JP2005008712A - Automobile part - Google Patents

Automobile part Download PDF

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Publication number
JP2005008712A
JP2005008712A JP2003172696A JP2003172696A JP2005008712A JP 2005008712 A JP2005008712 A JP 2005008712A JP 2003172696 A JP2003172696 A JP 2003172696A JP 2003172696 A JP2003172696 A JP 2003172696A JP 2005008712 A JP2005008712 A JP 2005008712A
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Japan
Prior art keywords
resin
derived
parts
weight
acid
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Application number
JP2003172696A
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Japanese (ja)
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JP4349006B2 (en
Inventor
Sadanori Kumazawa
Hirokazu Oome
裕千 大目
貞紀 熊澤
Original Assignee
Toray Ind Inc
東レ株式会社
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Priority to JP2003172696A priority Critical patent/JP4349006B2/en
Publication of JP2005008712A publication Critical patent/JP2005008712A/en
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Abstract

Disclosed is a resinous automotive part derived from plant resources having excellent mechanical properties, heat resistance, durability, dimensional stability, and quality.
An automotive part formed by molding a resin composition comprising 1 to 350 parts by weight of a naturally-derived organic filler with respect to 100 parts by weight of a resin derived from a plant resource. Is a polylactic acid resin, the natural organic filler is at least one selected from paper powder or wood powder, and 50% by weight or more of the paper powder is waste paper powder.
[Selection figure] None

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an automobile part having excellent mechanical properties, heat resistance, durability, dimensional stability, and texture.
[0002]
[Prior art]
In recent years, the problem of depletion of fossil resources such as petroleum has been highlighted, and biopolymers made of resin derived from plant resources have attracted attention as plastic materials.
[0003]
Among these, polylactic acid is a monomer that is produced at low cost by fermentation using microorganisms from plant resources such as corn and sweet potato, and has a high melting point of about 170 ° C. Has been.
[0004]
As one of its usage methods, it has been desired to use it for automobile parts that use plastics made from fossil resources such as polypropylene and ABS. When trying to use it under excessive external force, heating, or light rays such as ultraviolet rays as in the case of parts, the characteristics are not always sufficient and the application is limited. Patent Document 1 discloses that a biodegradable resin such as polylactic acid is used for a wire harness connector for an automobile, but the characteristics are insufficient for use in an environment where the automobile is used.
[0005]
[Patent Document 1]
JP-A-11-170928 (first page to third page)
[0006]
[Problems to be solved by the invention]
An object of the present invention is to improve the problems of conventional resins derived from plant resources and to provide automobile parts having excellent mechanical properties, heat resistance, durability, dimensional stability, and texture.
[0007]
[Means for Solving the Problems]
The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
[0008]
That is, the present invention
(A) An automobile part formed by molding a resin composition formed by blending 1 to 350 parts by weight of an organic filler derived from nature with respect to 100 parts by weight of a resin derived from plant resources,
(A) The automotive component according to the above, wherein the plant resource-derived resin is a polylactic acid resin,
(B) The automobile part according to the above, wherein the naturally-derived organic filler is at least one selected from paper powder or wood powder,
(B) The automobile part according to the above, wherein 50% by weight or more of the naturally-derived organic filler is waste paper powder;
The above description, wherein the resin composition is obtained by melt-kneading 0.01 to 10 parts by weight of (C) a carboxyl-terminal reactive end-blocking agent with respect to (A) 100 parts by weight of a plant resource-derived resin. Car parts,
The automotive component according to the above, wherein the resin composition is obtained by further blending 0.01 to 30 parts by weight of (D) a crystallization accelerator with respect to 100 parts by weight of the resin derived from (A) plant resources,
The resin composition comprises (A) 100 parts by weight of a plant resource-derived resin, and (E) 1 to 200 parts by weight of an aliphatic polyester resin and / or an aliphatic aromatic polyester resin other than the plant resource-derived resin. The automobile parts described above, which are blended
The automotive component as described above, wherein the resin composition is obtained by further blending (A) 100 parts by weight of a plant resource-derived resin with 1 to 100 parts by weight of (F) an impact resistance improver,
The automotive component according to the above, wherein the resin composition is obtained by further blending 1 to 100 parts by weight of (G) an inorganic filler with respect to (A) 100 parts by weight of a plant resource-derived resin,
The resin derived from plant resources is a polylactic acid resin, the crystallization temperature at the time of temperature drop from the polylactic acid resin in the composition can be observed, and the crystallization enthalpy at the time of temperature drop from the polylactic acid resin is 35% of the crystal melting enthalpy The automotive part according to the above, comprising a resin composition having the above values,
The above-mentioned automobile part comprising a resin composition, wherein the resin derived from plant resources is a polylactic acid resin, and the crystallization temperature at the time of cooling from the polylactic acid resin in the composition is 110 ° C. or higher,
The automobile part according to the above, wherein the paper powder contains aluminum, silicon, calcium,
The above-mentioned automobile part, wherein the paper powder contains aluminum, silicon, calcium, sulfur,
The automotive part described above, wherein the automotive part is an automotive interior part,
The automotive part as described above, wherein the automotive part is an automotive exterior part,
The automobile part described above, wherein the automobile part is an automobile underhood part,
The automobile part described above, wherein the automobile part is selected from a decorative panel for automobile interior, a trunk cover, a spire tire cover, and a door trim,
It is.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The (A) plant resource-derived resin used in the present invention is melt-moldable, and part or all of the monomer units forming the resin are made from plant resources such as corn, sweet potato, sugar cane, and wood. If it is, it will not be restrict | limited in particular. The resin derived from a plant resource may be made directly from a plant resource by a microorganism or the like (for example, polyhydroxybutyrate obtained by using a microorganism from glucose which is a plant resource). Once the monomer is made, it may be made by polymerization of the monomer (an example of this is polylactic acid obtained by obtaining lactic acid from glucose by a microorganism and polymerizing it). Specific examples of monomer units obtained from these plant resources include lactic acid units, glycolic acid units, hydroxycarboxylic acid units such as hydroxybutanoic acid units, diol units such as butanediol, dicarboxylic acid units such as succinic acid, and glucose units. Is mentioned. When the monomer unit has optically active carbon, the optical purity of the monomer unit is usually high. Specific examples of resins derived from plant resources include polyhydroxyalkanoate resins such as polylactic acid resins, polyglycolic acid resins, and polyhydroxybutyrate resins, cellulose ester resins, polypropylene terephthalate resins, and polybutylene succinate resins. However, polylactic acid resin is particularly preferable from the viewpoint of heat resistance.
[0010]
Plant resource-derived resins may be used alone or in combination of two or more, but when two or more types are used in combination, polylactic acid resin and other plant resource-derived resins should be used in combination. It is preferable to use 1 to 200 parts by weight of resin derived from other plant resources, and more preferably 10 to 100 parts by weight, based on 100 parts by weight of the polylactic acid resin.
[0011]
The polylactic acid resin used in the present invention is a polymer mainly composed of L-lactic acid and / or D-lactic acid, but may contain other copolymerization components other than lactic acid. Other monomer units include ethylene glycol, propylene glycol, butanediol, heptanediol, hexanediol, octanediol, nonanediol, decanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, glycerin, pentane. Glycol compounds such as erythritol, bisphenol A, polyethylene glycol, polypropylene glycol and polytetramethylene glycol, oxalic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malonic acid, glutaric acid, cyclohexanedicarboxylic acid, terephthalic acid , Isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4′-diphenyl ether dicarbohydrate Acids, dicarboxylic acids such as 5-sodium sulfoisophthalic acid, 5-tetrabutylphosphonium isophthalic acid, hydroxycarboxylic acids such as glycolic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid, and caprolactone And lactones such as valerolactone, propiolactone, undecalactone, and 1,5-oxepan-2-one. Such a copolymer component is preferably contained in an amount of generally 0 to 30 mol%, preferably 0 to 10 mol%, in all monomer components.
[0012]
In the present invention, it is preferable to use a polylactic acid resin having a high optical purity of the lactic acid component from the viewpoint of heat resistance. That is, among the total lactic acid components of the polylactic acid resin, it is preferable that 70% or more of the L isomer or 70% or more of the D isomer, and 80% or more of the L isomer or 80% or more of the D isomer. It is particularly preferred that 90% or more of the L isomer or 90% or more of the D isomer is contained, and 98% or more of the L isomer or 98% or more of the D isomer is contained. More preferably, the L-form is contained at 99% or more, or the D-form is contained at 99% or more. Moreover, the upper limit of the content of L-form or D-form is usually 100% or less.
[0013]
As a method for producing the polylactic acid resin, a known polymerization method can be used, and examples thereof include a direct polymerization method from lactic acid and a ring-opening polymerization method via lactide.
[0014]
The molecular weight and molecular weight distribution of the polylactic acid resin are not particularly limited as long as it can be substantially molded, but the weight average molecular weight is usually 10,000 or more, preferably 40,000 or more, and further 8 It is desirable to be 10,000 or more. The weight average molecular weight here refers to the molecular weight in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography.
[0015]
The melting point of the polylactic acid resin is not particularly limited, but is preferably 120 ° C. or higher, more preferably 150 ° C. or higher, and particularly preferably 160 ° C. or higher. The melting point of the polylactic acid resin is usually increased by increasing the optical purity of the lactic acid component, and the polylactic acid resin having a melting point of 120 ° C. or higher contains 90% or more of the L form or 90% or more of the D form. In addition, a polylactic acid resin having a melting point of 150 ° C. or higher can be obtained by containing 95% or more of L-form or 95% or more of D-form.
[0016]
The (B) naturally-derived organic filler used in the present invention is derived from a natural product, preferably contains cellulose, and is not particularly limited.
[0017]
Specific examples of naturally-occurring organic fillers include rice husks, wood chips, okara, waste paper pulverized materials, chip materials such as clothing pulverized materials, cotton fibers, hemp fibers, bamboo fibers, wood fibers, kenaf fibers, jute Fiber, banana fiber, plant fiber such as coconut fiber, pulp or cellulose fiber processed from these plant fibers, and fiber such as animal fibers such as silk, wool, Angola, cashmere, camel, paper powder, wood flour , Bamboo powder, cellulose powder, rice husk powder, fruit husk powder, chitin powder, chitosan powder, protein, starch, etc. From the viewpoint of moldability, paper powder, wood powder, bamboo powder, cellulose powder , Powdered powder such as rice husk powder, fruit husk powder, chitin powder, chitosan powder, protein powder, starch etc., paper powder, wood powder, bamboo powder, cellulose powder are more preferred , More preferably paper dust and wood flour, paper powders are particularly preferred. In addition, these naturally-derived organic fillers may be collected directly from natural products, but from the viewpoint of protecting the global environment and conserving resources, waste materials such as waste paper, waste wood and old clothes are recycled. May be used. Waste paper is newspaper, magazine, other recycled pulp, or paperboard such as corrugated cardboard, cardboard, paper tube, etc. Any one can be used as long as it is processed from plant fiber. From the viewpoint of safety, crushed paperboard such as newspaper and corrugated cardboard, cardboard and paper tube is preferred. Specific examples of the wood include coniferous wood such as pine, cedar, oak, and fir, and broad-leaved wood such as beech, shii, and eucalyptus, and the type is not limited.
[0018]
Although it does not specifically limit as paper powder, It is preferable that an adhesive agent is included from a viewpoint of a moldability. The adhesive is not particularly limited as long as it is usually used when processing paper. Emulsion adhesives such as vinyl acetate resin emulsions and acrylic resin emulsions, polyvinyl alcohol adhesives, Examples include cellulose-based adhesives, natural rubber-based adhesives, starch paste, and hot-melt adhesives such as ethylene-vinyl acetate copolymer resin-based adhesives and polyamide-based adhesives. Emulsion-based adhesives, polyvinyl alcohol-based adhesives An adhesive and a hot melt adhesive are preferable, and an emulsion adhesive and a polyvinyl alcohol adhesive are more preferable. These adhesives are also used as binders for paper processing agents. Adhesives include clay, bentonite, talc, kaolin, montmorillonite, mica, synthetic mica, zeolite, silica, graphite, carbon black, magnesium oxide, calcium oxide, titanium oxide, calcium sulfide, magnesium carbonate, calcium carbonate, carbonic acid. Inorganic fillers such as barium, barium sulfate, aluminum oxide and neodymium oxide are preferably contained, and clay, bentonite, talc, kaolinite, montmorillonite, synthetic mica and silica are more preferable.
[0019]
Moreover, as a paper powder, from a moldability viewpoint, it is preferable that an ash content is 5 weight% or more, It is more preferable that it is 5.5 weight% or more, It is further more preferable that it is 8 weight% or more. The upper limit is not particularly limited, but is preferably 60% by weight or less, and more preferably 30% by weight or less. Here, the ash content is a ratio of the weight of the remaining ash content when the organic filler is baked at a high temperature of 450 ° C. or higher for 8 hours using an electric furnace or the like to the weight of the paper powder before baking.
[0020]
The paper powder preferably contains 5 to 20% by weight of an inorganic compound in the paper powder, more preferably contains aluminum, silicon, or calcium as an element of the inorganic compound, aluminum, silicon, calcium, Those containing sulfur are more preferred, those containing aluminum, silicon, calcium, sulfur and magnesium are particularly preferred, and those containing aluminum at least twice the content of magnesium are particularly preferred.
[0021]
The abundance ratio of aluminum, silicon, calcium, sulfur, and magnesium is not particularly limited. For example, when the total number of the elements is 100, aluminum is 1 to 60% and silicon is 20 to 90%. , 1-30% calcium, 1-20% sulfur, 0-20% magnesium, 10-55% aluminum, 20-85% silicon, 1-25% calcium, sulfur It is more preferable that it is 1 to 15% and magnesium is 0 to 10%, aluminum is 20 to 50%, silicon is 25 to 80%, calcium is 3 to 20%, sulfur is 2 to 10%, and magnesium is 0 to 0%. More preferably, it is 8%. About these elemental analysis, although it can measure even if it uses either the simple substance of a natural origin organic filler, or the ash content of a natural origin organic filler, it is preferable to use an ash content. Elemental analysis is performed by using an apparatus that combines X-ray fluorescence analysis, atomic absorption spectrometry, scanning electron microscope (SEM) or transmission electron microscope (TEM), and energy dispersive X-ray microanalyzer (XMA). Although it can be measured, it is preferable to use fluorescent X-ray analysis.
[0022]
Moreover, as a paper powder, it is preferable from the viewpoint of a moldability to contain the cellulose which microparticles | fine-particles adhere on the surface. The fine particles are not particularly limited, and may be an inorganic filler contained in the adhesive as described above, and may be either an organic material or other inorganic material. The thing containing is preferable. The shape of the fine particles may be any of a needle shape, a plate shape, and a spherical shape. The size of the fine particles is not particularly limited, but is preferably distributed in the range of 1 to 5000 nm, more preferably in the range of 1 to 1000 nm, and distribution in the range of 1 to 500 nm. More preferably, it is distributed in the range of 1 to 100 nm, and most preferably in the range of 1 to 80 nm. Here, “distributed” in a specific range means that 80% or more of the total number of fine particles is included in the specific range. The adhesion form of the fine particles may be either in an aggregated state or a dispersed state, but is more preferably adhered in a dispersed state. The size of the fine particles is such that a molded product obtained from a resin composition containing a plant-derived resin and a naturally-derived organic filler can be observed with a transmission electron microscope at a magnification of 80,000 times. The total number is arbitrarily 1000.
[0023]
Moreover, also in the organic filler derived from other natural products other than paper dust, it is preferable to select and use the above characteristics, that is, the ash content, the composition having the ash content, and the fine particles adhered.
[0024]
Moreover, in this invention, as long as the resin composition of this invention is obtained, the organic filler derived from a natural product can be used by 1 type, or 2 or more types, However, It should contain the paper powder which has the said preferable characteristic. preferable. Moreover, it is preferable that the used paper powder is contained 50% by weight or more.
[0025]
In the present invention, it is preferable to further melt knead (C) a carboxyl group-reactive end-blocking agent. The carboxyl group-reactive end-blocking agent used in the present invention is not particularly limited as long as it is a compound that can block the carboxyl end group of the polymer, and those used as the carboxyl-terminal blocking agent of the polymer are used. be able to. In the present invention, the carboxyl group-reactive endblocker not only blocks the end of a plant resource-derived resin, but also generates acid by thermal decomposition or hydrolysis of a plant resource-derived resin or a natural-derived organic filler. The carboxyl group of the low molecular compound can also be blocked. Further, the end-capping agent is more preferably a compound that can also block the hydroxyl end where an acidic low molecular weight compound is generated by thermal decomposition.
[0026]
As such a carboxyl group-reactive end-blocking agent, it is preferable to use at least one compound selected from an epoxy compound, an oxazoline compound, an oxazine compound, and a carbodiimide compound, and among them, an epoxy compound and / or a carbodiimide compound are preferable. .
[0027]
As an epoxy compound that can be used as a carboxyl group-reactive end-blocking agent in the present invention, a glycidyl ether compound, a glycidyl ester compound, a glycidyl amine compound, a glycidyl imide compound, and an alicyclic epoxy compound can be preferably used. By blending these, a molded product having excellent mechanical properties, moldability, heat resistance and durability can be obtained.
[0028]
Examples of glycidyl ether compounds include butyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, o-phenylphenyl glycidyl ether, ethylene oxide lauryl alcohol glycidyl ether, ethylene oxide phenol glycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol Diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane trig Bisphenols such as sidyl ether, pentaerythritol polyglycidyl ether, 2,2-bis- (4-hydroxyphenyl) propane, 2,2-bis- (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) sulfone; Examples thereof include a bisphenol A diglycidyl ether type epoxy resin, a bisphenol F diglycidyl ether type epoxy resin, a bisphenol S diglycidyl ether type epoxy resin obtained from a condensation reaction with epichlorohydrin. Among these, bisphenol A diglycidyl ether type epoxy resin is preferable.
[0029]
Examples of glycidyl ester compounds include benzoic acid glycidyl ester, p-toluic acid glycidyl ester, cyclohexanecarboxylic acid glycidyl ester, stearic acid glycidyl ester, lauric acid glycidyl ester, palmitic acid glycidyl ester, versatic acid glycidyl ester, oleic acid glycidyl ester Ester, linoleic acid glycidyl ester, linolenic acid glycidyl ester, terephthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, phthalic acid diglycidyl ester, naphthalene dicarboxylic acid diglycidyl ester, bibenzoic acid diglycidyl ester, methyl terephthalic acid diglycidyl ester , Hexahydrophthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, Hexane dicarboxylic acid diglycidyl ester, adipic acid diglycidyl ester, succinic acid diglycidyl ester, sebacic acid diglycidyl ester, dodecanedioic acid diglycidyl ester, octadecanedicarboxylic acid diglycidyl ester, trimellitic acid triglycidyl ester, pyromellitic acid tetra A glycidyl ester etc. can be mentioned. Among these, benzoic acid glycidyl ester and versatic acid glycidyl ester are preferable.
[0030]
Examples of glycidylamine compounds include tetraglycidylaminodiphenylmethane, triglycidyl-paraaminophenol, triglycidyl-metaaminophenol, diglycidylaniline, diglycidyltoluidine, tetraglycidylmetaxylenediamine, diglycidyltribromoaniline, tetraglycidylbisamino Examples include methylcyclohexane, triglycidyl cyanurate, and triglycidyl isocyanurate.
[0031]
Examples of glycidylimide compounds include N-glycidylphthalimide, N-glycidyl-4-methylphthalimide, N-glycidyl-4,5-dimethylphthalimide, N-glycidyl-3-methylphthalimide, N-glycidyl-3,6- Dimethylphthalimide, N-glycidyl-4-ethoxyphthalimide, N-glycidyl-4-chlorophthalimide, N-glycidyl-4,5-dichlorophthalimide, N-glycidyl-3,4,5,6-tetrabromophthalimide, N -Glycidyl-4-n-butyl-5-bromophthalimide, N-glycidyl succinimide, N-glycidyl hexahydrophthalimide, N-glycidyl-1,2,3,6-tetrahydrophthalimide, N-glycidyl maleimide, N- Glycidyl-α, β-dimethyl Succinimide, N-glycidyl-α-ethylsuccinimide, N-glycidyl-α-propylsuccinimide, N-glycidylbenzamide, N-glycidyl-p-methylbenzamide, N-glycidylnaphthamide, N-glycidylsteramide, etc. be able to. Of these, N-glycidylphthalimide is preferable.
[0032]
Examples of alicyclic epoxy compounds include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene diepoxide, N-methyl-4, 5-epoxycyclohexane-1,2-dicarboxylic imide, N-ethyl-4,5-epoxycyclohexane-1,2-dicarboxylic imide, N-phenyl-4,5-epoxycyclohexane-1,2-dicarboxylic imide N-naphthyl-4,5-epoxycyclohexane-1,2-dicarboxylic imide, N-tolyl-3-methyl-4,5-epoxycyclohexane-1,2-dicarboxylic imide, and the like.
[0033]
Further, as other epoxy compounds, epoxy-modified fatty acid glycerides such as epoxidized soybean oil, epoxidized linseed oil, and epoxidized whale oil, phenol novolac type epoxy resins, cresol nozolac type epoxy resins, and the like can be used.
[0034]
Examples of the oxazoline compound that can be used as a carboxyl group-reactive end-blocking agent used in the present invention include 2-methoxy-2-oxazoline, 2-ethoxy-2-oxazoline, 2-propoxy-2-oxazoline, 2-butoxy 2-oxazoline, 2-pentyloxy-2-oxazoline, 2-hexyloxy-2-oxazoline, 2-heptyloxy-2-oxazoline, 2-octyloxy-2-oxazoline, 2-nonyloxy-2-oxazoline, 2 -Decyloxy-2-oxazoline, 2-cyclopentyloxy-2-oxazoline, 2-cyclohexyloxy-2-oxazoline, 2-allyloxy-2-oxazoline, 2-methallyloxy-2-oxazoline, 2-crotyloxy-2-oxazoline , 2-pheno Ci-2-oxazoline, 2-cresyl-2-oxazoline, 2-o-ethylphenoxy-2-oxazoline, 2-o-propylphenoxy-2-oxazoline, 2-o-phenylphenoxy-2-oxazoline, 2-m -Ethylphenoxy-2-oxazoline, 2-m-propylphenoxy-2-oxazoline, 2-p-phenylphenoxy-2-oxazoline, 2-methyl-2-oxazoline, 2-ethyl-2-oxazoline, 2-propyl- 2-oxazoline, 2-butyl-2-oxazoline, 2-pentyl-2-oxazoline, 2-hexyl-2-oxazoline, 2-heptyl-2-oxazoline, 2-octyl-2-oxazoline, 2-nonyl-2- Oxazoline, 2-decyl-2-oxazoline, 2-cyclopentyl-2-oxy Zolin, 2-cyclohexyl-2-oxazoline, 2-allyl-2-oxazoline, 2-methallyl-2-oxazoline, 2-crotyl-2-oxazoline, 2-phenyl-2-oxazoline, 2-o-ethylphenyl-2 -Oxazoline, 2-o-propylphenyl-2-oxazoline, 2-o-phenylphenyl-2-oxazoline, 2-m-ethylphenyl-2-oxazoline, 2-m-propylphenyl-2-oxazoline, 2-p -Phenylphenyl-2-oxazoline, 2,2'-bis (2-oxazoline), 2,2'-bis (4-methyl-2-oxazoline), 2,2'-bis (4,4'-dimethyl- 2-oxazoline), 2,2'-bis (4-ethyl-2-oxazoline), 2,2'-bis (4,4'-diethyl-2-oxy) Sazoline), 2,2'-bis (4-propyl-2-oxazoline), 2,2'-bis (4-butyl-2-oxazoline), 2,2'-bis (4-hexyl-2-oxazoline) 2,2'-bis (4-phenyl-2-oxazoline), 2,2'-bis (4-cyclohexyl-2-oxazoline), 2,2'-bis (4-benzyl-2-oxazoline), 2 , 2'-p-phenylenebis (2-oxazoline), 2,2'-m-phenylenebis (2-oxazoline), 2,2'-o-phenylenebis (2-oxazoline), 2,2'-p -Phenylenebis (4-methyl-2-oxazoline), 2,2'-p-phenylenebis (4,4'-dimethyl-2-oxazoline), 2,2'-m-phenylenebis (4-methyl-2) -Oxazoline), 2, 2 -M-phenylenebis (4,4'-dimethyl-2-oxazoline), 2,2'-ethylenebis (2-oxazoline), 2,2'-tetramethylenebis (2-oxazoline), 2,2'- Hexamethylene bis (2-oxazoline), 2,2'-octamethylene bis (2-oxazoline), 2,2'-decamethylene bis (2-oxazoline), 2,2'-ethylenebis (4-methyl-2) -Oxazoline), 2,2'-tetramethylenebis (4,4'-dimethyl-2-oxazoline), 2,2'-9,9'-diphenoxyethanebis (2-oxazoline), 2,2'- Examples include cyclohexylenebis (2-oxazoline), 2,2'-diphenylenebis (2-oxazoline), and the like. Furthermore, the polyoxazoline compound etc. which contain the above-mentioned compound as a monomer unit can be mentioned.
[0035]
Examples of oxazine compounds as carboxyl group-reactive endblockers that can be used in the present invention include 2-methoxy-5,6-dihydro-4H-1,3-oxazine, 2-ethoxy-5,6-dihydro. -4H-1,3-oxazine, 2-propoxy-5,6-dihydro-4H-1,3-oxazine, 2-butoxy-5,6-dihydro-4H-1,3-oxazine, 2-pentyloxy- 5,6-dihydro-4H-1,3-oxazine, 2-hexyloxy-5,6-dihydro-4H-1,3-oxazine, 2-heptyloxy-5,6-dihydro-4H-1,3- Oxazine, 2-octyloxy-5,6-dihydro-4H-1,3-oxazine, 2-nonyloxy-5,6-dihydro-4H-1,3-oxazine, 2-decyloxy-5 6-dihydro-4H-1,3-oxazine, 2-cyclopentyloxy-5,6-dihydro-4H-1,3-oxazine, 2-cyclohexyloxy-5,6-dihydro-4H-1,3-oxazine, 2-allyloxy-5,6-dihydro-4H-1,3-oxazine, 2-methallyloxy-5,6-dihydro-4H-1,3-oxazine, 2-crotyloxy-5,6-dihydro-4H- 1,3-oxazine and the like, and further, 2,2′-bis (5,6-dihydro-4H-1,3-oxazine), 2,2′-methylenebis (5,6-dihydro-4H— 1,3-oxazine), 2,2'-ethylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2'-propylenebis (5,6-dihydro-4H-1,3- Oxazi ), 2,2'-butylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2'-hexamethylenebis (5,6-dihydro-4H-1,3-oxazine), 2, 2'-p-phenylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2'-m-phenylenebis (5,6-dihydro-4H-1,3-oxazine), 2, 2'-naphthylene bis (5,6-dihydro-4H-1,3-oxazine), 2,2'-P, P'-diphenylene bis (5,6-dihydro-4H-1,3-oxazine), etc. Can be mentioned. Furthermore, the polyoxazine compound etc. which contain an above-described compound as a monomer unit are mentioned.
[0036]
Among the oxazoline compounds and oxazine compounds, 2,2′-m-phenylenebis (2-oxazoline) and 2,2′-p-phenylenebis (2-oxazoline) are preferable.
[0037]
The carbodiimide compound that can be used as a carboxyl group-reactive end-blocking agent in the present invention is a compound having at least one carbodiimide group represented by (—N═C═N—) in the molecule. The organic isocyanate can be heated in the presence of a simple catalyst and produced by a decarboxylation reaction.
[0038]
Examples of carbodiimide compounds include diphenylcarbodiimide, di-cyclohexylcarbodiimide, di-2,6-dimethylphenylcarbodiimide, diisopropylcarbodiimide, dioctyldecylcarbodiimide, di-o-toluylcarbodiimide, di-p-toluylcarbodiimide, di-p- Nitrophenylcarbodiimide, di-p-aminophenylcarbodiimide, di-p-hydroxyphenylcarbodiimide, di-p-chlorophenylcarbodiimide, di-o-chlorophenylcarbodiimide, di-3,4-dichlorophenylcarbodiimide, di-2 , 5-dichlorophenylcarbodiimide, p-phenylene-bis-o-toluylcarbodiimide, p-phenylene-bis-dicyclohexylcarbodiimide, p-phenylene- Su-di-p-chlorophenylcarbodiimide, 2,6,2 ', 6'-tetraisopropyldiphenylcarbodiimide, hexamethylene-bis-cyclohexylcarbodiimide, ethylene-bis-diphenylcarbodiimide, ethylene-bis-dicyclohexylcarbodiimide, N , N′-di-o-triylcarbodiimide, N, N′-diphenylcarbodiimide, N, N′-dioctyldecylcarbodiimide, N, N′-di-2,6-dimethylphenylcarbodiimide, N-triyl-N ′ -Cyclohexylcarbodiimide, N, N'-di-2,6-diisopropylphenylcarbodiimide, N, N'-di-2,6-di-tert-butylphenylcarbodiimide, N-toluyl-N'-phenylcarbodiimide, N, N'-di-p-nitrof Nylcarbodiimide, N, N'-di-p-aminophenylcarbodiimide, N, N'-di-p-hydroxyphenylcarbodiimide, N, N'-di-cyclohexylcarbodiimide, N, N'-di-p-toluylcarbodiimide N, N'-benzylcarbodiimide, N-octadecyl-N'-phenylcarbodiimide, N-benzyl-N'-phenylcarbodiimide, N-octadecyl-N'-tolylcarbodiimide, N-cyclohexyl-N'-tolylcarbodiimide, N -Phenyl-N'-tolylcarbodiimide, N-benzyl-N'-tolylcarbodiimide, N, N'-di-o-ethylphenylcarbodiimide, N, N'-di-p-ethylphenylcarbodiimide, N, N'- Di-o-isopropylphenylcarbodiimide, N, N ′ -Di-p-isopropylphenyl carbodiimide, N, N'-di-o-isobutylphenyl carbodiimide, N, N'-di-p-isobutylphenyl carbodiimide, N, N'-di-2,6-diethylphenyl carbodiimide, N, N'-di-2-ethyl-6-isopropylphenylcarbodiimide, N, N'-di-2-isobutyl-6-isopropylphenylcarbodiimide, N, N'-di-2,4,6-trimethylphenylcarbodiimide Mono- or dicarbodiimide compounds such as N, N'-di-2,4,6-triisopropylphenylcarbodiimide, N, N'-di-2,4,6-triisobutylphenylcarbodiimide, poly (1,6- Hexamethylenecarbodiimide), poly (4,4'-methylenebiscyclohexylcarbodiimi ), Poly (1,3-cyclohexylenecarbodiimide), poly (1,4-cyclohexylenecarbodiimide), poly (4,4'-diphenylmethanecarbodiimide), poly (3,3'-dimethyl-4,4'-diphenylmethane) Carbodiimide), poly (naphthylenecarbodiimide), poly (p-phenylenecarbodiimide), poly (m-phenylenecarbodiimide), poly (tolylcarbodiimide), poly (diisopropylcarbodiimide), poly (methyl-diisopropylphenylenecarbodiimide), poly (triethyl) And polycarbodiimides such as phenylene carbodiimide) and poly (triisopropylphenylene carbodiimide). Of these, N, N′-di-2,6-diisopropylphenylcarbodiimide and 2,6,2 ′, 6′-tetraisopropyldiphenylcarbodiimide are preferable.
[0039]
As the carboxyl group-reactive end-blocking agent, one or more compounds can be arbitrarily selected and used.
[0040]
In the resin composition of the present invention, the carboxyl terminal and the acidic low molecular compound may be appropriately blocked according to the use to be used as a molded product, but the specific carboxyl terminal and acidic low molecular compound are blocked. The acid concentration in the composition is 10 equivalents / 10 6 g or less is preferable from the viewpoint of hydrolysis resistance, and 5 equivalents / 10 6 More preferably, it is 1 g / 10 or less. 6 It is particularly preferred that it is g or less. The acid concentration in the polymer composition can be measured by dissolving the polymer composition in a suitable solvent and then titrating with an alkali compound solution such as sodium hydroxide having a known concentration, or by NMR.
[0041]
The amount of the carboxyl group-reactive end-blocking agent is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, when the plant resource-derived resin is 100 parts by weight.
[0042]
In the present invention, it is preferable to further add a reaction catalyst of a carboxyl group reactive end-blocking agent. The reaction catalyst referred to here is a compound that has an effect of promoting the reaction between the carboxyl group-reactive end-blocking agent and the carboxyl end of the polymer end or acidic low molecular weight compound. Certain compounds are preferred. Examples of such compounds include alkali metal compounds, alkaline earth metal compounds, tertiary amine compounds, imidazole compounds, quaternary ammonium salts, phosphine compounds, phosphonium salts, phosphate esters, organic acids, Lewis acids. Specific examples thereof include sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium acetate, potassium acetate, lithium acetate, stearin Sodium phosphate, potassium stearate, lithium stearate, sodium borohydride, lithium borohydride, sodium phenyl borohydride, sodium benzoate, potassium benzoate, lithium benzoate, disodium hydrogen phosphate, hydrogen phosphate Dipotassium, Alkali metal compounds such as dilithium hydrogen phosphate, disodium salt of bisphenol A, dipotassium salt, dilithium salt, sodium salt of phenol, potassium salt, lithium salt, cesium salt, calcium hydroxide, water Alkaline earth such as barium oxide, magnesium hydroxide, strontium hydroxide, calcium bicarbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, magnesium stearate, strontium stearate Metal compounds, triethylamine, tributylamine, trihexylamine, triamylamine, triethanolamine, dimethylaminoethanol, triethylenediamine, dimethylphenylamine , Dimethylbenzylamine, 2- (dimethylaminomethyl) phenol, dimethylaniline, pyridine, picoline, tertiary amines such as 1,8-diazabicyclo (5,4,0) undecene-7, 2-methylimidazole, 2-ethyl Imidazole, 2-isopropylimidazole, 2-ethyl-4-methylimidazole, imidazole compounds such as 4-phenyl-2-methylimidazole, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium bromide, trimethylbenzylammonium chloride, triethylbenzyl Quaternary ammonium salts such as ammonium chloride, tripropylbenzylammonium chloride, N-methylpyridinium chloride, trimethylphosphine, Phosphine compounds such as triethylphosphine, tributylphosphine, trioctylphosphine, phosphonium salts such as tetramethylphosphonium bromide, tetrabutylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphonium bromide, triphenylbenzylphosphonium bromide, trimethyl phosphate, triethyl phosphate , Tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, tri (p-hydroxy) phenyl phosphate, tri (p-methoxy ) Phenyl phosphate Phosphoric acid esters, oxalic acid, p-toluenesulfonic acid, dinonylnaphthalenedisulfonic acid, organic acids such as dodecylbenzenesulfonic acid, Lewis acids such as boron trifluoride, aluminum tetrachloride, titanium tetrachloride, tin tetrachloride, etc. These may be used alone or in combination of two or more. Among these, it is preferable to use an alkali metal compound, an alkaline earth metal compound, and a phosphate ester, and particularly an alkali metal or an organic salt of an alkaline earth metal can be preferably used. Particularly preferred compounds are sodium stearate, potassium stearate, calcium stearate, magnesium stearate, sodium benzoate, sodium acetate, potassium acetate, calcium acetate and magnesium acetate. Further, an organic salt of an alkali metal or alkaline earth metal having 6 or more carbon atoms is preferable, and it is preferable to use one or more of sodium stearate, potassium stearate, calcium stearate, magnesium stearate, and sodium benzoate.
[0043]
The addition amount of the reaction catalyst is not particularly limited, but is preferably 0.001 to 1 part by weight and more preferably 0.01 to 0.2 part by weight with respect to 100 parts by weight of the plant resource-derived resin. More preferably, 0.02 to 0.1 parts by weight is most preferable.
[0044]
In the present invention, it is preferable to further blend (D) a crystallization accelerator. The crystallization accelerator used in the present invention can be selected from a wide variety of compounds, but the crystal nucleating agent that promotes the formation of crystal nuclei of the polymer, or the softening of the polymer to facilitate movement and promote crystal growth. A plasticizer can be preferably used.
[0045]
The blending amount of the crystallization accelerator used in the present invention is preferably 0.01 to 30 parts by weight and preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the plant resource-derived resin. More preferred is 1 to 10 parts by weight.
[0046]
In the present invention, the crystal nucleating agent used as the crystallization accelerator (D) can be used without particular limitation, and any of inorganic crystal nucleating agents and organic crystal nucleating agents can be used. Specific examples of inorganic crystal nucleating agents include talc, kaolin, montmorillonite, synthetic mica, clay, zeolite, silica, graphite, carbon black, zinc oxide, magnesium oxide, titanium oxide, calcium sulfide, boron nitride, calcium carbonate, sulfuric acid Examples thereof include metal salts of barium, aluminum oxide, neodymium oxide and phenylphosphonate. These inorganic crystal nucleating agents are preferably modified with an organic substance in order to enhance dispersibility in the composition.
[0047]
Specific examples of organic crystal nucleating agents include sodium benzoate, potassium benzoate, lithium benzoate, calcium benzoate, magnesium benzoate, barium benzoate, lithium terephthalate, sodium terephthalate, potassium terephthalate, Calcium oxide, sodium laurate, potassium laurate, sodium myristate, potassium myristate, calcium myristate, sodium octacosanoate, calcium octacosanoate, sodium stearate, potassium stearate, lithium stearate, calcium stearate, magnesium stearate, Barium stearate, sodium montanate, calcium montanate, sodium toluate, sodium salicylate, potassium salicylate, salicylic acid , Metal salts of organic carboxylic acids such as aluminum dibenzoate, potassium dibenzoate, lithium dibenzoate, sodium β-naphthalate, sodium cyclohexanecarboxylate, organic sulfonates such as sodium p-toluenesulfonate, sodium sulfoisophthalate, stearic acid Amide, ethylenebislauric acid amide, palmitic acid amide, hydroxystearic acid amide, erucic acid amide, carboxylic acid amides such as trimesic acid tris (t-butylamide), low density polyethylene, high density polyethylene, polypropylene, polyisopropylene, polybutene Polymers such as poly-4-methylpentene, poly-3-methylbutene-1, polyvinylcycloalkane, polyvinyltrialkylsilane, and high melting point polylactic acid, Sodium salt or potassium salt of a polymer having a carboxyl group such as sodium salt of ethylene-acrylic acid or methacrylic acid copolymer, sodium salt of styrene-maleic anhydride copolymer (so-called ionomer), benzylidene sorbitol and its derivatives, sodium-2, Phosphorus compound metal salts such as 2'-methylenebis (4,6-di-t-butylphenyl) phosphate and 2,2-methylbis (4,6-di-t-butylphenyl) sodium can be exemplified. .
[0048]
As the crystal nucleating agent used in the present invention, among those exemplified above, at least one selected from talc and an organic carboxylic acid metal salt is particularly preferable. The crystal nucleating agent used in the present invention may be used alone or in combination of two or more.
[0049]
The compounding amount of the crystal nucleating agent is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 10 parts by weight with respect to 100 parts by weight of the resin derived from plant resources. .1 to 5 parts by weight is particularly preferable.
[0050]
The plasticizer used as the crystal accelerator (D) in the present invention is not particularly limited. For example, a polyester plasticizer, a glycerin plasticizer, a polycarboxylic acid ester plasticizer, a phosphate ester plasticizer, Examples include polyalkylene glycol plasticizers and epoxy plasticizers.
[0051]
Specific examples of the polyester plasticizer include acid components such as adipic acid, sebacic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, propylene glycol, 1,3-butanediol, 1,4-butane. Examples thereof include polyesters composed of diol components such as diol, 1,6-hexanediol, ethylene glycol and diethylene glycol, and polyesters composed of hydroxycarboxylic acid such as polycaprolactone. These polyesters may be end-capped with a monofunctional carboxylic acid or monofunctional alcohol, or may be end-capped with an epoxy compound or the like.
[0052]
Specific examples of the glycerin plasticizer include glycerin monoacetomonolaurate, glycerin diacetomonolaurate, glycerin monoacetomonostearate, glycerin diacetomonooleate, and glycerin monoacetomonomontanate.
[0053]
Specific examples of polycarboxylic acid plasticizers include phthalates such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diheptyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, and trimellitic acid. Tributyl, trimellitic acid esters such as trioctyl trimellitic acid, trihexyl trimellitic acid, adipic acid esters such as diisodecyl adipate, n-octyl-n-decyl adipate, triethyl acetylcitrate, tributyl acetylcitrate, etc. Citrate esters, azelaic acid esters such as di-2-ethylhexyl azelate, sebacic acid esters such as dibutyl sebacate, and di-2-ethylhexyl sebacate.
[0054]
Specific examples of the phosphate ester plasticizer include tributyl phosphate, tri-2-ethylhexyl phosphate, trioctyl phosphate, triphenyl phosphate, diphenyl-2-ethylhexyl phosphate and tricresyl phosphate. .
[0055]
Specific examples of the polyalkylene glycol plasticizer include polyethylene glycol, polypropylene glycol, poly (ethylene oxide / propylene oxide) block and / or random copolymer, polytetramethylene glycol, ethylene oxide addition polymer of bisphenols, bisphenols Polyalkylene glycols such as propylene oxide addition polymers, tetrahydrofuran addition polymers of bisphenols, or terminal-capped compounds such as terminal epoxy-modified compounds, terminal ester-modified compounds, and terminal ether-modified compounds.
[0056]
The epoxy plasticizer generally refers to an epoxy triglyceride composed of an alkyl epoxy stearate and soybean oil, but there are also so-called epoxy resins mainly made of bisphenol A and epichlorohydrin. Can be used.
[0057]
Specific examples of other plasticizers include benzoic acid esters of aliphatic polyols such as neopentyl glycol dibenzoate, diethylene glycol dibenzoate, triethylene glycol di-2-ethylbutyrate, fatty acid amides such as stearamide, oleic acid Examples thereof include aliphatic carboxylic acid esters such as butyl, oxyacid esters such as methyl acetylricinoleate and butyl acetylricinoleate, pentaerythritol, various sorbitols, polyacrylic acid esters, silicone oils, and paraffins.
[0058]
Among the plasticizers used in the present invention, at least one selected from polyester plasticizers and polyalkylene glycol plasticizers is particularly preferable. Only one type of plasticizer may be used in the present invention, or two or more types may be used in combination.
[0059]
Moreover, the compounding amount of the plasticizer is preferably 0.01 to 30 parts by weight, more preferably 0.1 to 20 parts by weight, with respect to 100 parts by weight of the resin derived from plant resources. 5 to 10 parts by weight is particularly preferable.
[0060]
In the present invention, each of the crystal nucleating agent and the plasticizer may be used alone, but it is preferable to use both in combination.
[0061]
In the present invention, it is preferable to further blend (E) an aliphatic polyester resin and / or an aliphatic aromatic polyester resin other than the plant resource-derived resin.
[0062]
The aliphatic polyester resin of the present invention is not particularly limited, and a polymer mainly composed of an aliphatic hydroxycarboxylic acid, an aliphatic polyvalent carboxylic acid and an aliphatic polyhydric alcohol as main structural components. A polymer etc. are mentioned. Specifically, polymers having aliphatic hydroxycarboxylic acid as a main component include polyglycolic acid, poly-3-hydroxybutyric acid, poly-4-hydroxybutyric acid, poly-4-hydroxyvaleric acid, poly-3-hydroxyhexanoic acid. Or, polycaprolactone and the like, and examples of the polymer mainly composed of aliphatic polycarboxylic acid and aliphatic polyhydric alcohol include polyethylene adipate, polyethylene succinate, polybutylene adipate or polybutylene succinate. . These aliphatic polyesters can be used alone or in combination of two or more. Among these aliphatic polyesters, polybutylene succinate is preferable.
[0063]
The aliphatic aromatic polyester of the present invention is a polyester comprising an aliphatic dicarboxylic acid component, an aromatic dicarboxylic acid component, and an aliphatic diol component. Examples of the aliphatic dicarboxylic acid component include succinic acid, adipic acid, suberic acid, sebacic acid, and dodecanedioic acid. Examples of the aromatic dicarboxylic acid component include isophthalic acid, terephthalic acid, and 2,6-naphthalenedicarboxylic acid. Examples of the aliphatic diol include ethylene glycol, 1,4-butanediol, 1,3-propanediol, 1,4-cyclohexanedimethanol, and the like. The aromatic dicarboxylic acid component of the aliphatic aromatic polyester used in the present invention is preferably 60 mol% or less, more preferably 50 mol% or less. Two or more types of aliphatic dicarboxylic acid component, aromatic dicarboxylic acid component, or aliphatic diol component can be used. In the present invention, it is preferable to use an aliphatic aromatic polyester resin composed of terephthalic acid, adipic acid, and 1,4-butanediol.
[0064]
In addition, in aliphatic polyester resins other than plant resource-derived resins and aliphatic aromatic polyester resins, when the optically active carbon is contained in the monomer unit, the resin is usually low in optical purity.
[0065]
In the present invention, the blending amount of the aliphatic polyester resin other than the plant resource-derived resin and the aliphatic aromatic polyester resin is not particularly limited, but when the plant resource-derived resin is 100 parts by weight, It is preferably 1 to 200 parts by weight, more preferably 5 to 150 parts by weight, and even more preferably 10 to 100 parts by weight.
[0066]
Moreover, in this invention, it is preferable to mix | blend (F) impact resistance improving agents. The impact resistance improver used in the present invention is not particularly limited as long as it can be used for improving the impact resistance of a thermoplastic resin. For example, at least one selected from the following various impact resistance improvers can be used.
[0067]
That is, specific examples of the impact modifier include polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-propylene-nonconjugated diene copolymer, ethylene-butene-1 copolymer, various acrylic rubbers, ethylene- Acrylic acid copolymer and its alkali metal salt (so-called ionomer), ethylene-glycidyl (meth) acrylate copolymer, ethylene-alkyl acrylate copolymer (for example, ethylene-ethyl acrylate copolymer, ethylene-acrylic) Acid butyl copolymer), acid-modified ethylene-propylene copolymer, diene rubber (for example, polybutadiene, polyisoprene, polychloroprene), copolymer of diene and vinyl monomer (for example, styrene-butadiene random copolymer, styrene) -Butadiene block Polymer, styrene-butadiene-styrene block copolymer, styrene-isoprene random copolymer, styrene-isoprene block copolymer, styrene-isoprene-styrene block copolymer, polybutadiene grafted with styrene, Butadiene-acrylonitrile copolymer), polyisobutylene, copolymer of isobutylene and butadiene or isoprene, natural rubber, thiocol rubber, polysulfide rubber, polyurethane rubber, polyether rubber, epichlorohydrin rubber, polyester elastomer, polyamide elastomer Etc.
[0068]
Furthermore, it is composed of those having various degrees of cross-linking, various micro structures such as those having a cis structure, a trans structure, etc., those having a vinyl group, etc., a core layer and one or more shell layers covering it, A so-called core-shell type multi-layered polymer in which adjacent layers are made of different polymers can also be used.
[0069]
The various (co) polymers listed in the above specific examples may be used as the impact resistance improver of the present invention, regardless of whether they are random copolymers, block copolymers, and graft copolymers. it can.
[0070]
Furthermore, in making these (co) polymers, it is also possible to copolymerize monomers such as other olefins, dienes, aromatic vinyl compounds, acrylic acid, acrylic ester and methacrylic ester. is there.
[0071]
Among these impact modifiers, a polymer containing an acrylic unit and a polymer containing a unit having an acid anhydride group and / or a glycidyl group are preferable. Preferable examples of the acrylic unit herein include methyl methacrylate units, methyl acrylate units, ethyl acrylate units and butyl acrylate units. Preferred examples of units having an acid anhydride group or glycidyl group May include maleic anhydride units and glycidyl methacrylate units.
[0072]
The impact resistance improver is a so-called core-shell type multi-layer polymer composed of a core layer and one or more shell layers covering the core layer, and adjacent layers are composed of different polymers. It is preferable that the polymer is a multilayer structure polymer containing methyl methacrylate units or methyl acrylate units in the shell layer. Such a multilayer structure polymer preferably contains an acrylic unit, or preferably contains a unit having an acid anhydride group and / or a glycidyl group. Preferred examples of the acrylic unit include a methyl methacrylate unit, an acrylic acid A methyl unit, an ethyl acrylate unit, and a butyl acrylate unit can be mentioned, As a suitable example of a unit which has an acid anhydride group and a glycidyl group, a maleic anhydride unit and a glycidyl methacrylate unit can be mentioned. In particular, the shell layer contains at least one selected from methyl methacrylate units, methyl acrylate units, maleic anhydride units and glycidyl methacrylate units, and includes butyl acrylate units, ethyl hexyl acrylate units, styrene units and butadiene units. A multilayer structure containing at least one selected from the above in the core layer is preferably used.
[0073]
The glass transition temperature of the impact resistance improver is preferably −20 ° C. or lower, and more preferably −30 ° C. or lower.
[0074]
The blending amount of the impact resistance improver is preferably in the range of 1 to 100 parts by weight and more preferably in the range of 2 to 50 parts by weight with respect to 100 parts by weight of the plant resource-derived resin.
[0075]
In the present invention, it is preferable to further blend (G) an inorganic filler. As the inorganic filler used in the present invention, fibers, plates, granules, and powders that are usually used for reinforcing thermoplastic resins can be used. Specifically, glass fiber, asbestos fiber, carbon fiber, graphite fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium whisker, silicon whisker, wollastonite, sepiolite, asbestos, slag fiber, zonolite, Elastadite, gypsum fiber, silica fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber and boron fiber and other inorganic fillers, glass flakes, non-swellable mica, swellable mica, graphite, metal foil , Ceramic beads, talc, clay, mica, sericite, zeolite, bentonite, organic modified bentonite, organic modified montmorillonite, dolomite, kaolin, fine powder silicic acid, feldspar powder, potassium titanate, shirasu balloon, calcium carbonate , Magnesium carbonate, barium sulfate, calcium oxide, aluminum oxide, titanium oxide, aluminum silicate, silicon oxide, gypsum, novaculite, include plate-like or granular inorganic fillers such as dawsonite and white clay. Among these inorganic fillers, glass fiber, wollastonite, mica and kaolin are particularly preferable. The aspect ratio of the fibrous filler is preferably 5 or more, more preferably 10 or more, and further preferably 20 or more.
[0076]
The inorganic filler may be coated or focused with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin, or a coupling agent such as aminosilane or epoxysilane. May be processed.
[0077]
Moreover, 1-100 weight part is preferable with respect to 100 weight part of resin derived from a plant resource, and, as for the compounding quantity of an inorganic filler, 5-50 weight part is more preferable.
[0078]
For the present invention, one or more flame retardants can be contained. Specific examples of the flame retardant include halogen compounds containing bromine or chlorine, antimony compounds such as antimony trioxide, inorganic hydrates and phosphorus compounds.
[0079]
The composition of the present invention is a conventional additive, for example, an ultraviolet absorber (benzophenone compound, benzotriazole compound, aromatic benzoate compound, oxalic acid anilide compound, cyanoacrylate compound, as long as the object of the present invention is not impaired. Compounds and hindered amine compounds), heat stabilizers (hindered phenol compounds, phosphite compounds, thioether compounds), lubricants, foaming agents, mold release agents, and coloring agents including dyes and pigments The above can further be contained.
[0080]
The composition of the present invention is within the range not impairing the object of the present invention, and other thermoplastic resins such as acrylic resin, polyamide, aromatic polyester, polyacetal, polyphenylene sulfide resin, polyether ether ketone resin, polysulfone, polyphenylene oxide. , Polyimide, polyetherimide, etc.), thermosetting resins (eg, phenol resins, melamine resins, other polyester resins, silicone resins, etc.).
[0081]
In the present invention, when a polylactic acid resin is used as one of the resins derived from plant resources, it is preferable that the crystallization temperature (Tc) at the time of temperature decrease derived from the polylactic acid resin in the resin composition can be observed. Here, the crystallization temperature (Tc) at the time of temperature drop derived from the polylactic acid resin is a crystallization temperature derived from the polylactic acid resin measured by a differential scanning calorimeter (DSC) at a temperature drop rate of 20 ° C./min. Tc is not particularly limited, but is preferably 100 ° C. or higher, more preferably 105 ° C. or higher, and further preferably 110 ° C. or higher from the viewpoint of moldability.
[0082]
In the present invention, when a polylactic acid resin is used as one of the plant resource-derived resins, the crystallization enthalpy (ΔHc) at the time of cooling from the polylactic acid resin is 35% or more of the crystal melting enthalpy (ΔHm), The value is preferably 50% or more, more preferably 70% or more, further preferably 80% or more, and most preferably 100%. Here, the crystallization enthalpy (ΔHc) at the time of temperature decrease derived from polylactic acid resin is the crystallization enthalpy derived from polylactic acid resin measured by DSC at a temperature decrease rate of 20 ° C./min. The crystal melting enthalpy (ΔHm) derived from polylactic acid resin is the crystal melting enthalpy derived from polylactic acid resin measured by DSC at a heating rate of 20 ° C./min, but the heating rate of 20 in the first measurement (1stRUN). After raising the temperature from 30 ° C. to 200 ° C. at a rate of 20 ° C./min, the temperature was cooled to 30 ° C. at a rate of temperature drop of 20 ° C./min, and further from 30 ° C. to 200 ° C. at a rate of temperature rise of 20 ° C./min in the second measurement (2ndRUN). Is the crystal melting enthalpy measured at 2ndRUN when the temperature is raised to.
[0083]
The resin composition of the present invention having such crystal characteristics is preferably the organic filler derived from the above-mentioned preferred natural product, that is, a specific ash content, a specific ash content, a specific particle size fine particle adhered It can obtain by selecting from and using.
[0084]
The production method of the composition of the present invention is not particularly limited, but after pre-blending a plant resource-derived resin, a naturally-derived organic filler and other additives as necessary, the plant resource-derived resin Above the melting point, a method of supplying to a hopper of a twin screw extruder or a Banbury mixer and uniformly melting and kneading, a method of directly kneading with a molding machine, or the like is preferably used. Moreover, when using fine powder, it is also preferable to supply to a hopper independently of another additive.
[0085]
The automobile part of the present invention can be obtained by any method such as generally known injection molding, extrusion molding, press molding, blow molding, foam molding, or sheet molding.
[0086]
The shape of the automobile part of the present invention is not particularly limited, but various shapes such as a fiber shape, a film shape, a sheet shape, a plate shape, a box shape, a lump shape, and a tube shape can be used.
[0087]
The automobile parts of the present invention are particularly suitable for automobile interior parts by taking advantage of their excellent characteristics. Specific examples of automotive interior parts include instrument panels, trims, torque control levers, safety belt parts, register blades, washer levers, window regulator handles, window regulator handle knobs, passing light levers, sun visor brackets, and consoles. Box, trunk cover, spare tire cover, ceiling material, floor material, inner plate, seat material, door panel, door board, steering wheel, rearview mirror housing, air duct panel, wind molding fastener, speed cable liner, sun visor bracket, headrest Examples include rod holders, various motor housings, various plates, and various panels.
[0088]
The automobile parts of the present invention are suitable for exterior parts for automobiles by taking advantage of their excellent characteristics. The automotive exterior parts of the present invention include a roof rail, fascia, fender, garnish, bumper, bumper corner, bumper skirt radiator grill, bonnet, door mirror stay, spoiler, hood louver, wheel cover, wheel cap, grill apron cover frame, lamp Examples include reflectors, lamp bezels, door handles, door panels, side mirror housings, center pillars, air outlet louvers, emblems, exterior trim moldings, slide roofs, and tail lamp rims.
[0089]
The automobile part of the present invention is suitable for an underhood part for automobiles utilizing its excellent characteristics. The underhood parts for automobiles of the present invention include an air flow meter, an air pump, a thermostat housing, an engine mount, an ignition hobbin, an ignition case, a clutch bobbin, a sensor housing, an idle speed control valve, a vacuum switching valve, an ECU housing, a vacuum pump case, Inhibitor switch, rotation sensor, acceleration sensor, distributor cap, coil base, actuator case for ABS, radiator tank top and bottom, cooling fan, fan shroud, engine cover, cylinder head cover, oil cap, oil pan, oil filter, fuel Cap, fuel strainer, distributor cap Vapor canister housing, air cleaner housing, a timing belt cover, brake booster parts, various cases, various tubes, various tanks, various hoses, various clips, various valves, various pipes and the like.
[0090]
The automobile parts of the present invention are suitable for electrical parts by taking advantage of their excellent characteristics. Examples of the automobile electrical component of the present invention include various connectors and switch boxes such as a wire harness connector, an SMJ connector, a PCB connector, and a door grommet connector.
[0091]
In the automobile part of the present invention, the crystallinity of the resin derived from plant resources in the part is preferably 10 to 60%, and more preferably 20 to 50%.
[0092]
In addition, in the automobile part of the present invention, when the plant resource-derived resin is a polylactic acid resin, the crystallization temperature (Tc) at the time of temperature drop from the polylactic acid resin in the resin composition in the part can be observed. preferable. Here, the crystallization temperature (Tc) at the time of temperature drop derived from the polylactic acid resin is a crystallization temperature derived from the polylactic acid resin measured by a differential scanning calorimeter (DSC) at a temperature drop rate of 20 ° C./min. Tc is not particularly limited, but is preferably 100 ° C. or higher, more preferably 105 ° C. or higher, and further preferably 110 ° C. or higher from the viewpoint of moldability.
[0093]
Such automobile parts are preferably selected from the above-mentioned preferred natural product-derived organic fillers, that is, a specific ash content, a specific ash content, a specific composition, and a resin composition with a specific particle size attached. It can be obtained by molding a product. In addition, the crystallinity degree of resin derived from a plant resource in an automobile part can be measured by X-ray diffraction of the part.
[0094]
The automobile parts of the present invention can be recycled after use and used again as automobile parts, or can be used as parts other than automobile parts.
[0095]
【Example】
Hereinafter, the present invention will be described in more detail by way of examples. All the parts in the examples are based on weight.
[0096]
Examples 1-9, Comparative Examples 1-2
Various materials such as plant resource-derived resins shown in Table 1 are mixed in the proportions shown in Table 1, and melt kneaded at a temperature of 190 ° C. and a rotational speed of 100 rpm in a 30 mm diameter twin screw extruder, A resin composition was obtained.
[0097]
In addition, the code | symbol in Table 1 shows the following content.
(A) Resin derived from plant resources
(A-1) Polylactic acid (D-form 1.2%, PMMA equivalent weight average molecular weight 170,000)
(B) Naturally derived organic filler
(B-1) Waste paper powder obtained by pulverizing paperboard with a thickness of 5 mm
(B-2) Waste paper powder crushed from newspaper
(B-3) Wood powder obtained by pulverizing coniferous trees
(B-4) Kenaf fiber (Thailand)
(C) Carboxyl terminal reactive terminal blocker
(C-1) Carbodiimide compound (Nisshinbo "Carbodilite")
(D) Crystallization accelerator
(D-1) Talc (Takehara Chemical "Hitron")
(D-2) Polyethylene glycol (manufactured by Sanyo Chemical "PEG4000")
(E) Polybutylene succinate (“Bionore” # 1001 made by Showa Polymer)
(F) Impact resistance improver
(F-1) Core shell rubber (Mitsubrene S2001, manufactured by Mitsubishi Rayon)
(G) Inorganic filler
(G-1) Clay (manufactured by Southern Clay, “Closite” 30B)
The obtained resin composition was injection molded at a cylinder temperature of 190 ° C. and a mold temperature of 90 ° C. to obtain a test piece having a thickness of 3 mm. Using the obtained test piece, a tensile test was performed according to ASTM method D638, a bending test was performed according to ASTM D790, and an Izod impact test was performed according to ASTM method D256.
[0098]
The obtained resin composition was injection molded at a cylinder temperature of 195 ° C. and a mold temperature of 90 ° C. to obtain a decorative panel for automobile interior having a thickness of 2 mm, a width of 50 mm, and a length of 300 mm. The deformation of the panel during molding was visually observed. A small amount of resin was cut out from the obtained panel, and the crystallization temperature (Tc) at the time of temperature decrease derived from the polylactic acid resin in the resin was measured by a differential scanning calorimeter (DSC: DSC7 manufactured by Perkin Elmer) at a temperature decrease rate of 20 ° C./min. Measured with
[0099]
The panel was placed on the instrument panel of the passenger car, and the texture was visually observed and judged in four stages (the larger the number, the better the texture, and the evaluation was made according to the following criteria. No 2: Heavy texture but rough texture 3: Heavy texture but slightly rough texture 4: Heavy texture and no rough texture) Further, the obtained panel was placed on an instrument panel, left in a closed car for 6 hours under a hot sun with a maximum temperature of 35 ° C., and the presence or absence of deformation was visually observed. The panel is placed on the instrument panel for 6 months from April to September. After using the car mainly outdoors, the tensile test piece is cut out and the tensile strength is measured and compared with the tensile strength before leaving. As a result, the tensile strength retention was calculated.
These results are also shown in Table 1.
[0100]
[Table 1]
[0101]
From the results of Table 1, it can be seen that the automobile part of the present invention has excellent mechanical properties, heat resistance, durability, dimensional stability, and texture.
[0102]
Moreover, about the waste paper paper powder (B-1 and B-2) used in the Example, it processed by 450 degreeC and 12 hours with the electric furnace, and calculated | required the ash content. Furthermore, the obtained ash was analyzed using a fluorescent X-ray apparatus. The analysis results are shown in Table 2.
[0103]
[Table 2]
[0104]
From the results shown in Tables 1 and 2, the automobile of the present invention was obtained by using paper powder containing aluminum, silicon, calcium, sulfur, and magnesium and having an aluminum content twice or more that of magnesium. It can be seen that the parts have excellent mechanical properties, heat resistance, durability, dimensional stability, and texture.
[0105]
Example 9
A board having a thickness of 4 mm was obtained using a single screw extruder in which the resin composition obtained in Example 3 was set to a cylinder temperature of 185 ° C and a die temperature of 190 ° C. After cutting the obtained board, cloth was pasted to create a trunk cover. The obtained trunk cover was used in a car for three months from June to August, but there was no particular problem.
[0106]
Example 10
A board having a thickness of 4 mm was obtained using a single screw extruder in which the resin composition obtained in Example 6 was set to a cylinder temperature of 185 ° C and a die temperature of 190 ° C. The obtained board was preheat-softened and then cold-press molded. At that time, a skin material lined with a polyolefin resin foam layer was simultaneously attached to the back surface of the vinyl chloride sheet to form a door trim. The obtained door trim was used in a car for one year, but there was no problem.
[0107]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, the resin-made automotive parts derived from a plant resource which have the outstanding mechanical characteristics, heat resistance, durability, dimensional stability, and texture are provided.

Claims (17)

  1. (A) An automobile part formed by molding a resin composition obtained by blending 1 to 350 parts by weight of (B) a natural-derived organic filler with respect to 100 parts by weight of a resin derived from plant resources.
  2. (A) The automotive component according to claim 1, wherein the resin derived from plant resources is a polylactic acid resin.
  3. (B) The automobile part according to claim 1 or 2, wherein the naturally-derived organic filler is at least one selected from paper powder or wood powder.
  4. The automobile part according to any one of claims 1 to 3, wherein (B) 50% by weight or more of the organic filler derived from nature is waste paper powder.
  5. 2. The resin composition is obtained by melting and kneading 0.01 to 10 parts by weight of (C) a carboxyl terminal reactive terminal blocker with respect to (A) 100 parts by weight of a plant resource-derived resin. The automobile part in any one of -4.
  6. The resin composition is obtained by further blending 0.01 to 30 parts by weight of (D) a crystallization accelerator with respect to 100 parts by weight of the resin derived from (A) plant resources. Or described auto parts.
  7. The resin composition comprises (A) 100 parts by weight of a plant resource-derived resin, and (E) 1 to 200 parts by weight of an aliphatic polyester resin and / or an aliphatic aromatic polyester resin other than the plant resource-derived resin. The automobile part according to any one of claims 1 to 6, which is blended.
  8. The resin composition is obtained by further blending 1 to 100 parts by weight of (F) an impact resistance improving agent with respect to (A) 100 parts by weight of a plant resource-derived resin. Auto parts as described.
  9. The resin composition is obtained by further blending 1 to 100 parts by weight of (G) inorganic filler with respect to (A) 100 parts by weight of resin derived from plant resources. Car parts.
  10. The resin derived from plant resources is a polylactic acid resin, the crystallization temperature at the time of temperature drop from the polylactic acid resin in the composition can be observed, and the crystallization enthalpy at the time of temperature drop from the polylactic acid resin is 35% of the crystal melting enthalpy The automobile part according to any one of claims 1 to 9, comprising a resin composition having the above values.
  11. The resin derived from plant resources is a polylactic acid resin, and the crystallization temperature at the time of temperature-fall derived from the polylactic acid resin in a composition is 110 degreeC or more, It consists of a resin composition characterized by the above-mentioned. Auto parts as described.
  12. The automobile part according to any one of claims 1 to 11, wherein the paper powder contains aluminum, silicon, and calcium.
  13. The automobile part according to any one of claims 1 to 12, wherein the paper powder contains aluminum, silicon, calcium, and sulfur.
  14. The automobile part according to claim 1, wherein the automobile part is an automobile interior part.
  15. The automobile part according to claim 1, wherein the automobile part is an automobile exterior part.
  16. The automobile part according to any one of claims 1 to 13, wherein the automobile part is an automobile underhood part.
  17. The automobile part according to any one of claims 1 to 13, wherein the automobile part is selected from a decorative panel for automobile interior, a trunk cover, a spare tire cover, and a door trim.
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JP2006213828A (en) * 2005-02-04 2006-08-17 Toray Ind Inc Polyester containing polylactic acid component segment and its manufacturing method
JP2006298949A (en) * 2005-04-15 2006-11-02 Toyo Ink Mfg Co Ltd Resin composition for lactic acid-based resin and its utilization
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JP4665540B2 (en) * 2005-02-04 2011-04-06 東レ株式会社 Polylactic acid component segment-containing polyester and method for producing the same
JP2006213828A (en) * 2005-02-04 2006-08-17 Toray Ind Inc Polyester containing polylactic acid component segment and its manufacturing method
JP2007204727A (en) * 2005-03-10 2007-08-16 Tohcello Co Ltd Polylactic acid composition and molded product composed of the composition
JP2006298949A (en) * 2005-04-15 2006-11-02 Toyo Ink Mfg Co Ltd Resin composition for lactic acid-based resin and its utilization
JP2007119730A (en) * 2005-09-30 2007-05-17 Toray Ind Inc Resin composition and molded article composed of the same
JP2007270391A (en) * 2006-03-31 2007-10-18 Toray Ind Inc Aliphatic polyester staple fiber
JP2009057494A (en) * 2007-08-31 2009-03-19 Toyota Boshoku Corp Method for producing thermoplastic resin composition and method for producing molded article
US8716373B2 (en) 2008-08-08 2014-05-06 Kao Corporation Biodegradable resin composition
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JP2010222491A (en) * 2009-03-24 2010-10-07 Nishikawa Rubber Co Ltd Polylactic acid resin composition
WO2010122761A1 (en) * 2009-04-20 2010-10-28 エヌ・ケイ・ケイ株式会社 Absorber for spray can and spray can product
JP2010249291A (en) * 2009-04-20 2010-11-04 Nkk Kk Absorber for spray can and spray can product
JP2013001719A (en) * 2011-06-13 2013-01-07 Osaka Gas Co Ltd Polylactic acid resin composition
WO2013141548A1 (en) * 2012-03-19 2013-09-26 주식회사 에스에이치글로벌 Plastic, for automotive interior parts, manufactured from biomass pellets, and method for manufacturing the plastic
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