JP2006137799A - Composite composition and molded article using the composite composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a composite composition having excellent heat resistance and practically sufficient storage stability, and biodegradable in the natural environment. <P>SOLUTION: The composite composition comprises at least one kind of organic polymer compound having biodegradability, a carbon fiber and a hydrolysis suppressant for the organic polymer compound having the biodegradability. A molded article is produced by using the composition. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a composite composition that is biodegradable in a natural environment and has practically sufficient heat resistance and durability for use.

  In recent years, a wide variety of synthetic resin materials have been developed and provided, and the amount used in various industrial fields is increasing year by year. As a result, the amount of synthetic resin waste also tends to increase, but when it is discarded, if it is incinerated as it is, harmful gases are generated or the incinerator is damaged by large combustion heat. Sometimes, the burden on the environment is a major issue.

Conventionally, as a method for treating a discarded resin, for example, a method of incineration or landfilling after making the waste resin low molecular by performing a treatment such as thermal decomposition or chemical decomposition is known.
However, incineration is accompanied by carbon dioxide emissions, which causes global warming.
If the resin contains sulfur, nitrogen, halogen, or the like, harmful gases are discharged by incineration and cause air pollution.
On the other hand, when the resin is reclaimed, most of the resins that are currently widely used are chemically very stable and remain without being decomposed for a long period of time, causing soil contamination.

In recent years, various biodegradable resins have been developed and put into practical use for the problem of the influence on the environment as described above (see, for example, Patent Document 1).
Biodegradable resins have the property of being biochemically decomposed into carbon dioxide and water by microorganisms, etc., and even when discarded to the natural environment, they are easily decomposed to lower their molecular weight. It turns into a harmless compound. Therefore, it has the feature that adverse effects on the global environment due to disposal can be reduced. For these reasons, biodegradable resins are being put to practical use in disposable products such as daily goods, sanitary goods, and play goods.

As described above, the biodegradable resin can be said to have an excellent effect in terms of conservation of the natural environment, but still has many problems to be solved from a practical viewpoint. .
For example, in industrial / civil engineering / fishery materials, machine parts, medical members, etc., it is required to have excellent heat resistance as a material characteristic, but conventionally known biodegradable resins are used as materials themselves. Since the heat resistance is relatively low, there has been a demand for improvement in this respect.

  Conventionally, mechanical properties such as tensile strength can be obtained by incorporating carbon fibers into a resin having biodegradable properties such as polylactic acid, or by examining the chemical structure of the resin. There has been a proposal regarding a technique of improving (see, for example, Patent Documents 2 and 3).

JP 2003-192925 A JP 2004-231910 A JP 2003-306599 A

  However, considering the use of biodegradable resins in various molded products such as electrical products and automobile interior materials that will become more sophisticated and precise in the future, in order to function practically, heat resistance In addition, it has been required to have improved storage stability, sufficient rigidity, and storage stability (use durability) that can withstand practical use while having biodegradability.

  For example, even when heat is generated from the drive source or when local heat is generated from a precise actuator, it is required not to be thermally deformed. When polylactic acid, which is an example, is applied, there is a problem that the storage elastic modulus significantly decreases in the temperature range exceeding the glass transition temperature (58 ° C) of polylactic acid. It is necessary to improve.

  For example, in a small audio product, considering practical usability, it is necessary to maintain physical properties such as strength at 30 ° C. and a relative humidity of 80% for at least 5 to 7 years. However, in the various technologies that have been proposed previously, sufficient storage characteristics have not been realized, and in the future, durability (in a constant temperature and humidity environment) to solve this problem It is necessary to improve durability.

  Therefore, in the present invention, it has excellent biodegradability, has very little influence on the natural environment at the time of disposal, has practically sufficient heat resistance and excellent mechanical strength, and is used for electronic equipment and automobile interior materials. Even when used in the above, a composite composition having sufficient durability, that is, storage characteristics was provided.

  In the present invention, a composite composition containing at least one organic polymer compound having biodegradability, carbon fiber, and a hydrolysis inhibitor of the organic polymer compound having biodegradability, and Provided is a molded product produced by using the product.

According to the present invention, by adding carbon fiber to the biodegradable resin, the heat resistance is improved, and a practically sufficient mechanical strength is maintained even in a temperature range higher than the glass transition temperature of the resin. Can now. Moreover, the storage durability was improved by adding a hydrolysis inhibitor.
The composite composition of the present invention is finally biodegraded into a harmless substance in the natural environment, and can effectively reduce the influence on the environment, and for example, a device having a heat source such as a drive source or a power source. Even when used as a casing, it was able to exhibit practically sufficient mechanical strength, heat resistance, and durability (storage characteristics).
That is, since the composite composition of the present invention has a ternary system of biodegradable resin, carbon fiber, and hydrolysis inhibitor, any of biodegradability, heat resistance, mechanical strength, and storage durability can be obtained. It has the characteristics that can be satisfied in practical use.

Hereinafter, specific embodiments of the present invention will be described, but the present invention is not limited to the following examples.
The composite composition of the present invention contains at least one organic polymer compound having biodegradability, carbon fiber, and a hydrolysis inhibitor.

First, a biodegradable organic polymer compound will be described.
A biodegradable organic polymer compound (hereinafter referred to as “biodegradable polymer compound”) is a low molecular weight compound that eventually decomposes into water and carbon dioxide with the participation of microorganisms in nature after use ( Biodegradable Plastics Research Society, ISO / TC-207 / SC3).
The biodegradable polymer compound is preferably a biodegradable resin, specifically, a biodegradable polysaccharide, peptide, aliphatic polyester, polyamino acid, polyvinyl alcohol, polyamide, polyalkylene glycol, or the like. And any one or a copolymer containing at least one of them.

In particular, aliphatic polyester is a practically preferable material because of its excellent mixing property and mass productivity.
As the aliphatic polyester, polylactic acid such as poly-L-lactic acid (PLLA), a random copolymer of L-lactic acid and D-lactic acid, or a derivative thereof is more preferable. Since polylactic acid is made of plant raw materials, it is a particularly preferable material from the viewpoint of environmental conservation, and has high strength and low price, and is also preferable from the viewpoint of cost reduction.
General polylactic acid is a crystalline polymer excellent in biodegradability having a melting point of about 160 to 170 ° C. and a glass transition temperature of about 58 ° C. According to the present invention, as described later, this temperature is higher than this temperature. The heat resistance can be improved, and the storage stability required as a durable consumer can also be ensured.
Besides these, for example, polycaprolactone, polyhydroxybutyric acid, polyhydroxyvaleric acid, polyethylene succinate, polybutylene succinate, polybutylene adipate, polymalic acid, polyglycolic acid, polysuccinic acid ester, polyoxalic acid ester, polydiglycolic acid Butylene, polydioxanone, microbial synthetic polyester, and the like can also be applied. Examples of the microbial synthetic polyester include 3-hydroxybutyrate (3HB), 3-hydroxyvalerate (3HV), and copolymers thereof.

The molecular weight (number average molecular weight) of the aliphatic polyester is preferably about 30,000 to 200,000.
When the molecular weight is less than 30000, the strength of the finally obtained composite composition becomes insufficient. On the other hand, when it exceeds 200000, the moldability and workability deteriorate.

Examples of the polysaccharide include cellulose, starch, chitin, chitosan, dextran, a derivative thereof, and a copolymer containing at least one of these.
Examples of the peptide include collagen, casein, fibrin, gelatin and the like.
Examples of the polyamide include nylon 4, nylon 2 / nylon 6 copolymer, and the like.

Moreover, when applying polysaccharide, in order to provide thermoplasticity, you may add various plasticizers.
Furthermore, organic polymer compounds that are biodegradable at low molecular weights but are not biodegradable at high molecular weights can also be biodegradable by graft copolymerization with biodegradable polymer compounds, etc. If so, it can be applied. For example, polyethylene, polyacrylic acid derivatives, polypropylene, polyurethane and the like can be mentioned.
Further, the molecular weights and end groups of these resins are not particularly limited as long as mechanical strength can be obtained by polymerization.

The biodegradable polymer compound can be produced by a known method.
For example, the biodegradable polyester is prepared by a method such as lactide method, polycondensation of polyhydric alcohol and polybasic acid, or intermolecular polycondensation of hydroxycarboxylic acid having a hydroxyl group and a carboxyl group in the molecule. Can do.

Next, the carbon fiber which comprises the composite composition of this invention is demonstrated.
As the carbon fibers, those produced by any known method, for example, a so-called organic bricker method such as a polyacrylonitrile method, a pitch method, a rayon method, or a quinol method, or a vapor phase growth method can be applied.

The fiber length and average fiber diameter of the carbon fiber are not particularly limited, but it is preferable to select the size in consideration of the dispersibility in the resin and the effect of improving the heat resistance of the resin.
In particular, the carbon fiber produced by the vapor phase growth method is excellent in dispersibility in the biodegradable polymer compound. Therefore, in order to improve the heat resistance which is the object of the present invention, the carbon fiber is excellent in a smaller addition amount. It has the advantage that the effect can be demonstrated. Further, the fiber diameter and fiber length of the carbon fiber are not limited as long as the dispersibility is not affected.

The mixing ratio (weight ratio) of the biodegradable polymer compound (for example, aliphatic polyester) and the filler that is the carbon fiber is aliphatic polyester / filler = 99.9 / 0.1 to 40/60. It is preferable that 99.5 / 0.5 to 50/50 is particularly preferable, and 99/1 to 60/40 is more preferable.
When the carbon fiber content is less than 0.1% by weight, a sufficient heat resistance improvement effect cannot be obtained. On the other hand, when the carbon fiber content exceeds 60% by weight, the strength of the composite composition finally obtained is reduced. This is to invite a problem as a typical material.

Furthermore, it is preferable to perform a chemical surface treatment in order to improve the affinity and dispersibility between the filler, which is the carbon fiber, and the biodegradable polymer compound.
Examples of the surface treatment method include acylation treatment such as acetylation and benzoylation, and silane coupling treatment.
By performing such a surface treatment, surface adhesion with the above-described biodegradable polymer compound, for example, aliphatic polyester is improved, and a reduction in strength due to interfacial peeling between the resin and the carbon fiber is suppressed.

Next, the hydrolysis inhibitor will be described.
The hydrolysis inhibitor is an additive that suppresses hydrolysis of the biodegradable polymer compound, and examples thereof include compounds having reactivity with active hydrogen of the biodegradable polymer compound. Thereby, the amount of active hydrogen in the biodegradable polymer compound is reduced, and it can be avoided that active hydrogen hydrolyzes the biodegradable polymer chain catalytically.

Note that active hydrogen is hydrogen in a bond (N—H bond or O—H bond) of oxygen, nitrogen, or the like with hydrogen, and such hydrogen is hydrogen in a bond of carbon and hydrogen (C—H bond). Reactivity is higher than Specific examples include hydrogen in a carboxyl group: —COOH, a hydroxyl group: —OH, an amino group: —NH ₂ , or an amide bond: —NHCO— in the biodegradable polymer compound.

  Examples of the compound reactive with active hydrogen in the biodegradable polymer compound include carbodiimide compounds, isocyanate compounds, and oxozoline compounds. In particular, the carbodiimide compound can be melt kneaded with the biodegradable polymer compound, and the effect of suppressing the hydrolyzability can be exhibited with a small amount of addition.

A carbodiimide compound is a compound having one or more carbodiimide groups in the molecule, and includes a polycarbodiimide compound.
Examples of the synthesis method of the carbodiimide compound include, as a catalyst, O, O-dimethyl-O- (3-methyl-4-nitrophenyl) phosphorothioate, O, O-dimethyl-O- (3-methyl-4- (methylthio). ) Phenyl) phosphorothioate, O, O-diethyl-O-2-isopropyl-6-methylpyrimidin-4-ylphosphorothioate and the like (◯ is any number), or a rhodium complex, a titanium complex, Using organometallic compounds such as tungsten complexes and palladium complexes, various polymer isocyanates are decarboxylated by polycondensation in a solvent-free or inert solvent (eg, hexane, benzene, dioxane, chloroform, etc.) at a temperature of about 70 ° C. or higher. The method of manufacturing is mentioned.

  Examples of monocarbodiimide compounds that are one type of carbodiimide compounds include dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, diphenylcarbodiimide, naphthylcarbodiimide, and the like, which are particularly easily industrially available dicyclohexylcarbodiimide and diisopropyl. Carbodiimide is preferred.

  Examples of the isocyanate compound include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 2, 2'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate , Trimethylhexamethylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexyl Examples include methane diisocyanate or 3,3′-dimethyl-4,4′-dicyclohexylmethane diisocyanate.

The said isocyanate compound can be synthesize | combined by a well-known method, and a commercial item can be used suitably.
As a commercially available polyisocyanate compound, an aromatic isocyanate adduct such as coronate (trade name: hydrogenated diphenylmethane diisocyanate manufactured by Nippon Polyurethane) or millionate (trade name: manufactured by Japan Polyurethane) can be used.
In particular, a solid material, for example, a polyisocyanate compound in which an isocyanate group is blocked with a mask agent (polyhydric aliphatic alcohol, aromatic polyol, etc.) is more preferable than a liquid.

  Examples of the oxazoline compound include 2,2′-o-phenylenebis (2-oxazoline), 2,2′-m-phenylenebis (2-oxazoline), 2,2′-p-phenylenebis (2- Oxazoline), 2,2'-p-phenylenebis (4-methyl-2-oxazoline), 2,2'-m-phenylenebis (4-methyl-2-oxazoline), 2,2'-p-phenylenebis (4,4′-dimethyl-2-oxazoline), 2,2′-m-phenylenebis (4,4′-dimethyl-2-oxazoline), 2,2′-ethylenebis (2-oxazoline), 2, 2'-tetramethylene bis (2-oxazoline), 2,2'-hexamethylene bis (2-oxazoline), 2,2'-octamethylene bis (2-oxazoline), 2,2'-ethylenebi (4-methyl-2-oxazoline), or 2,2'- diphenylenebis (2-oxazoline).

Since the biodegradation rate and mechanical strength of the finally obtained composite composition can be controlled by the types or addition amounts of the various hydrolysis inhibitors described above, the composite composition of the present invention is used for production. The type and blending amount are determined according to the type of the molded product.
Specifically, the addition amount of the hydrolysis inhibitor is preferably about 7% by weight or less.
Moreover, the hydrolysis inhibitor may use each compound mentioned above independently, and may use 2 or more types together.

It does not specifically limit as a method of manufacturing the composite composition of this invention, A well-known method is applicable.
For example, it can be produced by melt-kneading the above-described carbon fiber and hydrolysis inhibitor into a biodegradable organic polymer compound.
Specifically, carbon fiber and a hydrolysis inhibitor are added and mixed in the previous step of melting the organic polymer compound having biodegradability, or in the melting step.
The carbon fiber and the hydrolysis inhibitor may be added at the same time or may be added individually. When added individually, the order of addition may be arbitrary.
In addition, after melting the organic polymer compound having biodegradability, either carbon fiber or a hydrolysis inhibitor is added and mixed, and then the obtained composite composition is melted again to obtain a hydrolysis inhibitor or carbon. Any one of the fibers may be added and mixed.

The composite composition of the present invention includes flame retardants, lubricants, waxes, plasticizers, heat stabilizers, reinforcing materials, inorganic / organic fillers, colorants, antioxidants, UV absorbers, crystallization accelerators, and the like. Various additives may be added.
The content of the additive is not particularly limited, but is preferably 0.1 or more and less than 50% by weight. When the content is less than 0.1% by weight, the respective functions are hardly expressed. When the content exceeds 60% by weight, the intended physical properties (biodegradability, heat resistance, storage durability) of the composite composition of the present invention are inhibited. It is because there is a possibility of doing.

  Examples of the flame retardant include various boric acid flame retardant compounds, phosphorus flame retardant compounds, inorganic flame retardant compounds, nitrogen flame retardant compounds, halogen flame retardant compounds, organic flame retardant compounds, colloid flame retardants. Compounds and the like. Specific materials are shown below, but these may be used alone or in combination of two or more.

  Examples of the boric acid flame retardant compound include compounds such as zinc borate hydrate, barium metaborate, and borax.

  Examples of phosphorus-based flame retardant compounds include ammonium phosphate, ammonium polyphosphate, melamine phosphate, red phosphorus, phosphate ester, tris (chloroethyl) phosphate, tris (monochloropropyl) phosphate, tris (dichloropropyl) phosphate, tri Allyl phosphate, tris (3-hydroxypropyl) phosphate, tris (tribromophenyl) phosphate, tris-β-chloropropyl phosphate, tris (dibromophenyl) phosphate, tris (tribromoneopentyl) phosphate, tetrakis (2-chloroethyl) ) Ethylene diphosphate, dimethylmethyl phosphate, tris (2-chloroethyl) orthophosphate, aromatic condensed phosphate, halogen-containing condensed organophosphate , Ethylene bis tris (2-cyanoethyl) phosphonium bromide, ammonium polyphosphate, β-chloroethyl acid phosphate, butyl pyrophosphate, butyl acid phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid Examples thereof include compounds such as dophosphate, melamine phosphate, halogen-containing phosphonate, and phenylphosphonic acid.

  Examples of inorganic flame retardant compounds include zinc sulfate, potassium hydrogen sulfate, aluminum sulfate, antimony sulfate, sulfate ester, potassium sulfate, cobalt sulfate, sodium hydrogen sulfate, iron sulfate, copper sulfate, sodium sulfate, nickel sulfate, and barium sulfate. , Metal sulfate compounds such as magnesium sulfate, ammonium flame retardant compounds such as ammonium sulfate, iron oxide combustion catalysts such as ferrocene, metal nitrate compounds such as copper nitrate, titanium-containing compounds such as titanium oxide, guanidine sulfamate, etc. Examples thereof include guanidine compounds, zirconium compounds, molybdenum compounds, tin compounds, carbonate compounds such as potassium carbonate, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, and modified products thereof.

  Examples of the nitrogen flame retardant compound include a cyanurate compound having a triazine ring.

  Examples of halogen-based flame retardant compounds include chlorinated paraffin, perchlorocyclopentadecane, hexabromobenzene, decabromodiphenyl oxide, bis (tribromophenoxy) ethane, ethylene bis-dibromonorbornane dicarboximide, and ethylene bis-tetrabromo. Phthalimide, dibromoethyl dibromocyclohexane, dibromoneopentyl glycol, 2,4,6-tribromophenol, tribromophenyl allyl ether, tetrabromo bisphenol A derivative, tetrabromo bisphenol S derivative, tetradecabromo diphenoxybenzene, tris -(2,3-dibromopropyl) -isocyanurate, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy) Loxyethoxy-3,5-dibromophenyl) propane, poly (pentabromobenzyl acrylate), tribromostyrene, tribromophenyl maleide, tribromoneopentyl alcohol, tetrabromodipentaerythritol, pentabromobenzyl acrylate, pentabromo Phenol, pentabromotoluene, pentabromodiphenyl oxide, hexabromocyclododecane, hexabromodiphenyl ether, octabromophenol ether, octadibromodiphenyl ether, octabromodiphenyl oxide, magnesium hydroxide, dibromoneopentyl glycol tetracarbonate, bis (tribromo Phenyl) fumaramide, N-methylhexabromodiphenylamine, styrene bromide, or di Flame retardant compounds containing halogens such as Lil chlorendate the like.

  Examples of the organic flame retardant compound include chlorendic anhydride, phthalic anhydride, bisphenol A-containing compounds, glycidyl compounds such as glycidyl ether, polyhydric alcohols such as diethylene glycol and pentaerythritol, modified carbamide, silicone oil, or dioxide. Silica-based compounds such as silicon, low-melting glass, and organosiloxane are listed.

  Examples of colloidal flame retardant compounds include conventionally known hydroxides such as aluminum hydroxide, magnesium hydroxide, and calcium hydroxide having flame retardancy, calcium aluminate, dihydrate gypsum, zinc borate, and metaboric acid. Hydrates such as barium, borax and kaolin clay, nitric acid compounds such as sodium nitrate, colloids of flame retardant compounds such as molybdenum compounds, zirconium compounds, antimony compounds, dawsonite, and progopite.

The flame retardant additive is preferably one that does not give a load to the environment during disposal, for example, generation of toxic gas during incineration.
From the viewpoint of environmental consideration, flame retardant additives include hydroxide compounds such as aluminum hydroxide, magnesium hydroxide, or calcium hydroxide, phosphorus compounds such as those mentioned above, particularly ammonium phosphate. Or, an ammonium phosphate compound such as ammonium polyphosphate, a silica compound such as silicon dioxide, low-melting glass, or organosiloxane is preferable.

As the silica compound of the flame retardant additive, those having a silicon dioxide content of about 50% or more are suitable. Since silica-based compounds are collected from naturally derived minerals, substances other than silica-based compounds (for example, MgO, CaO, Fe ₂ O ₃ , Al ₂ O _3, etc.) are contained to some extent, but are difficult. It is desirable that the fuel effect is not hindered by impurities.

As the hydroxide compound of the flame retardant additive, those having a purity of about 99.5% or more are suitable. This is because the higher the purity, the better the storage stability when combined with the hydrolysis control agent described later.
The purity of the hydroxide compound can be measured by a known method. For example, the purity of the hydroxide compound can be obtained by measuring the content of impurities contained in the hydroxide compound by a known method and subtracting the content of impurities from the total amount. Specifically, for example, in the case of aluminum hydroxide, the impurities include Fe ₂ O ₃ , SiO ₂ , T-Na ₂ O, S-Na ₂ O and the like. The content of Fe ₂ O ₃ is obtained by melting in a sodium carbonate-boric acid solution and then by O-phenanthroline spectrophotometry (JIS H 1901). The content of SiO ₂ is obtained by melting in sodium carbonate-boric acid solution and then by the molybdenum blue absorptiometry (JIS H 1901).
The content of T-Na ₂ O is determined by flame photometry after melting in sulfuric acid, and S-Na ₂ O is determined by flame photometry after extraction with hot water. The purity of the hydroxide can be obtained by reducing the content determined as described above from the weight of aluminum hydroxide. Of course, as long as the purity is 99.5% or more, a plurality of different flame retardant hydroxide compounds can be used in combination.

The shape of the flame retardant additive described above is not particularly limited, but is preferably granular. The particle size is appropriately selected according to the type.
For example, when the flame retardant additive is a silica compound such as SiO ₂ or glass, it is preferable that the average particle size obtained by the laser diffraction method is about 50 μm or less. In this case, the particle size distribution is not particularly limited.
Further, when the flame retardant additive is a hydroxide compound such as Al (OH) ₃ , Mg (OH) ₂ , Ca (OH) ₂ , the average particle size determined by the laser diffraction method is about 100 μm or less. It is preferable that In this case, the particle size distribution is not particularly limited.

Considering the injection moldability in the molding process and the dispersibility during kneading when producing a molded article using the composite composition of the present invention, the average particle size of the flame retardant additive should be in the above range. Among these ranges, a numerically smaller value is more preferable.
In order to improve the filling rate of the composition, a plurality of flame retardant additives having different average particle diameters may be used in combination.

Further, when the flame retardant additive is a hydroxide compound such as Al (OH) ₃ , Mg (OH) ₂ , Ca (OH) _{2, the} BET specific surface area determined by the nitrogen gas adsorption method is about Particles of 5.0 m ² / g or less are preferred.
In order to improve the filling rate of the composition, a plurality of flame retardant hydroxylated compounds having different BET specific surface areas may be used in combination.
In consideration of moldability, the BET specific surface area is preferably about 5.0 m ² / g or less, and particularly preferably smaller.

The addition amount of the flame retardant additive is arbitrarily determined within a range in which the mechanical strength of the composite composition of the present invention can be secured.
Specifically, when the flame retardant additive is a hydroxide compound such as Al (OH) ₃ , Mg (OH) ₂ , Ca (OH) ₂ , about 5 to 50% by weight, The amount is preferably about 7.5 to 45% by weight, more preferably about 10 to 40% by weight.
When the flame retardant additive is a (poly) ammonium phosphate compound such as (NH ₄ ) ₃ (PhO _{3n + 1} ) _{n + 2} (n is a natural number), about 1 to 25% by weight, preferably About 2 to 20% by weight, more preferably about 3 to 15% by weight is desirable.
When the flame retardant additive is a silica-based compound such as SiO ₂ or glass, it is about 5 to 40% by weight, preferably about 10 to 35% by weight, and further about 15 to 30% by weight. It is desirable.

Examples of reinforcing materials include glass microbeads, fibers such as plant fibers and glass fibers, quartz such as chalk and novoculite, asbestos, feldspar, mica, silicates such as talc and wollastonite, kaolin and the like. Can be mentioned.
Examples of inorganic fillers include carbon, silicon dioxide, metal oxide fine particles such as alumina, silica, magnesia, or ferrite, silicates such as talc, mica, kaolin, and zeolite, barium sulfate, calcium carbonate, silicon nitride, and carbonized. Examples thereof include silicides such as silicon, borides such as boron carbide and boron nitride, and fine particles such as fullerene.
Examples of the organic filler include epoxy resin, melamine resin, urea resin, acrylic resin, phenol resin, polyimide resin, polyamide resin, polyester resin, and Teflon (registered trademark) resin.
In particular, carbon, silicon dioxide, and silicide are suitable. The various fillers mentioned above may be used alone or in combination of two or more.

  Examples of the antioxidant include phenol-based, amine-based, phosphorus-based, sulfur-based, hydroquinone-based, and quinoline-based antioxidants.

  Phenol antioxidants include hindered phenols such as 2,6-di-t-butyl-p-cresol, 1,3,5-trimethyl-2,4,6-tris (3,5-di- -T-butyl-4-hydroxybenzyl) benzene, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4,4'-methylenebis (2,6-di-t-butylphenol), 4, C2-10 such as 4'-butylidenebis (3-methyl-6-tert-butylphenol), 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] Alkylene diol-bis [3- (3,5-di-branched C3-6 alkyl-4-hydroxyphenyl) propionate], for example triethylene glycol-bis [3- (3-t-butyl) Di- or trioxy C2-4 alkylenediol-bis [3- (3,5-di-branched C3-6 alkyl-4-hydroxyphenyl) propionate] such as -5-methyl-4-hydroxyphenyl) propionate], for example glycerin C 3-8 alkanetriol-bis [3- (3,5-di-branched C 3-6 alkyl-4-hydroxy) such as tris [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] Phenyl) propionate], for example C4-8 alkanetetraol tetrakis [3- (3,5-di-branched) such as pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]. C3-6 alkyl-4-hydroxyphenyl) propionate], for example n-octadecyl-3- (4 ′, 5′-di-t Butylphenol) propionate, n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-t-butylphenol) propionate, stearyl-2- (3,5-di-t-butyl-4-hydroxyphenol) Propionate, distearyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, 2-t-butyl-6- (3-t-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenyl Acrylate, N, N′-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocymamide), 3,9-bis {2- [3- (3-tert-butyl-4 -Hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] un Kang, 4,4'-thiobis (3-methyl -6-t-butylphenol), or 1,1,3-tris (2-methyl-4-hydroxy -5-t-butylphenol) butane and the like.

  Examples of amine-based antioxidants include phenyl-1-naphthylamine, phenyl-2-naphthylamine, N, N′-diphenyl-1,4-phenylenediamine, or N-phenyl-N′-cyclohexyl-1,4- Examples include phenylenediamine.

  Examples of phosphorus antioxidants include triisodecyl phosphite, triphenyl phosphite, trisnonylphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, 2,2-methylenebis (4,6-di-). t-butylphenyl) octyl phosphite, 4,4′-butylidenebis (3-methyl-6-tert-butylphenyl) ditridecyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris ( 2-t-butyl-4-methylphenyl) phosphite, tris (2,4-di-t-amylphenyl) phosphite, tris (2-t-butylphenyl) phosphite, bis (2-t-butylphenyl) ) Phenyl phosphite, tris [2- (1,1-dimethylpropyl) -pheny ] Phosphite, tris [2,4- (1,1-dimethylpropyl) -phenyl] phosphite, tris (2-cyclohexylphenyl) phosphite, tris (2-t-butyl-4-phenylphenyl) phosphite, etc. Phosphite compounds; triethylphosphine, tripropylphosphine, tributylphosphine, tricyclohexylphosphine, diphenylvinylphosphine, allyldiphenylphosphine, triphenylphosphine, methylphenyl-p-anisylphosphine, p-anisyldiphenylphosphine, p-tolyl Diphenylphosphine, di-p-anisylphenylphosphine, di-p-tolylphenylphosphine, tri-m-aminophenylphosphine, tri-2,4-dimethylphenylphosphine, tri-2,4, -Trimethylphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tri-o-anisylphosphine, tri-p-anisylphosphine, or 1,4-bis (diphenyl) And phosphine compounds such as phosphino) butane.

Examples of the hydroquinone antioxidant include 2,5-di-t-butylhydroquinone.
Examples of the quinoline antioxidant include 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline.
Examples of the sulfur-based antioxidant include dilauryl thiodipropionate, distearyl thiodipropionate, and the like.

Among the above antioxidants, phenolic antioxidants (particularly hindered phenols) such as polyol-poly [(branched C 3-6 alkyl group and hydroxy group-substituted phenyl) propionate] are particularly suitable.
The antioxidant mentioned above may be used independently and may use 2 or more types together.

Examples of the heat stabilizer include nitrogen-containing compounds such as polyamides, poly-β-alanine copolymers, polyacrylamides, polyurethanes, melamines, cyanoguanidines, basic nitrogen-containing compounds such as melamine-formaldehyde condensates, and organic carboxylic acid metals. Salt (calcium stearate, calcium 12-hydroxystearate, etc.), metal oxide (magnesium oxide, calcium oxide, aluminum oxide, etc.), metal hydroxide (magnesium hydroxide, calcium hydroxide, aluminum hydroxide, etc.), metal carbonate And alkaline earth metal-containing compounds, zeolite, hydrotalcite, and the like.
In particular, alkali or alkaline earth metal-containing compounds (especially alkaline earth metal-containing compounds such as magnesium compounds and calcium compounds), zeolite, hydrotalcite and the like are suitable.
The heat stabilizer mentioned above may be used independently and may use 2 or more types together.

Examples of the ultraviolet absorber include conventionally known benzophenone-based, benzotriazole-based, cyanoacrylate-based, salicylate-based, oxalic acid anilide-based, and the like.
Specifically, [2-hydroxy-4- (methacryloyloxyethoxy) benzophenone] -methyl methacrylate copolymer, [2-hydroxy-4- (methacryloyloxymethoxy) benzophenone] -methyl methacrylate copolymer, [ 2-hydroxy-4- (methacryloyloxyoctoxy) benzophenone] -methyl methacrylate copolymer, [2-hydroxy-4- (methacryloyloxidedecyloxy) benzophenone] -methyl methacrylate copolymer, [2-hydroxy- 4- (methacryloyloxybenzyloxy) benzophenone] -methyl methacrylate copolymer, [2,2′-dihydroxy-4- (methacryloyloxyethoxy) benzophenone] -methyl methacrylate copolymer, [2,2′-dihydroxy -4- (methacryl Yl oxy) benzophenone] - methyl methacrylate copolymer, or 2,2'-dihydroxy-4- (methacryloyloxy-octoxybenzophenone) - methyl methacrylate copolymer, and the like.
The ultraviolet absorber mentioned above may be used independently and may use 2 or more types together.

Examples of lubricants include petroleum-based lubricating oils such as liquid paraffin, halogenated hydrocarbons, diester oils, silicone oils, synthetic silicone oils such as fluorine silicon, and various modified silicone oils (epoxy-modified, amino-modified, alkyl-modified, Ether-modified, etc.), silicon-based lubricants such as polyoxyalkylene glycol and silicon copolymers, various fluorosurfactants such as silicon copolymers and fluoroalkyl compounds, trifluoromethylene chloride low Examples thereof include fluorine-based lubricating substances such as polymers, waxes such as paraffin wax and polyethylene wax, higher aliphatic alcohols, higher aliphatic amides, higher fatty acid esters, higher fatty acid salts, and molybdenum disulfide.
In particular, a silicon copolymer (a resin obtained by polymerizing silicon with a block or graft) is preferable.
Silicon copolymers include acrylic resins, polystyrene resins, polynitrile resins, polyamide resins, polyolefin resins, epoxy resins, polybutyral resins, melamine resins, vinyl chloride resins, polyurethane resins or polyvinyl resins. Any ether-based resin or the like obtained by blocking or graft polymerization of silicon may be used, and a silicon graft copolymer is preferably used.
The above-described lubricants may be used alone or in combination of two or more.

Examples of the waxes include olefin waxes such as polypropylene wax and polyethylene wax, paraffin wax, Fischer-Tropsch wax, microcrystalline wax, montan wax, fatty acid amide wax, higher aliphatic alcohol wax, higher fatty acid wax, Fatty acid ester wax, carnauba wax, rice wax and the like can be applied.
The waxes described above may be used alone or in combination of two or more.

Examples of the colorant include inorganic pigments, organic pigments, and dyes.
Examples of inorganic pigments include chromium pigments, cadmium pigments, iron pigments, cobalt pigments, ultramarine blue, and bitumen.
Specific examples of organic pigments and dyes include carbon black, phthalocyanine pigments such as phthalocyanine copper, quinacridone pigments such as quinacridone magenta and quinacridone red, azo such as hansa yellow, disazo yellow, permanent yellow, permanent red, and naphthol red. Pigment, Spirit Black SB, Nigrosine Base, Nigrosine Dye such as Oil Black BW, Oil Blue, Pigment Yellow, Pigment Blue, Pigment Red, Alkali Blue and the like.
The above-mentioned colorants may be used alone or in combination of two or more.

As crystallization accelerators, organic acid salts such as sodium pt-butylbenzoate, sodium montanate, calcium montanate, sodium palmitate, calcium stearate, calcium carbonate, calcium silicate, magnesium silicate, calcium sulfate, barium sulfate And inorganic salts such as talc, and metal oxides such as zinc oxide, magnesium oxide and titanium oxide.
The above-described crystallization accelerators may be used alone or in combination of two or more.

The composite composition of the present invention may be subjected to various conventionally known treatments.
For example, active energy rays may be irradiated in order to suppress hydrolysis of the biodegradable polymer compound. In this case, examples of the active energy ray source include an electromagnetic wave, an electron beam, a particle beam, and a combination thereof.
Examples of the electromagnetic wave include ultraviolet rays (UV) and X-rays, and examples of the particle beam include rays of elementary particles such as protons and neutrons. In particular, it is desirable to perform an electron beam irradiation process using an electron accelerator.
The active energy ray can be irradiated using a known apparatus. For example, a UV irradiation apparatus, an electron accelerator, etc. are mentioned. The irradiation dose and irradiation intensity are not particularly limited as long as the hydrolysis of the biodegradable polymer compound is effectively delayed in the composite composition of the present invention. For example, in the case of an electron beam, the acceleration voltage is preferably about 100 to 5000 kV, and the irradiation dose is preferably about 1 kGy or more.

The composite composition of the present invention can be applied to various molded product applications.
For example, a DVD ((Digital Versatile Disc or Digital VideoDisk)) player, a CD (compact disc) player, a stationary AV device such as an amplifier, a speaker, an in-vehicle AV / IT device, a mobile phone terminal, a PDA such as an electronic book, VCR, TV, projector, TV receiver, digital video camera, digital still camera, printer, radio, radio cassette player, system stereo, microphone, headphones, TV, keyboard, headphone stereo, etc. The present invention can be applied to any molded product such as a casing of an electric product such as a device.

  In addition, it is applicable not only to the housing | casing of an electric product but to uses, such as components and a packaging material which comprise an electric product, and it can apply also to an automotive interior material etc.

Examples of the method for producing a molded article using the composite composition of the present invention include pressure forming, film forming, extrusion molding, injection molding and the like, and injection molding is particularly preferable.
Specifically, the extrusion molding can be performed according to a conventional method using a known extrusion molding machine such as a single-screw extruder, a multi-screw extruder, a tandem extruder, or the like.
The injection molding can be performed according to a conventional method using a known injection molding machine such as an inline screw type injection molding machine, a multilayer injection molding machine, or a two-head injection molding machine.

Hereinafter, samples of molded articles produced using the composite composition according to the present invention were produced, and characteristics were evaluated.
In addition, this invention is not limited to the example shown below.

[Examples 1 to 5], [Comparative Examples 1 to 3]
(Sample preparation)
(A) Biodegradable resin: polylactic acid (Lacia (H100J, manufactured by Mitsui Chemicals))
(B) Carbon fiber: Vapor grown carbon fiber Showa Denko product name VGCF (fiber length: 10-20 μm, average fiber diameter: 150 nm)
Showa Denko product name VGCF-H (fiber length: 10-20 μm, average fiber diameter: 150 nm)
(C) Hydrolysis inhibitor As shown in Table 1 below, the above (A) to (C) were mixed by the melt-kneading method in the amounts described in the table.
As a kneading machine, a minimax-mix ruder (manufactured by Toyo Seiki Co., Ltd.) is used. A kneading process was performed.
The composite composition obtained by the above process was pulverized and pressed at 180 ° C. at 400 kg / cm ² to produce a plate-shaped molded product having a thickness of 1.0 mm. Thereafter, the molded article of the composite composition was allowed to stand for 1 hour in an environment of 120 ° C. to prepare a sample.

  As shown below, a heat resistance test (viscoelasticity test under a high temperature condition) and a storage stability test were performed on a molded product sample of the composite composition produced as described above.

[Heat resistance test (viscoelasticity test under high temperature conditions)]
Measuring apparatus: Rheometric viscoelasticity analyzer Sample piece: Composite composition having the composition shown in Table 1 above (length 50 mm × width 7 mm × thickness 1 mm)
Frequency: 6.28 (rad / s)
Measurement start temperature: 0 ° C
Final measurement temperature: 160 ° C
Temperature increase rate: 5 ° C / min Strain: 0.05%

[Preservation test]
The storage stability test was performed by measuring the change in the molecular weight of the prepared composite composition.
Using the molecular weight of each sample as the initial molecular weight, the sample is stored in a constant temperature and humidity chamber at 80 ° C. and a relative humidity of 80% for 100 hours, and the molecular weight of the sample measured thereafter is defined as the molecular weight after storage.
The value obtained by dividing the molecular weight after storage by the initial molecular weight is defined as the molecular weight retention rate. When this molecular weight retention rate exceeds 90%, the practical storage stability is good (◯), and the molecular weight retention rate is 90 % Or less, the practical storage stability was judged to be insufficient (x), and the results are shown in Table 2 below.
In addition, the measuring method of molecular weight is shown below.
Molecular weight is a weight average molecular weight (polystyrene conversion molecular weight), and is measured using gel permeation chromatography (GPC).
Device: MILLIPORE Waters600E system controller
Detector: UV (Waters484) and RI (Waters410)
Standard sample: polystyrene Operation: The sample was dissolved in chloroform so that the concentration was 0.15% by weight, stirred for 2 hours, and then this solution was passed through a filter of φ0.25 μm as an evaluation sample of the above apparatus.

[Evaluation of heat resistance test (viscoelasticity test under high temperature conditions)]
Fig. 1 shows examples 1 and 2 using Showa Denko product name VGCF as carbon fiber, and each sample of Comparative Example 1, and Fig. 2 shows Showa Denko product name VGCF-H as carbon fiber. Each viscoelasticity test result of each sample of Examples 3 to 5 and Comparative Example 1 is shown, and the evaluation is shown in Table 2 below.
As shown in FIGS. 1 and 2, in the samples of Examples 1 to 5 which are composite compositions containing carbon fibers, than the glass transition temperature (about 58 ° C.) of the biodegradable resin (polylactic acid). Even in a high temperature range, practically excellent strength was maintained, and it was confirmed that a significant heat resistance improvement effect was obtained as compared with the sample of Comparative Example 1 containing no carbon fiber.

[Evaluation of preservation test]
Table 2 below shows the evaluation results of the storage stability tests of the samples of Examples 1 to 7 and Comparative Examples 1 to 3.

  As shown in Table 2 above, the samples of Examples 1 to 5 according to the present invention can realize extremely good storage characteristics in a constant temperature and humidity environment by including a hydrolysis inhibitor, and the present invention. According to the above, it was confirmed that a molded product having practically sufficient stability can be obtained. On the other hand, in the samples of Comparative Examples 2 and 3 that did not contain a hydrolysis inhibitor, practically sufficient stability could not be obtained.

  As is clear from the results described above, according to the composite composition of the present invention, biodegradability is achieved by including carbon fiber and a hydrolysis inhibitor in the organic polymer compound having biodegradability. Even if it is used for a device that has heat resistance and storability, such as an electronic device casing, etc. that generates heat by an internal power source or drive source, it is practically sufficient for storage. Stability was realized.

  That is, the composite composition of the present invention has high heat resistance and stability, can be used for various practical molded products, and, when discarded, is finally a component that is safe to living bodies and the global environment, for example, Water and carbon dioxide are also decomposed, and the material has very little impact on the environment. By using this for molded products such as casings and packaging materials for various electrical products, environmental pollution caused by disposal is reduced. I was able to.

The viscoelasticity test result of an Example and a comparative example sample is shown. The viscoelasticity test result of an Example and a comparative example sample is shown.

Claims (5)

  A composite composition comprising at least one kind of organic polymer compound having biodegradability, carbon fiber, and a hydrolysis inhibitor of the organic polymer compound having biodegradability.   The organic polymer compound having biodegradability is at least one of polysaccharides, aliphatic polyesters, polyamino acids, polyvinyl alcohol, and polyalkylene glycols, or a copolymer containing at least one of these. The composite composition according to claim 1.   The aliphatic polyester is at least one of polylactic acid, polycaprolactone, polyhydroxybutyric acid, polyhydroxyvaleric acid, polyethylene succinate, polybutylene succinate, polybutylene adipate, polymalic acid, microbial synthetic polyester, or The composition according to claim 3, which is a copolymer containing at least any one of these.   The composite composition according to claim 1, wherein the hydrolysis inhibitor is at least one of a carbodiimide compound, an isocyanate compound, and an oxozoline compound. It is produced by using a composite composition containing at least one kind of biodegradable organic polymer compound, carbon fiber, and a hydrolysis inhibitor of the biodegradable organic polymer compound. Molded product.

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