CN101070681A - Mud leather and preparing method - Google Patents

Mud leather and preparing method Download PDF

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Publication number
CN101070681A
CN101070681A CN 200710027925 CN200710027925A CN101070681A CN 101070681 A CN101070681 A CN 101070681A CN 200710027925 CN200710027925 CN 200710027925 CN 200710027925 A CN200710027925 A CN 200710027925A CN 101070681 A CN101070681 A CN 101070681A
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China
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leather
mud
compound
emulsion
acrylate
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CN 200710027925
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Chinese (zh)
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石磊
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石磊
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Publication of CN101070681A publication Critical patent/CN101070681A/en

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Abstract

This invention discloses using ordinary soil and the acrylic acid ester emulsion as the primary material spreading on radical cloth to makethe synthetic leather. It mixes the putty powder or the mud and the propylene acids emulsion, flexible, the defoamer, against static, the coloring agent into the compound mud. Then spread bond mud in the adhesive-bonded cloth or on the chemical fiber grid cloth, roasting, till the conjunctiva. To press the need pattern on preheating or has not been preheat press machine, make out the compound putty leather. This invention in the production, use process does not produce the noxious gas and solution, the product is low cost, the good elasticit, anti-rips pulls.and so on.

Description

Mud leather and manufacture method thereof
Technical field
The present invention relates to a kind of synthetic leather, particularly a kind of with common soil and acrylic emulsion synthetic leather and manufacture method thereof as main raw material.
Background technology
The production of synthetic leather in the past mainly is synthetic skin of PU (polyurethane) and the synthetic skin of PVC (polyvinyl chloride), and the main raw material of making the synthetic skin use of PU is PU resin and the retarder thinner that contains the high solvent composition; The main raw material that the synthetic skin of manufacturing PVC uses is PVC powder and liquid plasticizer, utilizes modes such as coating, applying to make leatheret, and the shortcoming that this dermatine exists is:
1, the PU synthetic leather adopts the base stock of the PU resin of organic solvent type as production leather product basic unit and surface layer, and manufacture method mainly is with coating machine that PU is resin-coated on the base cloth or on the release liners, utilizes explained hereafter such as cohesion, washing and drying.All solvent in the PU resin formula all is a harmful substance, has toxicity in various degree, and environment is damaged pollution, and the foreign odor flavor is serious.
2, the PVC synthetic leather uses powder-type polyvinyl chloride resin and plasticizer to be main raw material, and it carries out in the high temperature open system during owing to operation in mixing calender line for a long time, easily causes dust to produce and the plasticizer volatilization, thereby environment is easily polluted.In addition, can produce dioxin, chlorine and heavy metal particle during the incineration of garbage of PVC goods, heavy metal can be separated out and contaminated environment when burying.
3, poor, the light color of the hydrolytic stability of PU synthetic leather, not anti-mould, thermo-labile, poisture-penetrability is poor.
4, there is poor flexibility in the PVC synthetic leather, surfaces of tacky, and embrittlement easily takes place in hardening during low temperature, and shortcoming such as sanitation performance difference.
In recent years, people study the performance of acrylic resin, find as leather filler or finishing agent the physical property of leather products, the hot property of filming are improved acrylic resin, through retrieval, we have also found some pertinent literatures, now take passages as follows:
1, [autograph] acrylate copolymer emulsion is used for research [author] Chen Yuanwu [mechanism] the Fujian textile chemical fiber Group Co.,Ltd of toughening modifying water-based PU, Yongan, Fujian 366016[prints name] chemistry and bonding .2006,28 (2) .-91-93[digests] introduced a kind of acrylate copolymer emulsion with hand modified water-soluble PU leather finish liquid, hardness and toughness to water-based PU are regulated modification, increase its pliable and tough and plumpness.The influence of this emulsion to water-based PU emulsion property has been discussed.Adopted conventional acrylic acid ester emulsion copolymerization process, obtained the translucent anionic acrylic acid ester emulsion of a kind of outward appearance, can mix with this water-based PU product is stable.Air dry and 95 ℃ of heat drying film forming are transparent, pliable and tough and plentiful, and good with the adhesive force of leather, the comprehensively modifying effect is better.
2, synthetic and application [author] Gao Futang [1] Zhang Xiaolei [2] Feng Jianyan [2] Wang Zhao intercalation [2] [mechanism] [1] the Shaanxi Tech Univ's chemistry and the chemical engineering institute of [autograph] hydroxyl silicon oil modified acrylic resin leather finishing agent, Xianyang [2] resource and environment institute of Shaanxi Tech Univ, [periodical name] leather science and engineering .2006,16 (1) .-63-66[digests] in the hydroxy silicon oil molecule, introduce the two keys of C=C by the hydrolysate and the hydroxy silicon oil generation condensation reaction of silane coupler (KH570), under ammonium persulfate caused, condensation product had synthesized the hydroxyl silicon oil modified acrylic resin leather finishing agent with acrylate monomer generation emulsion polymerisation again.Utilize infrared spectrum (FT-IR) and differential scanning calorimetry means such as (DSC) that product structure and application performance are characterized and study.The result shows: organosilyl introducing, improved the defective of acrylic resin " hot sticky cold crisp " effectively, and be coated with dressing leather and have excellent properties such as hydrophobic, soft, smooth, Bearable dry and wet wipe.
3, all duckweed Zhao Yun rocs [mechanism] of the preparation of [autograph] silicone-modified polyacrylate leather finishing agent and sign [author] Song Xu plum Qiqihar University, [periodical name] western leather .2005,27 (8) .-30-34[digests] to have studied with organosiloxane, acrylate be main raw material, adopt the method for emulsion polymerization way synthetic leather finishing agent, investigated of the influence of factors such as dosage of crosslinking agent, initiator amount, reaction time, reaction temperature reaction result.This class finishing agent has fabulous surface property and weatherability, and the finished leather softness is smooth, coating thin, intensity is high, kishke feel is strong, meets modern leather processing and application performance requirement.
4, the modification of [autograph] fluorine resin is synthesized and is investigated system as research [author] Qin Zonggen [mechanism] the Guangdong police officer institute of leather filler, [periodical name] leather chemical industry 1.2006,23 (3) .-16-19, the 36[digest] employing seeded emulsion polymerization technology, N hydroxymethyl acrylamide (NMA), acrylic acid (AA) modification by copolymerization fluorine resin, the modified fluoride-containing resin leather filler that has synthesized nucleocapsid structure. NMA has been discussed, the AA consumption is to the modified resin hot property of filming, the influence of physical property etc., and utilize transmission electron microscope (TEM), differential thermal analyzer (DSC) and gel permeation chromatography (GPC) characterize. and the result shows, NMA, the AA consumption should not surpass 1.5%, 2%.
5, the modification of [autograph] little crosslinked acrylic resin is synthetic and as the just refined chemistry institute of big duckweed [mechanism] South China Science ﹠ Engineering University that is coated with of property research [author] Zhang Jingxia of leather filler, [periodical name] Chinese leather .2005,34 (7) .-24-27[digests] employing semi-continuous seed emulsion polymerization technology, N hydroxymethyl acrylamide (NMA), hydroxy-ethyl acrylate (HEA) modification by copolymerization conventional acrylic resin have been synthesized the acrylic acid modified leather filler of nucleocapsid structure.The concentration, addition manner of NMA has been discussed and when crosslinked on an equal basis to the influence of modified resin film properties, and utilize vitrification point (Tg) and gel permeation chromatography (GPC) to characterize.
6, the molecular weight of [autograph] acrylic resin filling emulsion and research [author] Zhang Jing that distributes thereof are coated with Chemical Engineering research institute of just refined [mechanism] South China Science ﹠ Engineering University of big duckweed summer, [periodical name] leather chemical industry .2005,22 (3) .-1-4, the 24[digest] adopt semi-continuous seed emulsion polymerization technology, synthesized little cross linked acrylic modified resin leather filler.The factors such as monomer concentration, initator, crosslinking agent and polymerization temperature of having discussed are filled the influence of using the acrylic polymer emulsion property to leather.Result of study shows, adopts this technology can obtain that molecular weight is of moderate size and the acrylate copolymer emulsion of wider distribution, uses it for the filling of leather, can satisfy the inequality of leather loose side degree.
7, [autograph] Si Taer releases Foamex [author] Wang Yi [mechanism] be used to improve the leather grade not quite clear [periodical name] Beijing leather: the leather Information page .2005 (3) of China and foreign countries .-70-70[digest] Si Taer develops a kind of thermoplastic expanded resin---RC-18-075 recently, and this resin is a main component with the acrylate copolymer emulsion through improvement.This product is added silane coupling agent, can give fabulous covering, uniformity and fillibility, and make the leather body keep soft.When pressing under 110 ℃ of temperature, because the effect of this product, filming expands, and highly-filled property produces by this mechanism just.The grade that RC-18-075 is used to improve low-grade leather is desirable, it in addition can be used for white Finish System.
8, Chinese patent, application (patent) number: 85102368 titles: synthesis of polymer coating material for leather application (patent right) people: Chengdu Univ. of Science ﹠ Technology, address: No. 24, one section in Dongcheng District, Chengdu, Sichuan Province loop south, summary: a kind of polymer coating material for leather, by acrylate, chlorobutadiene, acrylonitrile, styrene, monomers such as acrylic acid are synthesized under certain process conditions. and its prescription is reasonable, and technology is simple, easy operation control, constant product quality, and have good especially cold-resistant, flexible resistance and high cohesiveness. this product is applicable to pig, the obverse leather of ox, pig, the leather of having a shave of ox, the covering with paint of various clothing leathers and split leather. better especially for clothing leather and split leather effect. also can be used as the packing material of leather. adaptability is strong, and is of many uses, and cost is lower.
9, Chinese patent, application (patent) number: 95113049.8 titles: polyurethane-polyacrylate composite leather coating agent application (patent right) people: Wang Nan, address: No. 29, Su Jia lane, Sichuan Province's Luzhou City bazaar town, summary: the present invention is to provide a kind of aqueous emulsion type leather finishing agent that is composited by polyurethane and polyacrylate.This leather finishing agent is to wrap up crosslinked forming mutually by a plurality of multi-branched shape polyurethane particulate and polyacrylate particulates through the polyvinyl alcohol chain extension, have irregular out-phase " nuclear-shell " structure, and at the active group that has cross-linking reaction can be at drying and forming-film the time on the complex molecule chain.The solid branch weight ratio of polyurethane and polyacrylate is 9: 1~1: 9 in the compound, and the polyvinyl alcohol consumption is 2%~15% of polyurethane solid part.Compound resin with this structure can fully have the characteristics of polyurethane resin and acrylic resin concurrently, presents excellent comprehensive performances.
10, Chinese patent, application (patent) number: 00116784.7 title: fabric and leather are with composite waterproof material application (patent right) people: East China University of Science, address: No. 130, Meilong Road, Shanghai City, summary: the invention provides a kind of fabric and leather composite waterproof material, the present invention utilizes paraffin, hydrophobic material such as beeswax and organo-silicon compound and polyvinyl acetate, polyacrylate, polystyrene, polyvinyl chloride, poly-sulphur and organosilicon polymer and their blend, macromolecule waterproof materials such as copolymer, carry out polymerization and blend, form the network-type organic double compound, will bring special waterproof and breathable effect.Through the leather that waterproof material of the present invention is handled, waterproof in 3 hours, reached the excellent waterproof effect, can satisfy people's needs.
11, application (patent) number: 02134014.5 title: a kind of synthetic and preparation method of functional resin coating agent, application (patent right) people: Chengdu Organic Chemistry Inst., Chinese Academy of Sciences, the address: No. 9, Siduanjiu, Renmin Road(South), Chengdu City, Sichuan Province, summary the present invention relates to a kind ofly to can be used for weaving, at the bottom of the leather, the middle level synthetic and preparation method that covers with paint, lacquer, colour wash, etc. the high performance resin finishing agent of usefulness.The proportioning of this finishing agent is: A. functional monomer, B. acrylic ester monomer, C. reactive organosilicon compounds, D. complexed surfactant, E. initator, F. neutralizer, G. water.This finishing agent emulsion particle diameter is thin, the film forming good leveling property, and the film after the covering with paint has extremely comfortable lubricious feel, and coating is soft, is not clamminess, and has preferable water proofing property and moisture-proof wiping ability.This finishing agent is comparatively suitable to synthetic fiber cloth, sofa artificial leather, clothing leather etc., especially to sheepskin garment leather, can obviously improve the class of leather after the use.
12, application (patent) number: 200510049161.0 titles: a kind of preparation method of solvent-free, low-viscosity UV-cured polyurethane acrylate leather coating agent, application (patent right) people: Zhejiang University, the address: the No. 38, Zheda Road, Hangzhou City, Zhejiang Province, summary: the present invention is a kind of preparation method of solvent-free, low-viscosity UV-cured polyurethane acrylate leather coating agent.This method is utilized the uV curable and the soft adjustability advantage of polyurethane of acrylic double bond, react by the hydroxyl in the isocyano in the polyisocyanates and acrylate and the polyalcohol, obtain solvent-free, low viscous UV-cured polyurethane acrylate leather coating agent; Simultaneously, by the adding in batches or continuously of catalyst, can solve problems such as temperature control in the course of reaction, gel.This leather finishing agent has low viscosity, organic solvent-free, the fireballing characteristics of ultraviolet light polymerization, is especially suitable for use as the polishing coating agent of leather or artificial leather.
Open source literature is pointed out: nearly 1,000 ten thousand tons of the polymer of making about acrylic acid and ester class thereof and the output of copolymer resin (mainly being emulsion resin).Acrylate can be divided into non-functional monomer, functional monomer and many acrylic acid multielements alcohol ester three major types, have commodity production four, 50 kind.
Recognize from the data of above-mentioned retrieval: to mention the modification of little crosslinked acrylic resin synthetic and as the leather filler except document 5, general all is with the main component of acrylic resin as leather finishing agent, does not see about adopting common soil and the acrylic resin report as the synthetic leather main production raw material.
Summary of the invention
The objective of the invention is to overcome the above-mentioned shortcoming of prior art, providing a kind of is main raw material with common soil and acrylic emulsion, does not produce the synthetic leather of toxic and harmful and solution in production, use.This leather has that cost is low, good springiness, anti-tearly draw, good permeability, fire-retardant, ageing-resistant, anti-ultraviolet advantage.
The objective of the invention is to be achieved through the following technical solutions:
The present invention is to be that the composite sludge of main raw material is coated on the base cloth and makes with common soil and acrylic emulsion, and the composition and the parts by weight of its coating material are as follows:
Common soil 30-60;
Acrylic emulsion 25-65;
Softener 1-6;
Defoamer 0.5-2;
Antistatic agent 0.5-8
Colouring agent 0-6;
Water 2-15.
Described earth can adopt red soil, black mud, yellow mud or white clay etc., and preferred Tu Shan goes up or the clean earth darker apart from the face of land.Earth drying, pulverizing, mistake 200-400 mesh sieve get the mud powder; Or earth and water mixed after the 200-400 mesh filter screen filters, dry, pulverize, the mud powder;
The combination of one or more below described acrylic emulsion adopts: 1, methyl acrylate (MA); 2, ethyl acrylate (EA); 3, butyl acrylate (n-BA); 4, acrylic acid-2-ethyl caproite (2-ethyl hexyl acrylate, 2-EHA); 5, synthetic (styrene-butadiene emulsion) and natural polymer mixed emulsion, 6, acrylic ester high molecular type copolymer emulsion; 7, polyethyl acrylate, butyl polyacrylate, hydroxymethyl acrylamide copolymer; 8, selfing chain acrylate copolymer emulsion (unreacted monomer≤1%); 9, anion, nonionic phenotype are from interlinkage acrylate copolymer emulsion (unreacted monomer≤0.5%); 10, the multi-copolymerization emulsion of the acrylate copolymer of tool reactive group; 11, the compound of polyacrylate, its main component structure is:
12, compound emulsification system acrylic acid esters co-polymer (methyl methacrylate and butyl acrylate copolymer); 13, methyl methacrylate, butyl acrylate, acrylamide ternary copolymer emulsion; 14, butyl acrylate and acrylonitrile copolymer emulsion; 15, the copolymer emulsion of all acrylic ester class; 16, the copolymerized macromolecule compound of acrylic acid and ester thereof, main component structure is:
R is CH 3Or C 2H 5, C 4H 3,
Acrylic ester high molecular type copolymer emulsion of the present invention adopts the commercially available prod, is the water-soluble emulsion class, and its solid content requires between 30-50% weight.
Described softener is mainly used in the elasticity that improves leather, make it more smooth pliable, can improve feel, can adopt the general softener of chemical field, for example the emulsified body of organosilicon and fatty amine, organosilicon emulsion, polysiloxanes, two carboxylic acid amide derivative, octadecyl ethylene urea, quaternary sun lotus property activating agent with reactive functional groups.
Described defoamer is used for eliminating the foam that the batch mixing process produces, and in coating procedure, eliminates the foam that slurry and other component are pieced together the time spent generation, can significantly improve wettability.For example organosilicon emulsified body, alkyl ether phosphate, propanediol polyoxypropylene polyoxyethylene ether, the glycerin polyether defoamer that glycerine and expoxy propane are polymerized etc.
Described antistatic agent adopts potassium alkyl phosphate (antistatic additive PK), cationic quaternary ammonium type surfactant (antistatic additive SN), the alkyl imidazoline quaternary ammonium salt compound that has amide group, alkylamide nonionic surface active agent (antistatic additive ECH), and its chemical structural formula is:
Fatty alcohol-polyoxyethylene ether phosphate, its chemical constituent is:
Described colouring agent adopts paint-printing colour size, for example paint-printing colour size indigo plant, paint-printing colour size is black, paint-printing colour size is light yellow, paint-printing colour size is yellow, paint-printing colour size is golden yellow, paint-printing colour size is orange, paint-printing colour size is green, paint-printing colour size is red, paint-printing colour size palm fibre etc.; Or other series inorganic pigments such as carbon black, chromium titan yellow, chromium nickel yellow, molybdate red, tonyred, ultramarine blue (the artificial lapis lazuli look pigment of silicoaluminophosphate), zirconium system, cobalt series pigments, also can use organic pigment, for example AZO pigments, phthalocyanine color and heterocycle pigment etc.
Described base cloth is selected from by weaving cotton cloth or nonwoven fabric (nonwoven fabric) that polyester, cotton, nylon, polypropylene, wool, fiber crops, polyurethanes, polyacrylonitrile, polybutadiene, polystyrene, polymethyl methacrylate and derivative thereof are made.
The manufacture method of the compound mud leather of the present invention comprises following processing step:
1, earth drying, pulverizing, mistake 200-400 mesh sieve get the mud powder; Or earth and water mixed after the 200-400 mesh filter screen filters, dry, pulverize, the mud powder;
2, mixed soil powder, water, acrylic emulsion, softener, defoamer, colouring agents etc. make it become uniform composite sludge;
3, composite sludge is coated on the template that has decorative pattern or shiny surface, thickness is 0.15mm to 3.0mm, and baking temperature is 80 ℃-285 ℃, after the polishing back side, molding is cut edge, and produces the compound mud leather of no base cloth until conjunctiva; Or composite sludge is coated on the template that has decorative pattern or shiny surface, thickness is 0.15mm to 3.0mm, baking temperature is 80 ℃-285 ℃, behind conjunctiva, fit base cloth, side cut, or composite sludge is coated on the base cloth, thickness is 0.15mm to 3.0mm, baking temperature is 80 ℃-285 ℃, until conjunctiva, on preheating or the embossing machine that is not preheated, extrude required decorative pattern, produce the compound mud leather of base cloth.
The present invention compared with prior art has following advantage:
1, the compound mud leather produced of this method is water-soluble because additive therefor is, and is therefore, producing, do not produce in the use poisonous, harmful waste water, waste gas and foreign odor flavor, very friendly to environment.
2, the compound mud leather produced of this method takes place crosslinkedly making under the effect of additive between the mud particle, form the long-chain shaped polymer.Not only have pliable and tough, the anti-tear characteristics of drawing, also have the distinctive gas permeability of earth, fire-retardant, ageing-resistant characteristics.
3, the compound mud leather produced of this method utilizes the true qualities of mud, mixes colours by adding a spot of water paint print paste, forms colourful also under intensive ultraviolet, shine for a long time not can variable color color variety.
The specific embodiment
Below by embodiment the present invention is specifically described; be necessary to be pointed out that at this present embodiment can only further specify the present invention; can not be interpreted as limiting the scope of the invention, those skilled in the art can make some nonessential improvement and adjustment to the present invention according to foregoing.
Embodiment 1:
Yellow mud powder 50%, acrylic ester high molecular type copolymer emulsion 41.5%, water 4.5%, polysiloxanes flexibility agent 3%, fatty alcohol-polyoxyethylene ether phosphate antistatic agent 0.5%, alkyl ether phosphate defoamer 0.5% are mixed into and are uniform composite sludge.Composite sludge is coated on the template that has decorative pattern or shiny surface, and thickness is 1.4mm, and baking temperature is 100 ℃ (± 20 ℃), after polishing, molding is cut edge, and produces the yellow compound mud leather of no base cloth until conjunctiva.Need the compound mud leather of no base cloth of other color, add corresponding mill base or toner in mud, adopt identical method to make.
Embodiment 2:
Black mud powder 44%, anion, nonionic phenotype deceive 1% from interlinkage acrylate copolymer emulsion (unreacted monomer≤0.5%) 44%, water 5%, organosilicon flexibility agent 4%, propanediol polyoxypropylene polyoxyethylene ether defoaming agent 1%, potassium alkyl phosphate antistatic agent 1%, paint-printing colour size, are mixed into uniform composite sludge.Composite sludge is coated on the template that has decorative pattern or shiny surface, and thickness is 2mm, and baking temperature is 200 ℃ (± 30 ℃), after polishing, molding is cut edge, and produces the compound mud leather of black of no base cloth until conjunctiva.Need the compound mud leather of no base cloth of other color, add corresponding mill base or toner in mud, adopt identical method to make.
Embodiment 3:,
The multi-copolymerization emulsion 52% of the acrylate copolymer of yellow mud powder 40%, tool reactive group, two carboxylic acid amide derivative softener 3%, glycerin polyether defoamer 1%, potassium alkyl phosphate antistatic agent 2%, paint-printing colour size palm fibre 1% are mixed into uniform composite sludge.Composite sludge is coated on the template that has decorative pattern or shiny surface, and thickness is 2.3mm, and baking temperature is 200 ℃ (± 50 ℃), after polishing, molding is cut edge, and produces the brown compound mud leather of no base cloth until conjunctiva.Need the compound mud leather of no base cloth of other color, add corresponding mill base or toner in mud, adopt identical method to make.
Embodiment 4:
The emulsification softener C 1.4% of multi-copolymerization emulsion 57%, organosilicon and the fatty amine of the acrylate copolymer of white clay powder 38.5%, tool reactive group, silicone defoaming agent 0.5%, potassium alkyl phosphate antistatic agent 2%, paint-printing colour size indigo plant 0.6%, be mixed into uniform composite sludge.Composite sludge is coated on cotton or the chemical fibre grid cloth, and thickness is 0.15mm, and baking temperature is 100 ℃ (± 20 ℃), until conjunctiva, extrudes required decorative pattern on the embossing machine of 130 ℃ of preheatings, produces the light blue compound mud leather of base cloth.Need other color that the compound mud leather of base cloth is arranged, add corresponding mill base or toner, adopt identical method to make in mud.
Embodiment 5:
Red soil powder 43%, anion, nonionic phenotype are mixed into uniform composite sludge from interlinkage acrylate copolymer emulsion 50%, polysiloxane soft agent 3%, alkyl ether phosphate defoamer 1%, cationic quaternary ammonium type surfactant antistatic agent 2%, paint-printing colour size red 1%.Composite sludge is coated on cotton or the chemical fibre grid cloth, and thickness is 0.2mm, and baking temperature is 150 ℃ (± 20 ℃), until conjunctiva, extrudes required decorative pattern on the embossing machine of 130 ℃ of preheatings, produces the light blue compound mud leather of base cloth.Need other color that the compound mud leather of base cloth is arranged, add corresponding mill base or toner, adopt identical method to make in mud.
Embodiment 6:
White clay powder 43%, acrylate copolymer emulsion 48%, water 4%, two carboxylic acid amide and derivative softener 2.8% thereof, propanediol polyoxypropylene polyoxyethylene ether defoaming agent 0.6%, cationic quaternary ammonium type surfactant antistatic agent 1%, paint-printing colour size deceive 0.6%, are mixed into uniform composite sludge.Composite sludge is coated on cotton or the chemical fibre grid cloth, and thickness is 0.18mm, and baking temperature is 150 ℃ (± 20 ℃), until conjunctiva, extrudes required decorative pattern on the embossing machine of 130 ℃ of preheatings, produces the compound mud leather of light gray black of base cloth.Need other color that the compound mud leather of base cloth is arranged, add corresponding mill base or toner, adopt identical method to make in mud.
Embodiment 7:
The copolymer emulsion 53% of yellow mud powder 38%, all acrylic ester class, water 4%, quaternary sun lotus property softener 3%, alkyl ether phosphate defoamer 0.5%, to have alkyl imidazoline quaternary ammonium salt compound antistatic agent 1%, the paint-printing colour size of amide group golden yellow 0.5%, is mixed into uniform composite sludge.Composite sludge is coated on cotton or the chemical fibre grid cloth, and thickness is 0.28mm, and baking temperature is 160 ℃ (± 20 ℃), until conjunctiva, extrudes required decorative pattern on the embossing machine of 130 ℃ of preheatings, produces the yellow compound mud leather of base cloth.Need other color that the compound mud leather of base cloth is arranged, add corresponding mill base or toner, adopt identical method to make in mud.
Embodiment 8:
White clay powder 53%, polyethyl acrylate, butyl polyacrylate, hydroxymethyl acrylamide copolymer 31%, water 10%, quaternary sun lotus property activating agent softener 3%, glycerin polyether defoamer 1%, fatty alcohol-polyoxyethylene ether phosphate antistatic agent 2% are mixed into uniform composite sludge.Composite sludge is coated on the template that has decorative pattern or shiny surface, and thickness is 1mm, and baking temperature is 180 ℃ (± 50 ℃), fits behind conjunctiva and goes up base cloth, and molding is cut edge, and produces the white compound mud leather of base cloth.What need other color has a compound mud leather of base cloth, adds corresponding mill base or toner in mud, adopts identical method to make.
Embodiment 9:
The copolymerized macromolecule compound 50% of red soil powder 42.5%, acrylic acid and ester thereof, water 3%, quaternary sun lotus property activating agent softener 3%, glycerin polyether defoamer 0.5%, fatty alcohol-polyoxyethylene ether phosphate antistatic agent 1% are mixed into uniform composite sludge.Composite sludge is coated on the template that has decorative pattern or shiny surface, and thickness is 1mm, and baking temperature is 180 ℃ (± 50 ℃), fits behind conjunctiva and goes up base cloth, and molding is cut edge, and produces the red compound mud leather of mud of base cloth.What need other color has a compound mud leather of base cloth, adds corresponding mill base or toner in mud, adopts identical method to make.
Concrete parametric measurement of the present invention:
The compound mud leather that above-mentioned 1-9 embodiment production obtains is decided the test section gate test through method ground, and average physical parameter is as follows:
Peel strength 86.7%, TENSILE STRENGTH 35%, elongation at break 24.9%.Reach the technical parameter of common pig leather.
The compound mud leather that embodiment 1-9 production obtains carries out acute oral toxicity (LD 50) experiment:
Each dosage group mouse does not see bad reaction after giving sample, and diet is movable normal, and animal used as test does not have death in the observation period, obtains female, male its mouse oral LD 50>23.5g/Kg BW, the compound mud leather of submitted sample belong to nontoxic level material, the results are shown in following table.
Dosage (g/Kg BW) Number of animals (only) Animal dead (only)
Female Male Female Male
????23.5 ????19.5 ????15.4 ????12.7 ????9.63 ????6.62 ????4.24 ????2.15 ????5 ????5 ????5 ????5 ????5 ????5 ????5 ????5 ????5 ????5 ????5 ????5 ????5 ????5 ????5 ????5 ????0 ????0 ????0 ????0 ????0 ????0 ????0 ????0 ????0 ????0 ????0 ????0 ????0 ????0 ????0 ????0
This test basis GB15193.3-2003 " toxicological evaluation of food safety procedure and method "

Claims (9)

1, a kind of compound mud leather is characterized in that: it is to be that main raw material is coated on the base cloth and makes with common soil and acrylic emulsion, and the composition and the parts by weight of coating material are as follows:
Common soil 30-60;
Acrylic emulsion 25-65;
Softener 1-6;
Defoamer 0.5-2;
Antistatic agent 0.5-8
Colouring agent 0-6;
Water 2-15.
2, compound mud leather according to claim 1 is characterized in that: described common soil is common red soil, black mud, yellow mud or white clay.
3, compound mud leather according to claim 1 is characterized in that: the combination of one or more below described acrylic emulsion adopts: (1) methyl acrylate; (2) ethyl acrylate; (3) butyl acrylate; (4) acrylic acid-2-ethyl caproite; (5) synthetic styrene-butadiene emulsion and natural polymer mixed emulsion, (6) acrylic ester high molecular type copolymer emulsion; (7) polyethyl acrylate, butyl polyacrylate, hydroxymethyl acrylamide copolymer; (8) selfing chain acrylate copolymer emulsion; (9) anion, nonionic phenotype are from the interlinkage acrylate copolymer emulsion; (10) multi-copolymerization emulsion of the acrylate copolymer of tool reactive group; (11) compound emulsification system acrylic acid esters co-polymer; (12) methyl methacrylate, butyl acrylate, acrylamide ternary copolymer emulsion; (13) butyl acrylate and acrylonitrile copolymer emulsion; (14) copolymer emulsion of all acrylic ester class; (15) the copolymerized macromolecule compound of acrylic acid and ester thereof; (16) compound of polyacrylate.
4, compound mud leather according to claim 1, it is characterized in that: described softener adopts the general softener of chemical field, selects emulsified body, the organosilicon emulsion of organosilicon and fatty amine, the polysiloxanes with reactive functional groups, two carboxylic acid amide derivative, octadecyl ethylene urea or quaternary sun lotus property activating agent for use.
5, compound mud leather according to claim 1 is characterized in that: described defoamer is the glycerin polyether defoamer that organosilicon emulsified body, alkyl ether phosphate, propanediol polyoxypropylene polyoxyethylene ether or glycerine and expoxy propane are polymerized.
6, compound mud leather according to claim 1 is characterized in that: described antistatic agent adopts potassium alkyl phosphate (antistatic additive PK), cationic quaternary ammonium type surfactant (antistatic additive SN), the alkyl imidazoline quaternary ammonium salt compound that has amide group, alkylamide nonionic surface active agent (antistatic additive ECH)
7, compound mud leather according to claim 1 is characterized in that: described colouring agent adopts paint-printing colour size, carbon black, chromium titan yellow, chromium nickel yellow, molybdate red, tonyred, ultramarine blue, zirconium system, cobalt series pigments or uses organic pigment.
8, compound mud leather according to claim 1 is characterized in that: described base cloth is selected from by weaving cotton cloth or nonwoven fabric that polyester, cotton, nylon, polypropylene, wool, fiber crops, polyurethanes, polyacrylonitrile, polybutadiene, polystyrene, polymethyl methacrylate and derivative thereof are made.
9, a kind of manufacture method of compound mud leather as claimed in claim 1 is characterized in that: comprise following processing step:
(1) earth drying, pulverizing, mistake 200-400 mesh sieve get the mud powder; Or earth and water mixed after the 200-400 mesh filter screen filters, dry, pulverize, the mud powder;
(2) mixed soil powder or mud, water, acrylic emulsion, softener, defoamer, colouring agent makes it become uniform composite sludge;
(3) composite sludge is coated on the template that has decorative pattern or shiny surface, thickness is 0.15mm to 3.0mm, and baking temperature is 80 ℃-285 ℃, after the polishing back side, molding is cut edge, and produces the compound mud leather of no base cloth until conjunctiva; Or composite sludge is coated on the template that has decorative pattern, thickness is 0.15mm to 3.0mm, baking temperature is 80 ℃-285 ℃, behind conjunctiva, fit base cloth, side cut, or composite sludge is coated on the base cloth, thickness is 0.15mm to 3.0mm, baking temperature is 80 ℃-285 ℃, until conjunctiva, on preheating or the embossing machine that is not preheated, extrude required decorative pattern, produce the compound mud leather of base cloth.
CN 200710027925 2007-05-06 2007-05-06 Mud leather and preparing method CN101070681A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101792975A (en) * 2010-02-26 2010-08-04 四川大学 Ageing-resistant heat-insulation tarpaulin and production method thereof
CN102864683A (en) * 2012-08-21 2013-01-09 湖南中烟工业有限责任公司 Preparation process of laser golden vacuum aluminized paper and transfer coating used for preparation process
CN103306145A (en) * 2013-06-20 2013-09-18 吴江市美兰橡塑纺织有限公司 Coating slurry and production method for coating and dyeing base cloth by using coating slurry
CN103789465A (en) * 2012-11-05 2014-05-14 中国石油化工股份有限公司 Leather greasing treatment agent and preparation method thereof
CN105297426A (en) * 2015-10-12 2016-02-03 河北蓓特丽洗涤用品开发有限公司 Fabric softener
CN107903554A (en) * 2017-12-14 2018-04-13 段宝荣 A kind of preparation method using process hides chromium-bearing sludge modified acroleic acid esters resin

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101792975A (en) * 2010-02-26 2010-08-04 四川大学 Ageing-resistant heat-insulation tarpaulin and production method thereof
CN101792975B (en) * 2010-02-26 2012-08-08 四川大学 Ageing-resistant heat-insulation tarpaulin and production method thereof
CN102864683A (en) * 2012-08-21 2013-01-09 湖南中烟工业有限责任公司 Preparation process of laser golden vacuum aluminized paper and transfer coating used for preparation process
CN102864683B (en) * 2012-08-21 2015-03-11 湖南中烟工业有限责任公司 Preparation process of laser golden vacuum aluminized paper and transfer coating used for preparation process
CN103789465A (en) * 2012-11-05 2014-05-14 中国石油化工股份有限公司 Leather greasing treatment agent and preparation method thereof
CN103789465B (en) * 2012-11-05 2015-06-17 中国石油化工股份有限公司 Leather greasing treatment agent and preparation method thereof
CN103306145A (en) * 2013-06-20 2013-09-18 吴江市美兰橡塑纺织有限公司 Coating slurry and production method for coating and dyeing base cloth by using coating slurry
CN105297426A (en) * 2015-10-12 2016-02-03 河北蓓特丽洗涤用品开发有限公司 Fabric softener
CN107903554A (en) * 2017-12-14 2018-04-13 段宝荣 A kind of preparation method using process hides chromium-bearing sludge modified acroleic acid esters resin

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