 3 statistics indicate that, anion ecological artificial leather bacteriostasis rate with higher of the invention, and of the invention Various components mutually cooperate with, and play a role jointly.
Embodiment 7 discharges anionic property detection
The case where determining embodiment 1-3 release anion respectively using anionic textiles instrument, the results are shown in Table 3.
The Negative ion disengagement of 4 the present inventor's fabricate-leather of table
Group Negative ion concentration/cm3
Embodiment 1 1935
Embodiment 2 1940
Embodiment 3 1945
Table 4 the result shows that, 1-3 of the embodiment of the present invention have it is stronger release anion performance.

Claims (4)

1. a kind of anion ecological artificial leather, it is characterised in that the artificial leather includes polyvinyl chloride top, foaming layer and base fabric Layer, the polyvinyl chloride top are formed by polyvinyl chloride top slurry through 160~180 DEG C of drying, the polyvinyl chloride top slurry Material is made of the component of following parts by weight: 100-150 parts of PVC resin powder, 40-60 parts of triethyl citrate, and nano-tourmaline powder 15-30 parts, 2-5 parts of Bis(lauroyloxy)dioctyltin, 2-5 parts of nano zine oxide, 2-5 parts of barium stearate, sodium tripolyphosphate 1-3 Part, 10-15 parts of dioctyl azelate, 0.5-2 parts of white oil, 0.5-5 parts of dimethicone, 0.5-2 parts of dibenzyl sorbitol, face 0.5-3 parts, 0.1-3 parts of random copolymer of styrene and maleic anhydride, 0.5-3 parts of chitosan, 0.5-2 parts of titanium dioxide of material；Institute It states base cloth layer to be made of fabric, the fabric is pre-processed by Anti-bacterial and Crease agent；
Wherein the Anti-bacterial and Crease agent is by poly- Hydroxypropyldimonium Chloride 3-5 parts, 3-5 parts of bamboo vinegar, tea polyphenols 3-5 Part, 3-5 parts of Cocoamidopropyl betaine, 5-10 parts of sodium alginate, 0.5-3 parts of hydroxymethyl-2 dihydroxy-ethylene urea, isopropanol 5-10 parts, 3-5 parts of aqueous polyurethane and 50-80 parts of deionized water mix；
The foaming layer is between polyvinyl chloride top and base cloth layer, and the foaming layer is by foam polyvinyl chloride slurry through 180 ~190 DEG C of drying are formed, and the foam polyvinyl chloride slurry is made of the component of following parts by weight: polyvinyl chloride resin powder 100 Part, 50~70 parts of triethyl citrate, 0.5~2 part of foam stabilizer, 1~3 part of foaming agent, 0.5-1 parts of poly hexamethylene biguanide, oneself 10~20 parts of diacid propanediol polyester；
Antibacterial crease-resistant layer is coated on the polyvinyl chloride top, the antibacterial crease-resistant layer is by 20-30 parts of aqueous polyurethane, dimethyl 1-2 parts of silicone oil, 3-5 parts of nano zine oxide, 3-5 parts of hydroxypropyl methyl cellulose, 0.5-2 parts of triethanolamine, 0.5-2 parts of Boratex It is made.
2. anion ecological artificial leather according to claim 1, the polyvinyl chloride top slurry is prepared by following methods It obtains:
1) PVC resin powder for taking formula ratio, under 80~85 DEG C, the heating stirring condition of 100~150r/min with formula ratio Nano-tourmaline powder, lauric acid dioctyltin, nano zine oxide, barium stearate mix 5~10min；
2) triethyl citrate, dioctyl azelate, white oil, dimethicone, the dibenzylidene sorb of formula ratio are sequentially added Alcohol, sodium tripolyphosphate mix 30~40min under 50~60 DEG C, the heating stirring condition of 300~500r/min；
3) random copolymer, chitosan, titanium dioxide for sequentially adding pigment, styrene and maleic anhydride, in 30~40 DEG C, 1000 Under the heating stirring condition of~1500r/min mix 30~60min to get.
3. anion ecological artificial leather according to claim 1, the foam polyvinyl chloride slurry is prepared by following methods It obtains: by formula ratio polyvinyl chloride resin powder, triethyl citrate, foam stabilizer, foaming agent, poly hexamethylene biguanide, adipic acid Propanediol polyester is added in high speed disperser and is stirred, and is passed through air into slurry from slurry bottom in whipping process, stirs Mixing the time is 20~50 minutes, and mixing speed is 1000~1500r/min.
4. the preparation method of anion ecological artificial leather described in claim 1, includes the following steps:
(1) release paper and fabric are selected, fabric is pre-processed by Anti-bacterial and Crease agent, and prepares polyvinyl chloride top slurry；
(2) prepared polyvinyl chloride top slurry is coated uniformly in selected release paper, is formed after 160 DEG C of drying Polyvinyl chloride top；
(3) foam polyvinyl chloride slurry is prepared, prepared foam polyvinyl chloride slurry is coated uniformly on polyvinyl chloride top On, polyvinyl chloride foam layer is formed after 180 DEG C of drying；
(4) it is bonded fabric in polyvinyl chloride foam layer, is then dried through 170 DEG C；
(5) release paper is removed, with three printing machine roller coating, one layer of antibacterial crease-resistant layer in surface layer, is dried to get anion ecological Artificial leather.
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