CN102719064B - Fully degradable automobile internal and external decoration material and preparation method and application thereof - Google Patents
Fully degradable automobile internal and external decoration material and preparation method and application thereof Download PDFInfo
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- CN102719064B CN102719064B CN201210230631.3A CN201210230631A CN102719064B CN 102719064 B CN102719064 B CN 102719064B CN 201210230631 A CN201210230631 A CN 201210230631A CN 102719064 B CN102719064 B CN 102719064B
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Abstract
The invention relates to a fully degradable automobile internal and external decoration material and a preparation method and an application thereof. The preparation method of the automobile internal and external decoration material includes that a natural fiber with a water content of below 0.2% is processed by a silane coupling agent, the processed natural fiber and a polylactic acid fiber which has a density of 1.22g per cubic centimeter are respectively drawn and continuously fed into a mixed slurry to be subjected to an immersion treatment for 60 to 180 seconds, the natural fiber and the polylactic acid fiber which are subjected to the immersion treatment are dried until the water content is below 0.2%, then the natural fiber and the polylactic acid fiber are guided into a double-screw extruder, and the natural fiber and the polylactic acid fiber are extruded together through the double-screw extruder to obtain the automobile internal and external decoration material. The natural fiber and polylactic acid are used as raw materials for the automobile internal and external decoration material, and raw material source is environment-friendly, renewable and fully degradable.
Description
Technical field
The present invention relates to a kind of automobile inside/outside decorative material and preparation method thereof and application, relate in particular to a kind of raw material sources green, renewable, automobile inside/outside decorative material that can be degradable and preparation method thereof and application.
Background technology
Along with scientific and technical progress, the raising of living standards of the people, the filamentary material that automobile interior trim is used is by the future development from economical and practical type to functional, fashion-orientation, lightweight and environmental type.In automobile decoration material, conventional man-made fiber has following.1 functional fiber automobile decoration textiles has very high requirement to novel functional fibre raw material, and its processing and postfinishing process are also very complicated.These textiless are except meeting the routine of textiles requires, also have special, to material fire-retardant, refuse the requirement of the characteristics such as water, antistatic, antifouling, colour fastness, fast light photograph, resistance to cleaning, antibacterial and mouldproof; And waterproof, capable of washing, the fire-retardant common standards requirement that has become automobile inner decoration facing; In addition, thin dawn, high bulk, high contraction, high-tenacity, all kinds of profiled-cross-section, lead the common functions such as wet, insulation and differential performance and can make car offer the comfortable driving of passenger to experience.Terylene spandex fiber is also widely used on automotive trim as the substitute of nylon, along with the one-tenth heat of the production technology of PBT (terephthalic acid propylene diester), PTT (butylene terephthalate), the nylon fiber automotive trim field of gradually having faded out.High-strength polyester fiber, as the top-priority reason of security, is widely used on air bag and securing band.What ultra-fine polyester fiber was made spins leather fabric owing to having used phase change material (PCM), makes the temperature in automobile in summer at least reduce by 2～4 ~ C.
But these material resources are limited, non-renewable, energy consumption is large.Waste after use hard degradation in physical environment, has caused day by day serious pollution to physical environment.This has not only affected daily life, and national economy and industrial and agricultural production have been brought to huge harm.
Summary of the invention
The object of this invention is to provide a kind of raw material sources green, renewable, automotive interior/exterior material that can be degradable and preparation method thereof and application.
The preparation method of automotive interior/exterior material provided by the present invention, comprises the steps:
Comprise the steps:
Process water content lower than 0.2% natural fiber with silane coupling agent;
Be 1.22g/cm by natural fiber after treatment and density
3acid fiber by polylactic draw respectively and send into continuously in mixed slurry submergence and process 60 ~ 180s;
Natural fiber after treatment submergence and acid fiber by polylactic are dried to water content lower than 0.2%, then import twin screw extruder, after twin screw extruder is extruded jointly, obtain described automotive interior/exterior material;
The quality percentage composition of described natural fiber is 30-70%, preferably 45-55%;
The quality percentage composition of described acid fiber by polylactic is 30-70%, preferably 45-55%;
Described mixed slurry is containing fire retardant, antiseptic-germicide, oxidation inhibitor, anti ultraviolet agent and lubricant.
Acid fiber by polylactic is a kind of high strength heat resistant acid fiber by polylactic, and its chemical formula is as follows
Wherein, described silane coupling agent is treated to and will in the acetone or alcohol solution of the silane coupling agent of described natural fiber immersion massfraction 2%-7%, processes 2-10min.
Wherein, described extrusion temperature is 170 DEG C-190 DEG C.
Wherein, described natural fiber is any one or several in ramie, jute, mestha, hemp, flax, sisal hemp and bluish dogbane.
Wherein, the length of described natural fiber is 6 ~ 15mm, and the length of described acid fiber by polylactic is 6 ~ 15mm.
Wherein, the mass ratio of described fire retardant, antiseptic-germicide, oxidation inhibitor, anti ultraviolet agent and lubricant is (2-3): 0.2:0.1:0.1:1.
Wherein, described silane coupling agent is selected: KH550(3-aminopropyl triethoxysilane), KH560(3-glycidyl ether oxygen base propyl trimethoxy silicane), KH570(3-methacryloxy Trimethoxy silane), KH151, one or more in KH101;
Fire retardant is selected: three (1-oxo-1-phospha-2,6,7-trioxa-l-phosphabicyclos [2,2,2] octane-4-methylene radical) phosphoric acid ester, 1-oxygen-4-methylol-2,6, one or more in 7-trioxa-1-phospha dicyclo [2,2,2] octanes (PEPA) and ammonium sulfate halogen-free flame retardants;
Oxidation inhibitor is selected: tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites, Tyox B, four { β-(3,5-di-tert-butyl-4-hydroxy phenyl) propionic acid } tetramethylolmethane, (3,5-di-tert-butyl-4-hydroxy phenyl) propionic acid octadecyl ester, Tyox B, thio-2 acid 2 stearyl ester, 2,6-di-t-butyl is to one or more in potassium phenol;
Antiseptic-germicide is selected: 2,4,4-, tri-chlorine-2-hydroxyls-phenyl ether, 3-(dimethoxy silylation) one or more in propyl-dimethyl octadecyl ammonium chloride, polyoxygenated alkylene trialkyl ammonium salts; One or more in selecting of antioxidant;
Anti ultraviolet agent is selected: two (2,2,6,6-tetramethyl-piperidinyl) sebate or [[6-[1,1,3,3-tetramethyl butyl] amido]-guanamine-4-bis-] [[(2,2,6,6-tetramethyl--4-piperidinyl) imido grpup] methene [(2,2,6,6-tetramethyl--4-piperidinyl) imido grpup]] polymer in one;
Lubricant is selected: one or both in aluminum stearate or calcium stearate.
Automotive interior/exterior material of the present invention can be used for preparing automobile internal and external ornament.
It is raw material that automotive interior/exterior material of the present invention adopts natural fiber and poly(lactic acid), and raw material sources green is renewable, can be degradable.Adopt automobile inside/outside decorative material of the present invention can improve car load recovery utilization rate.Automotive interior/exterior material formaldehyde content of the present invention is low, low-temperature impact-resistant performance excellence, and fire-retardant, change of moisture content rate is low, and flexural strength and shock strength are high.
Embodiment
Embodiment 1 automotive trim
Sisal fibers by water content 0.2%, length between 6 ~ 15mm immerses in the ethanolic soln of silane coupling agent KH570 of massfraction 2%, processes 2min.
Be that 6 ~ 15mm, density are 1.22g/cm by sisal fibers after treatment and length
3acid fiber by polylactic is 30:70 in mass ratio, traction is sent in mixed slurry continuously respectively, in mixed fillers, contain fire retardant (three (1-oxo-1-phospha-2, 6, 7-trioxa-l-phosphabicyclo [2, 2, 2] octane-4-methylene radical) phosphoric acid ester), antiseptic-germicide (2, 4, the chloro-2 '-hydroxyl-phenyl ether of 4-tri-), oxidation inhibitor (four { β-(3, 5-di-tert-butyl-4-hydroxy phenyl) propionic acid } tetramethylolmethane), anti ultraviolet agent (two (2, 2, 6, 6-tetramethyl-piperidinyl) sebate), lubricant (aluminum stearate), its mass ratio is 2:0.2:0.1:0.1:1, 60s is processed in submergence.
Natural fiber after treatment and acid fiber by polylactic are dried, import twin screw extruder, 170 DEG C of extrusion temperatures by difference traction mouthful, imported after twin screw extruder is extruded jointly by difference traction mouthful, directly, through injection moulding machine injection moulding, 170 DEG C of injection temperatures, get final product to obtain inner plate of car door.
Embodiment 2 automotive trims
Continuous bastose by water content 0.1%, length between 6 ~ 15mm immerses in the acetone soln of silane coupling agent KH570 of massfraction 7%, processes 5min;
Be that 6 ~ 15mm, density are 1.22g/cm by bastose after treatment and length
3acid fiber by polylactic 45:55 in mass ratio, traction is sent in mixed slurry continuously respectively, in mixed fillers, contain fire retardant (ammonium sulfate), antiseptic-germicide (polyoxygenated alkylene trialkyl ammonium salts), oxidation inhibitor (Tyox B), anti ultraviolet agent (two (2,2,6,6-tetramethyl-piperidinyl) sebate) and lubricant (aluminum stearate), its mass ratio is 2.5:0.2:0.1:0.1:1,120s is processed in submergence.
By natural fiber after treatment and acid fiber by polylactic drying, import twin screw extruder by difference traction mouthful, 190 DEG C of extrusion temperatures, after twin screw extruder is extruded jointly, directly through injection moulding machine injection moulding, 190 DEG C of injection temperatures, get final product to obtain roof cover plate.
Embodiment 3 automobile exteriors
Kenaf and jute fiber by water content 0.15% length between 6 ~ 15mm immerses in the acetone soln of Silane coupling agent KH550 of massfraction 5%, processes 10min;
Be that 6 ~ 15mm, density are 1.22g/cm by bluish dogbane after treatment, jute fibre and length
3acid fiber by polylactic 25:25:50 in mass ratio, traction is sent in mixed slurry continuously respectively, mixed slurry is containing fire retardant (1-oxygen-4-methylol-2, 6, 7-trioxa-1-phospha dicyclo [2, 2, 2] octane), antiseptic-germicide (3-(dimethoxy silylation) propyl-dimethyl octadecyl ammonium chloride), oxidation inhibitor ((3, 5-di-tert-butyl-4-hydroxy phenyl) propionic acid octadecyl ester), anti ultraviolet agent (two (2, 2, 6, 6-tetramethyl-piperidinyl) sebate), and lubricant (calcium stearate), its mass ratio is 3:0.2:0.1:0.1:1, 180s is processed in submergence.
By natural fiber after treatment and acid fiber by polylactic drying, import twin screw extruder, 180 DEG C of extrusion temperatures by difference traction mouthful, imported after twin screw extruder is extruded jointly by difference traction mouthful, directly, through injection moulding machine injection moulding, 180 DEG C of injection temperatures, get final product to obtain back holding door inner panel.
Embodiment 4 automotive trims
Jute fibre by water content 0.2%, length between 6 ~ 15mm immerses in the ethanolic soln of silane coupling agent KH560 of massfraction 7%, processes 2min.
Be that 6 ~ 15mm, density are 1.22g/cm by jute fibre after treatment and length
3acid fiber by polylactic is 55:45 in mass ratio, traction is sent in mixed slurry continuously respectively, in mixed fillers, contain fire retardant (three (1-oxo-1-phospha-2, 6, 7-trioxa-l-phosphabicyclo [2, 2, 2] octane-4-methylene radical) phosphoric acid ester), antiseptic-germicide (2, 4, the chloro-2 '-hydroxyl-phenyl ether of 4-tri-), oxidation inhibitor (four { β-(3, 5-di-tert-butyl-4-hydroxy phenyl) propionic acid } tetramethylolmethane), anti ultraviolet agent (two (2, 2, 6, 6-tetramethyl-piperidinyl) sebate), lubricant (aluminum stearate), its mass ratio is 2:0.2:0.1:0.1:1, 60s is processed in submergence.
Natural fiber after treatment and acid fiber by polylactic are dried, import twin screw extruder, 170 DEG C of extrusion temperatures by difference traction mouthful, imported after twin screw extruder is extruded jointly by difference traction mouthful, directly, through injection moulding machine injection moulding, 170 DEG C of injection temperatures, get final product to obtain inner plate of car door.
Embodiment 5 automobile exteriors
Continuous ramee by water content 0.1%, length between 6 ~ 15mm immerses in the acetone soln of silane coupling agent KH560 of massfraction 5%, processes 5min;
Be that 6 ~ 15mm, density are 1.22g/cm by ramee after treatment and length
3acid fiber by polylactic 70:30 in mass ratio, traction is sent in mixed slurry continuously respectively, in mixed fillers, contain fire retardant (ammonium sulfate), antiseptic-germicide (polyoxygenated alkylene trialkyl ammonium salts), oxidation inhibitor (Tyox B), anti ultraviolet agent (two (2,2,6,6-tetramethyl-piperidinyl) sebate) and lubricant (aluminum stearate), its mass ratio is 2.5:0.2:0.1:0.1:1,120s is processed in submergence.
By natural fiber after treatment and acid fiber by polylactic drying, import twin screw extruder by difference traction mouthful, 190 DEG C of extrusion temperatures, after twin screw extruder is extruded jointly, directly through injection moulding machine injection moulding, 190 DEG C of injection temperatures, get final product to obtain roof cover plate.
Following table is the performance test results of the automotive interior/exterior material sheet material prepared of above-described embodiment.
Automotive interior/exterior material formaldehyde content prepared by embodiment 1-5 is low, low-temperature impact-resistant performance excellence, and fire-retardant, change of moisture content rate is low, and flexural strength and shock strength are high.
More than explanation is just illustrative for the purpose of the present invention; and nonrestrictive, those of ordinary skill in the art understand, in the case of not departing from the spirit and scope that claims limit; can make many amendments, variation or equivalence, but all will fall within the scope of protection of the present invention.
Claims (8)
1. a preparation method for automotive interior/exterior material, comprises the steps:
Process water content lower than 0.2% natural fiber with silane coupling agent;
Be 1.22g/cm by natural fiber after treatment and density
3acid fiber by polylactic draw respectively and send into continuously in mixed slurry submergence and process 60～180s;
Natural fiber after treatment submergence and acid fiber by polylactic are dried to water content lower than 0.2%, then import twin screw extruder, after twin screw extruder is extruded jointly, obtain described automotive interior/exterior material;
Described silane coupling agent is treated to and will in the acetone or alcohol solution of the silane coupling agent of described natural fiber immersion massfraction 2%-7%, processes 2-10min;
The quality percentage composition of described natural fiber is 30-70%;
The quality percentage composition of described acid fiber by polylactic is 30-70%;
Described mixed slurry is containing fire retardant, antiseptic-germicide, oxidation inhibitor, anti ultraviolet agent and lubricant, and the mass ratio of described fire retardant, antiseptic-germicide, oxidation inhibitor, anti ultraviolet agent and lubricant is (2-3): 0.2: 0.1: 0.1: 1.
2. method according to claim 1, is characterized in that, described silane coupling agent is selected from one or more in KH550, KH560, KH570, KH151.
3. method according to claim 1, is characterized in that, described natural fiber is any one or several in ramie, jute, mestha, hemp, flax, sisal hemp and bluish dogbane.
4. method according to claim 3, is characterized in that, the length of described natural fiber is 6～15mm, and the length of described acid fiber by polylactic is 6～15mm.
5. method according to claim 1, it is characterized in that, described fire retardant is selected from three (1-oxo-1-phospha-2,6,7-trioxa-l-phosphabicyclos [2,2,2] octane-4-methylene radical) phosphoric acid ester, 1-oxygen-4-methylol-2,6,7-trioxa-1-phospha dicyclo [2,2,2] one or more in octane and ammonium sulfate halogen-free flame retardants; Described antiseptic-germicide is selected from one or more in the chloro-2 '-hydroxyl-phenyl ether of 2,4,4-tri-, 3-(dimethoxy silylation) propyl-dimethyl octadecyl ammonium chloride, polyoxygenated alkylene trialkyl ammonium salts; Described oxidation inhibitor is selected from one or more in four { β-(3,5-di-tert-butyl-4-hydroxy phenyl) propionic acid } tetramethylolmethane, (3,5-di-tert-butyl-4-hydroxy phenyl) propionic acid octadecyl ester, Tyox B; Described anti ultraviolet agent is selected from two (2,2,6,6-tetramethyl-piperidinyl) sebate or [[6-[1,1,3,3-tetramethyl butyl] amido]-guanamine, 4-bis-] [[(2,2,6,6-tetramethyl--4-piperidinyl) imido grpup] methene [(2,2,6,6-tetramethyl--4-piperidinyl) imido grpup]] polymer in one; Described lubricant is selected from one or both in aluminum stearate or calcium stearate.
6. method according to claim 1, is characterized in that, described extrusion temperature is 170 DEG C-190 DEG C.
7. the automotive interior/exterior material that in claim 1-6 prepared by arbitrary described method.
8. automotive interior/exterior material claimed in claim 7 is in the application of preparing in automobile internal and external ornament.
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| EP2796434A1 (en) * | 2013-04-23 | 2014-10-29 | Redco NV | Process for the treatment of cellulose fibers |
| CN103554691B (en) * | 2013-11-05 | 2015-10-07 | 苏州万隆汽车零部件股份有限公司 | A kind of Automotive interior product |
| CN105419271A (en) * | 2015-12-23 | 2016-03-23 | 蒋金香 | Environment-friendly automotive interior composite material and preparation method thereof |
| CN105754145A (en) * | 2016-03-10 | 2016-07-13 | 浙江理工大学 | Preparation method of degradable composite materials for cars |
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| CN101003667A (en) * | 2006-01-20 | 2007-07-25 | 东丽纤维研究所（中国）有限公司 | Composite material of poly lactic acid / natural faric, and production method |
| CN101812773A (en) * | 2010-03-30 | 2010-08-25 | 奇瑞汽车股份有限公司 | Composite material for automobile interior part and production method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101003667A (en) * | 2006-01-20 | 2007-07-25 | 东丽纤维研究所（中国）有限公司 | Composite material of poly lactic acid / natural faric, and production method |
| CN101812773A (en) * | 2010-03-30 | 2010-08-25 | 奇瑞汽车股份有限公司 | Composite material for automobile interior part and production method thereof |
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| K.Oksman et al.Natural fibres as reinforcement in polylactic acid (PLA) composites.《Composites Science and Technology》.2003,第63卷(第9期),第1317-1324页. |
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