WO2011152371A1 - Thermoplastic resin composition and molded products thereof - Google Patents
Thermoplastic resin composition and molded products thereof Download PDFInfo
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- WO2011152371A1 WO2011152371A1 PCT/JP2011/062432 JP2011062432W WO2011152371A1 WO 2011152371 A1 WO2011152371 A1 WO 2011152371A1 JP 2011062432 W JP2011062432 W JP 2011062432W WO 2011152371 A1 WO2011152371 A1 WO 2011152371A1
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- flame retardant
- thermoplastic resin
- resin composition
- polylactic acid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
Definitions
- the present invention is a thermoplastic resin composition having excellent flame retardancy, impact resistance, and heat resistance and capable of being used in various versatile products, while using polylactic acid that is less dependent on petroleum products.
- the present invention relates to a molded body obtained by molding a product.
- biomass raw material resins such as polylactic acid have attracted attention from the viewpoint of environmental conservation.
- Polylactic acid is inexpensive because it can be mass-produced, and since it has high heat resistance among biomass-derived resins, its use in various fields including automobile parts and machine parts is being studied.
- polylactic acid has a problem that it has low flame retardancy and easily burns, and has a drawback that the impact resistance is low and the product is easily cracked by impact.
- flame retardancy is evaluated based on the US UL standard subject 94 (hereinafter abbreviated as UL94), and is preferably V-1 or higher.
- V-1 flame retardancy is achieved by adding a fluorine compound to a resin composition comprising polylactic acid, polycarbonate, styrene compatibilizer, monocarbodiimide, polyvalent carbodiimide, and a flame retardant.
- a fluorine compound is added, a toxic gas is generated during molding or incineration.
- Patent Document 2 describes a resin composition that is made of polylactic acid and an aromatic polyester and has flame retardancy by having a flame retardant.
- Patent Document 2 shows that this resin composition can be used for automobile parts, electrical / electronic parts and the like, and that flame retardancy of V-1 and V-0 can be achieved.
- the resin composition described in Patent Document 2 uses an aromatic polyester, and therefore has an impact resistance performance. It was low and did not have sufficient performance. Further, polylactic acid itself was not modified, and the heat resistance performance was not sufficiently satisfactory.
- the present invention solves the above-mentioned problems, and is excellent in flame retardancy without using a fluorine-based compound, can achieve at least the performance of V-1, and has excellent impact resistance and heat resistance.
- a thermoplastic resin composition that can be suitably used for automobile parts and electrical / electronic parts that are excellent in harsh usage environments and that are also environmentally friendly, and a molded body formed by molding the same. is there.
- the present inventor has used an amorphous thermoplastic resin having a bisphenol group as a resin component together with polylactic acid, an acrylic compatibilizer, and a specific flame retardant. It was found that a resin composition having good flame retardancy and excellent impact resistance and heat resistance can be obtained by using two types in combination, and the present invention has been achieved.
- the gist of the present invention is as follows. (1) A resin composition containing polylactic acid (A), an amorphous thermoplastic resin (B) having a bisphenol group, an acrylic compatibilizer (C) and a flame retardant (D),
- the content of the polylactic acid (A) is 25 to 60% by mass
- the content of the amorphous thermoplastic resin (B) having a bisphenol group is 30 to 60% by mass
- the content of the acrylic compatibilizer (C) Is 0.5 to 20% by mass
- the content of the flame retardant (D) is 5 to 30% by mass
- the flame retardant (D) is a phosphate ester flame retardant (D-1) and a phosphinic acid metal salt type.
- a flame retardant (D-2), and a mass ratio of the phosphate ester flame retardant (D-1) and the phosphinic acid metal salt flame retardant (D-2) [(D-1) / (D-2) ] Is a thermoplastic resin composition, characterized in that it is 10/90 to 50/50.
- the amorphous thermoplastic resin (B) having a bisphenol group is a polycarbonate resin (B-1) and / or a polyarylate resin (B-2) (1) to (3) The thermoplastic resin composition according to any one of the above.
- the phosphate ester flame retardant (D-1) is an aromatic condensed phosphate ester
- the phosphinic acid metal salt flame retardant (D-2) is an aluminum phosphinate ( 1)
- the aromatic carbodiimide compound (E) is an aromatic monocarbodiimide (E-1) and an aromatic polyvalent carbodiimide (E-2), and the aromatic monocarbodiimide (E-1) and the aromatic polyvalent polyvalent
- the thermoplastic resin composition of the present invention contains a non-crystalline thermoplastic resin having a bisphenol group, which is excellent in flame retardancy and impact resistance, and polylactic acid. Improved low flame resistance and low impact resistance, and excellent in flame retardancy and impact resistance. And since the thermoplastic resin composition of the present invention contains an acrylic compatibilizing agent as a compatibilizing agent, the compatibility between the polylactic acid and the amorphous thermoplastic resin having a bisphenol group is greatly improved, The high flame resistance and impact resistance of the amorphous thermoplastic resin having a bisphenol group are sufficiently exhibited. Further, since a specific flame retardant is used in combination as a flame retardant, further excellent flame retardancy is imparted, and the resin composition can have flame retardancy of V-1 and V-0 levels.
- the heat resistance of polylactic acid can be improved by using a polylactic acid having a D-form content that satisfies a specific range or using a cross-linked structure. And it becomes possible to improve the heat resistance of resin composition itself, and also to improve a flame retardance. Moreover, it becomes possible to improve the heat-and-moisture resistance of a resin composition by containing an aromatic carbodiimide compound.
- the thermoplastic resin composition of the present invention is remarkably excellent in flame retardancy, impact resistance, heat resistance, and further heat and moisture resistance, and uses a natural product-derived resin. The dependence on the products is low and the global environment is taken into consideration. And the thermoplastic resin composition of this invention can be made into various molded objects by injection molding etc. Since the molded article of the present invention is formed by molding the resin composition of the present invention as described above, it is suitable for various applications such as various machine parts, electrical / electronic parts, building members, automobile parts, daily necessities, etc. Can be used for
- thermoplastic resin composition of the present invention [hereinafter sometimes abbreviated as composition (X). ] Contains polylactic acid (A), an amorphous thermoplastic resin (B) having a bisphenol group, an acrylic compatibilizer (C), and a flame retardant (D).
- polylactic acid (A) refers to poly (L-lactic acid), poly (D-lactic acid), a mixture or a copolymer thereof.
- Polylactic acid has high heat resistance among aliphatic polyesters, but in order to further improve heat resistance, the D-form content of polylactic acid is 1.0 mol% or less, or 99.0. It is preferably at least mol%. Among them, the D-form content is preferably 0.1 to 0.6 mol% or 99.4 to 99.9 mol%.
- the polylactic acid (A) having a D-form content satisfying the above range has excellent crystallinity, thereby improving heat resistance and crystallization speed, thereby shortening the molding cycle and excellent moldability. It will be a thing.
- the D-form content of polylactic acid (A) refers to the proportion (mol%) occupied by D lactic acid units in the total lactic acid units constituting polylactic acid (A). Therefore, for example, in the case of polylactic acid having a D-form content of 1.0 mol%, this polylactic acid has a ratio of D lactic acid units of 1.0 mol% and a ratio of L lactic acid units of 99.0. Mol%.
- the D-form content of polylactic acid (A) is such that L lactic acid and D lactic acid obtained by decomposing polylactic acid (A) are all methyl esterified, and methyl ester of L lactic acid and methyl ester of D lactic acid are obtained. Is calculated by a method of analyzing with a gas chromatography analyzer.
- polylactic acid (A) satisfying such specific D-form content commercially available products can be used.
- lactide which is a cyclic dimer of lactic acid
- L-lactide having a sufficiently low D-form content or D-lactide having a sufficiently low L-form content is used as a raw material by a known melt polymerization method.
- those produced by further using a solid phase polymerization method can be used.
- polylactic acid (A) As a form of crosslinking, polylactic acid molecules may be directly crosslinked, indirectly crosslinked via a crosslinking aid, or may be a mixture of direct crosslinking and indirect crosslinking. By introducing the crosslinked structure, the heat resistance of the polylactic acid (A) is improved.
- a method for introducing a crosslinked structure into polylactic acid (A) there are known methods such as a method of irradiating an electron beam, a method of using a polyfunctional compound such as a polyvalent isocyanate compound, and a method of using a peroxide. Can be mentioned. In view of crosslinking efficiency, a method using a peroxide is preferred.
- Peroxides include benzoyl peroxide, bis (butylperoxy) trimethylcyclohexane, bis (butylperoxy) cyclododecane, butylbis (butylperoxy) valerate, dicumyl peroxide, butylperoxybenzoate, dibutyl peroxide, Examples thereof include bis (butylperoxy) diisopropylbenzene, dimethyldi (butylperoxy) hexane, dimethyldi (butylperoxy) hexyne, and butylperoxycumene.
- the amount of the peroxide used is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polylactic acid (A). Although it can be used even if it exceeds 10 parts by mass, the effect is saturated and it is not economical. In addition, since a peroxide decomposes
- the content thereof is preferably 1 to 50 parts by mass, and more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the peroxide. Although it can be used even if it exceeds 50 parts by mass, the effect is saturated and it is not economical.
- the (meth) acrylic acid ester compound includes a compound having two or more (meth) acrylic groups in the molecule, or one or more (meth) acrylic groups and one or more glycidyl groups or vinyl groups. preferable. These compounds have high reactivity with the biodegradable resin, the monomer hardly remains, and the resin is less colored.
- Specific examples of the (meth) acrylic acid ester compound include, for example, glycidyl (meth) acrylate, glycerol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, allyloxy polyethylene glycol mono (meth) acrylate, and polyethylene.
- Examples include glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, or a copolymer of alkylene glycol in which these alkylene glycol portions have different alkylene groups.
- Examples of the method for causing polylactic acid (A) to undergo a crosslinking reaction using a peroxide and a crosslinking aid include a method of melt-kneading using a general extruder.
- the peroxide and / or the crosslinking aid may be dissolved or dispersed in the medium in advance.
- a solution or dispersion of a crosslinking aid may be injected while melting and kneading polylactic acid (A) and a peroxide, and a crosslinking aid and a peroxide may be injected while melting and kneading polylactic acid (A).
- An oxide solution or dispersion may be injected and melt kneaded.
- the medium for dissolving or dispersing the peroxide and / or crosslinking aid is not particularly limited, but a plasticizer excellent in compatibility with the resin composition of the present invention is preferable.
- the plasticizer include aliphatic polyvalent carboxylic acid ester derivatives, aliphatic polyhydric alcohol ester derivatives, aliphatic oxyester derivatives, aliphatic polyether derivatives, aliphatic polyether polyvalent carboxylic acid ester derivatives, and the like. .
- plasticizer compounds include glycerin diacetomonolaurate, glycerin diacetomonocaprate, polyglycerin acetate, polyglycerin fatty acid ester, fatty acid triglyceride, dimethyl adipate, dibutyl adipate, triethylene glycol diacetate, acetylricinoleic acid Examples include methyl, acetyltributyl citrate, polyethylene glycol, dibutyl diglycol succinate, bis (butyl diglycol) adipate, and bis (methyl diglycol) adipate.
- the polylactic acid (A) is more preferably a polylactic acid having a D-form content of 1.0 mol% or less, or 99.0 mol% or more and having a crosslinked structure introduced therein. .
- the heat resistance of polylactic acid (A) is improved, and further the composition (X) Heat resistance is improved.
- the heat distortion temperature of the composition (X) is set to 110 ° C. or higher by using polylactic acid (A) having a specific D-form content or having a crosslinked structure introduced. Is possible.
- the heat distortion temperature is 110 ° C. or higher, fields and applications in which the obtained molded body can be used are widened, and can be used for various automobile parts, electric / electronic parts, and the like.
- the composition (X) using such polylactic acid (A) (X) ) Is formed at a high temperature, or heat treatment is performed after the forming, whereby the crystallinity of the obtained formed body can be further improved.
- the composition (X) of this invention when using the specific flame retardant (D) mentioned later and using polylactic acid (A) which was excellent in such crystallinity, the molded object obtained will be, The crystallinity is improved and the flame retardancy is also improved.
- the two specific flame retardants (D-1) and (D-) contained in the composition (X) are changed. It is assumed that the function of 2) is activated and works in a direction in which the flame retardant performance is sufficiently exhibited. That is, in the present invention, the poly (lactic acid) (A) having a specific D-form content or having a cross-linked structure introduced makes it difficult for the composition (X) to have improved heat resistance. The flammability is also improved.
- the polylactic acid (A) preferably has a melt flow rate (hereinafter abbreviated as MFR) measured by the measurement method described later in the range of 0.1 to 50 g / 10 minutes, preferably 0.2 to 20 g / 10 minutes. Is more preferably 0.5 to 15 g / 10 min. If the MFR exceeds 50 g / 10 min, the melt viscosity is too low and the mechanical properties and heat resistance of the molded product may be inferior. On the other hand, if the MFR is less than 0.1 g / 10 minutes, the load during the molding process is increased, and the operability is lowered.
- MFR melt flow rate
- the content of polylactic acid (A) in the composition (X) needs to be 25 to 60% by mass, and preferably 30 to 50% by mass.
- the content of the polylactic acid (A) is less than 25% by mass, the ratio of using the resin of the biomass raw material in the composition (X) is small, and the merit in the environment is small.
- the content exceeds 60% by mass, the proportion of the amorphous thermoplastic resin (B) having a bisphenol group decreases, so that the composition (X) is inferior in impact resistance and flame retardancy. become.
- amorphous thermoplastic resin refers to a thermoplastic resin whose melting point is not observed by the melting point measurement method described below.
- Measurement method of melting point Using a DSC (Differential Scanning Calorimetry) device (Pyrisl DSC manufactured by PerkinElmer), the temperature was raised from ⁇ 100 ° C. to 300 ° C. at 20 ° C./min, then to ⁇ 100 ° C. at 50 ° C./min, Subsequently, the temperature is raised from ⁇ 100 ° C. to 300 ° C. at a rate of 20 ° C./min. The melting peak in the second temperature raising process is defined as the melting point.
- Amorphous thermoplastic resin (B) having a bisphenol group [hereinafter abbreviated as amorphous thermoplastic resin (B). ]
- amorphous thermoplastic resin (B) From the point of being excellent in impact resistance and flame retardancy, polycarbonate resin (B1), polyarylate resin (B2), resin (B3) containing both polycarbonate resin (B1) and polyarylate resin (B2) Is preferred.
- the polycarbonate resin (B1) will be described.
- the polycarbonate resin (B1) refers to a resin composed of bisphenol residues and carbonate residues.
- bisphenols examples include 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as bisphenol A), 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (hereinafter referred to as “bisphenol A”).
- bisphenol TMC Abbreviated as bisphenol TMC
- 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane
- 1,1 -Bis (4-hydroxyphenyl) cyclohexane 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane
- 1,1-bis (4-hydroxyphenyl) decane 1,3-bis (4- Hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclododecane
- 4,4'-dihydroxydiph Vinyl ether 4,4'-dithio-diphenol, 4,4'-dihydroxy-3,3'-dichloro-diphenyl ether, 4,4'-dihydroxy-2,5-dihydroxydiphenyl ether, and the like.
- bisphenol A and bisphenol TMC are preferable from the viewpoint of versatility. These may be used alone or in combination of two
- Polycarbonate resin (B1) can be produced by a known method. For example, a method of reacting bisphenols and phosgene or reacting bisphenols and diphenyl carbonate can be mentioned.
- the intrinsic viscosity of the polycarbonate resin (B1) is preferably in the range of 0.35 to 0.64.
- the intrinsic viscosity of the polycarbonate resin (B1) is less than 0.35, the impact strength of the obtained molded product may be insufficient.
- the intrinsic viscosity exceeds 0.64, the melt viscosity of the resin composition becomes high, and kneading extrusion and injection molding may be difficult.
- the polyarylate resin (B2) will be described.
- the polyarylate resin (B2) is a resin composed of an aromatic dicarboxylic acid residue and a bisphenol residue.
- Bisphenols include bisphenol A, bisphenol TMC, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, , 2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl Examples include ketones, 4,4'-dihydroxydiphenylmethane, 1,1-bis (4-hydroxyphenyl) cyclohexane and the like. These may be used alone or in combination of two or more. Among these, the combined use of bisphenol A and bisphenol TMC is preferable.
- aromatic dicarboxylic acid examples include terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, 4,4′-dicarboxyphenyl, and the like.
- terephthalic acid and isophthalic acid are preferable from the viewpoint of melt processability and mechanical properties, and the combined use of both is more preferable.
- the molar ratio of the two is not particularly limited, but is preferably in the range of 90/10 to 10/90, more preferably in the range of 70/30 to 30/70.
- 50/50 is more preferable.
- the degree of polymerization can be sufficiently increased when interfacial polymerization is performed.
- the production method of the polyarylate resin (B2) is not particularly limited, and examples thereof include an interfacial polymerization method and a melt polymerization method.
- the intrinsic viscosity of the polyarylate resin (B2) is preferably 0.35 to 0.65.
- the intrinsic viscosity of the polyarylate resin (B2) is less than 0.35, the impact strength of the obtained molded product may be insufficient.
- the intrinsic viscosity exceeds 0.65, the melt viscosity becomes high and injection molding may be difficult.
- the resin (B3) containing both the polycarbonate resin (B1) and the polyarylate resin (B2) will be described.
- the resin (B3) containing both the polycarbonate resin (B1) and the polyarylate resin (B2) a resin obtained by mixing the polycarbonate resin (B1) and the polyarylate resin (B2), the polycarbonate resin (B1), and the polyarylate resin It contains a resin copolymerized with (B2).
- the resin obtained by mixing the polycarbonate resin (B1) and the polyarylate resin (B2) may be a simple blend of chips or powders of the polycarbonate resin (B1) and the polyarylate resin (B2).
- a mixed resin prepared by melt-kneading the polycarbonate resin (B1) and the polyarylate resin (B2) is preferable.
- the content ratio [(B1) / (B2)] of the polycarbonate resin (B1) and the polyarylate resin (B2) is preferably in the range of 70/30 to 30/70 (mass ratio) from the viewpoint of heat resistance and fluidity. .
- the intrinsic viscosity of the resin (B3) containing both is preferably 0.55 or less from the viewpoint of compatibility, mechanical properties and heat resistance, and preferably 0.35 or more from the viewpoint of impact strength.
- the content of the amorphous thermoplastic resin (B) in the composition (X) needs to be 30 to 60% by mass, and preferably 35 to 50% by mass.
- the content of the amorphous thermoplastic resin (B) is less than 30% by mass, the composition (X) is inferior in impact resistance and flame retardancy.
- the content of the amorphous thermoplastic resin (B) exceeds 60% by mass, the ratio of the polylactic acid (A) decreases, so that the environmental advantage is reduced.
- the acrylic compatibilizer (C) will be described.
- the compatibility between the polylactic acid (A) and the amorphous thermoplastic resin (B) is remarkably improved by containing the acrylic compatibilizing agent (C). And by improving compatibility, the impact resistance, strength, etc. of the composition (X) are improved. Furthermore, by improving the compatibility, the flame retardant performance of the amorphous thermoplastic resin (B) having a higher flame retardant performance than the polylactic acid (A) is exhibited to the maximum. For this reason, the flame retardancy of the composition (X) is greatly improved in comparison with the case of using a compatibilizer that is not an acrylic compatibilizer, in combination with the effect of improving the flame retardancy by adding a specific flame retardant. Improve.
- Acrylic compatibilizers (C) include (meth) acrylic copolymers, copolymers of styrene monomers and (meth) acrylic monomers, rubber-reinforced acrylic compounds, core-shell acrylic compounds, acrylic olefins Examples thereof include acrylic compounds having an epoxy group. Among them, an acrylic compound having an epoxy group is preferable because compatibility can be remarkably improved.
- the (meth) acrylic copolymer is obtained by polymerizing a (meth) acrylic monomer alone or by copolymerizing two or more (meth) acrylic monomers.
- alkyl groups including cycloalkyl groups
- alkyl groups such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and isobornyl methacrylate have 1 carbon atom.
- the copolymer of a styrene monomer and a (meth) acrylic monomer is obtained by copolymerizing a styrene monomer and a monomer constituting the (meth) acrylic copolymer.
- Styrene monomers include styrene, ⁇ -methyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, vinyl xylene, ethyl styrene, dimethyl styrene, p-tert-butyl styrene, vinyl naphthalene, methoxy styrene, Examples thereof include styrene derivatives of monobromostyrene, dibromostyrene, fluorostyrene, and tribromostyrene. Of these, styrene, ⁇ -methylstyrene and the like are preferable. These may be used
- the rubber-reinforced acrylic compound is obtained by copolymerizing a (meth) acrylic monomer in the presence of a rubbery polymer, or by copolymerizing two or more kinds of monomers.
- rubber-like polymers include polybutadiene, polyisoprene, butadiene / styrene copolymers, isoprene / styrene copolymers, butadiene / acrylonitrile copolymers, butadiene / isoprene / styrene copolymers, diene rubbers such as polychloroprene, Ethylene / propylene copolymers, ethylene / propylene / nonconjugated diene copolymers, ethylene / propylene rubbers such as ethylene / butene / nonconjugated diene copolymers, acrylic rubbers such as polybutyl acrylate, polyorganosiloxane rubber
- the core-shell type acrylic compound is composed of a layer having a rubber layer as an inner layer and a (meth) acrylic resin as an outer layer.
- the core (inner layer) is composed of rubber obtained by polymerizing an acrylic component, a silicone component, a styrene component, a nitrile component, a conjugated diene component, a urethane component or an ethylene propylene component, and the shell (outer layer)
- the thing comprised from a methyl methacrylate polymer etc. is mentioned.
- Examples of commercially available products include METABRENE manufactured by Mitsubishi Rayon, Kaneace manufactured by Kaneka Chemical Co., Ltd., Paraloid manufactured by Kureha Chemical Co., Ltd., Acryloid manufactured by Rohm and Haas Co., Ltd., Staphyloid manufactured by Takeda Pharmaceutical Co., Ltd., and Parapet SA manufactured by Kuraray Co., Ltd. These may be used alone or in combination of two or more.
- the acrylic olefin compound is a modified olefin compound obtained by graft copolymerization of a (meth) acrylic acid ester polymer.
- a (meth) acrylic acid ester polymer As a commercial item, Nippon Oil & Fats Modiper etc. are mentioned.
- An acrylic compound having an epoxy group is a compound having at least one epoxy group and one acrylic group in the molecule.
- copolymers of (meth) acrylic acid ester monomers having an epoxy group copolymers of (meth) acrylic acid ester monomers having an epoxy group and (meth) acrylic acid ester monomers, (meth) having an epoxy group A copolymer of an acrylate monomer and a styrene monomer, a compound obtained by graft copolymerization of a (meth) acrylate polymer having an epoxy group to a styrene copolymer, and a (meth) acrylate polymer is ethylene / glycidyl A compound copolymerized with a methacrylate copolymer, or a core (inner layer) composed of a rubber obtained by polymerizing an acrylic component, a silicone component, a styrene component, a nitrile component, a conjugated diene component, a
- the shell has an epoxy group Those such as core-shell structure composed of methyl methacrylate copolymer, and the like.
- Examples of commercially available products include ARUFON UG-4000 series manufactured by Toagosei Co., Ltd., RESEDA manufactured by Toagosei Co., Ltd., Modiper A4200 manufactured by Nippon Oil & Fats Co., Ltd., and Metabrene S-2200 manufactured by Mitsubishi Rayon Co., Ltd.
- the content of the acrylic compatibilizer (C) in the composition (X) needs to be 0.5 to 20% by mass, and preferably 3 to 10% by mass.
- the content of the acrylic compatibilizer (C) is less than 0.5% by mass, the polylactic acid (A) and the amorphous thermoplastic resin (B) cannot be sufficiently compatibilized. And it becomes difficult to produce the effect which arises by making it compatibilize, ie, an impact resistance, intensity
- content exceeds 20 mass% the problem that the heat resistance and flame retardance of composition (X) fall will arise.
- the flame retardant (D) will be described.
- the combustion phenomenon of a polymer material is continued by generating combustion gas by combustion and further burning the combustion gas.
- a flame retardant it is preferable to select a flame retardant according to the resin.
- phosphate ester flame retardant (D-1) for amorphous thermoplastic resin (B) Each is particularly effective as a flame retardant.
- the flame retardance of the resulting composition (X) can be dramatically improved.
- D-1 and D-2 a phosphate ester flame retardant (D-1) and a phosphinic acid metal salt flame retardant (D-2) in combination
- D the flame retardant
- a composition containing specific amounts of polylactic acid (A), amorphous thermoplastic resin (B), and acrylic compatibilizer (C) as described above, these two types of flame retardants are used in a specific ratio.
- the flame retardancy can be dramatically improved. Therefore, the composition (X) of the present invention can achieve flame retardancy at the V-1 level or V-0 level without adding other additives such as a fluorine-based compound.
- Examples of the phosphate ester flame retardant (D-1) include trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl 2,6-xylenyl phosphate
- Examples include phosphoric acid esters, condensed phosphoric acid esters, and aromatic condensed phosphoric acid esters. Of these, condensed phosphates are preferable, and aromatic condensed phosphates are more preferable.
- phosphate ester flame retardant examples include TMP, TEP, TPP, TCP, TXP, CDP, PX-110, etc. manufactured by Daihachi Chemical Industry Co., Ltd.
- phosphate esters examples include PX-200, PX-201, PX-202, CR-733S, CR-741, and CR-747 manufactured by Daihachi Chemical Co., Ltd.
- Examples of the phosphinic acid metal salt flame retardant (D-2) include calcium phosphinate, magnesium phosphinate, zinc phosphinate, aluminum phosphinate, and aluminum phosphinate is preferable.
- Commercially available phosphinic acid metal salts include Clariant's OP series (OP930, OP935, OP1230, OP1312, OP1240, etc.).
- the phosphinic acid metal salt-based flame retardant (D-2) has improved flame retardancy as the average particle size is smaller.
- the average particle diameter of the phosphinic acid metal salt flame retardant (D-2) is preferably 15 ⁇ m or less, more preferably 10 ⁇ m or less, and further preferably 2 to 5 ⁇ m.
- the average particle diameter of the phosphinic acid metal salt is measured using a laser diffraction / scattering particle size distribution analyzer LA-910 (manufactured by Horiba, Ltd.).
- the content of the flame retardant (D) in the composition (X) needs to be 5 to 30% by mass, and preferably 10 to 25% by mass.
- the content of the flame retardant (D) in the present invention means the total amount of the phosphate ester flame retardant (D-1) and the phosphinic acid metal salt flame retardant (D-2).
- the content of the flame retardant (D) is less than 5% by mass, sufficient flame retardancy cannot be imparted.
- content of a flame retardant (D) exceeds 30 mass%, the impact resistance and heat resistance of the composition (X) obtained will fall.
- the mass ratio of the phosphate ester flame retardant (D-1) and the phosphinic acid metal salt flame retardant (D-2) added to the composition (X) [(D-1) / (D-2) ] Needs to be 10/90 to 50/50, more preferably 20/80 to 40/60. That is, by using both of the phosphate ester flame retardant (D-1) and the phosphinic acid metal salt flame retardant (D-2) and using a specific mass ratio, the resulting composition (X) has difficulty. The flammability is dramatically improved. And it can suppress that the heat resistance of composition (X) falls by adding a flame retardant.
- composition (X) of the present invention it is preferable to further contain an aromatic carbodiimide compound (E). Since polylactic acid (A) has high hygroscopicity and is easily hydrolyzed, the composition (X) containing polylactic acid (A) tends to have low heat and moisture resistance. However, by containing the aromatic carbodiimide compound (E), the heat and humidity resistance can be improved without reducing the flame retardancy of the composition (X), and the versatility and practicality of the composition (X). Can be increased. In addition, when an aliphatic or alicyclic carbodiimide compound is contained as the carbodiimide compound, the heat and humidity resistance can be improved, but the flame retardancy is lowered, which is not preferable.
- an aromatic carbodiimide compound (E) Since polylactic acid (A) has high hygroscopicity and is easily hydrolyzed, the composition (X) containing polylactic acid (A) tends to have low heat and moisture resistance. However, by containing the aromatic carbodiimide compound
- the aromatic carbodiimide compound (E) refers to a compound produced by a reaction between a compound having a carbodiimide group represented by (—N ⁇ C ⁇ N—) and an aromatic compound.
- a compound having one carbodiimide group in the molecule is referred to as an aromatic monocarbodiimide compound (E-1), and a compound having two or more carbodiimide groups in the molecule is referred to as an aromatic polyvalent carbodiimide compound (E-2).
- an aromatic monocarbodiimide (E-1) and an aromatic polyvalent carbodiimide (E-2) in combination as the aromatic carbodiimide compound (E).
- the wet heat resistance of the composition (X) obtained can be improved compared with the case where each is used independently. The reason is not clear, but can be estimated as follows.
- the aromatic monocarbodiimide compound (E-1) has a low molecular weight and is easy to move, so that it has excellent dispersibility and quickly reacts with the carboxylic acid end of the polylactic acid molecule, thus blocking the end of the polylactic acid molecule and suppressing hydrolysis.
- the aromatic polyvalent carbodiimide compound (E-2) reacts with a carboxylic acid terminal newly generated by hydrolysis of polylactic acid to increase the molecular weight by chain extension, and suppresses a decrease in molecular weight. It is presumed that the two effects are combined to drastically improve the heat and humidity resistance of the composition (X).
- the mass ratio [(E-1) / (E-2)] of the aromatic monocarbodiimide compound (E-1) and the aromatic polyvalent carbodiimide compound (E-2) is in the range of 10/90 to 90/10. Preferably, it is more preferably in the range of 30/70 to 70/30. By making the mass ratio of the aromatic monocarbodiimide and the aromatic polyvalent carbodiimide within this range, extremely excellent moisture and heat resistance can be obtained.
- aromatic monocarbodiimide compound examples include N, N′-di-p-chlorophenylcarbodiimide, N, N′-di-o-chlorophenylcarbodiimide, N, N′-di-3,4-dichlorophenylcarbodiimide, N, N'-di-2,5-dichlorophenylcarbodiimide, p-phenylene-bis-o-toluylcarbodiimide, p-phenylene-bis-dicyclohexylcarbodiimide, p-phenylene-bis-di-p-chlorophenylcarbodiimide, Ethylene-bis-diphenylcarbodiimide, N, N'-diphenylcarbodiimide, N, N'-di-2,6-dimethylphenylcarbodiimide, N, N'-di-2,6-diisopropylphenylcarbodiimide
- Aromatic polyvalent carbodiimide compounds include poly (4,4'-diphenylmethanecarbodiimide), poly (3,3'-dimethyl-4,4'-diphenylmethanecarbodiimide), poly (naphthylenecarbodiimide), and poly (p-phenylene).
- Carbodiimide poly (m-phenylenecarbodiimide), poly (methyl-diisopropylphenylenecarbodiimide), poly (triethylphenylenecarbodiimide), poly (triisopropylphenylenecarbodiimide), poly (1,3,5-triisopropylbenzene) carbodiimide, poly (1,5-diisopropylbenzene) carbodiimide, poly (4,4'-methylenebiscyclohexylcarbodiimide).
- poly (4,4′-methylenebiscyclohexylcarbodiimide), poly (1,3,5-triisopropylbenzene) carbodiimide, and poly (1,5-diisopropylbenzene) carbodiimide are preferable.
- the content of the aromatic carbodiimide compound (E) in the composition (X) is preferably 0.1 to 5% by mass, and more preferably 0.5 to 4% by mass.
- content of the aromatic carbodiimide compound (E) is less than 0.1% by mass, the moisture and heat resistance is hardly improved. On the other hand, if the content exceeds 5% by mass, the heat resistance may decrease, which is not preferable.
- content in a composition (X) shall be the total amount of all the aromatic carbodiimide compounds.
- the composition (X) of the present invention can be obtained by adding V-1 or V-0 without adding a fluorine-based compound which is essential for improving flame retardancy in Patent Document 1 described in the Background Art section. A level of flame retardancy can be achieved.
- the composition (X) of the present invention preferably has a fluorine atom content of 0.1 ppm or less. When the content of fluorine atoms exceeds 0.1 ppm, there is a problem of generation of harmful gases during molding or incineration, which is not preferable.
- the composition (X) of the present invention may contain a biodegradable resin other than polylactic acid (A) as long as the effect is not impaired.
- biodegradable resins include, for example, poly (ethylene succinate), poly (butylene succinate), poly (butylene succinate-co-butylene adipate) and other aliphatic polyesters composed of diol and dicarboxylic acid, polyglycol Acid, poly (3-hydroxybutyric acid), poly (3-hydroxyvaleric acid), poly (3-hydroxycaproic acid) and other polyhydroxycarboxylic acids, poly ( ⁇ -caprolactone) and poly ( ⁇ -valerolactone) Poly ( ⁇ -hydroxyalkanoate), poly (butylene succinate-co-butylene terephthalate), poly (butylene adipate-co-butylene terephthalate), polyester amide, polyester And polysaccharides such as carbonate and starch . These may be used alone or in combination of two or more.
- the heat stabilizer, the antioxidant, the weathering agent, the light-proofing agent, the pigment, the plasticizer, the lubricant, the mold release agent, and the antistatic are within the range not greatly impairing the characteristics.
- An agent, a filler, a crystal nucleating agent and the like may be contained.
- heat stabilizers and antioxidants include hindered phenols, phosphorus compounds, hindered amines, sulfur compounds, copper compounds, alkali metal halides, vitamin E, and the like.
- filler for the purpose of improving mechanical strength and heat resistance, it is preferable to use a fibrous reinforcing material such as glass fiber, metal fiber, or carbon fiber, and it is preferable to use glass fiber or the like.
- fillers other than fibrous reinforcement talc, calcium carbonate, zinc carbonate, wollastonite, silica, alumina, magnesium oxide, calcium silicate, sodium aluminate, calcium aluminate, sodium aluminosilicate, magnesium silicate, glass Balloon, carbon black, zinc oxide, antimony trioxide, zeolite, hydrotalcite, metal whisker, ceramic whisker, potassium titanate, boron nitride, graphite and other inorganic fillers, starch, cellulose fine particles, wood powder, okara, fir Organic fillers such as naturally occurring polymers such as shells and bras.
- composition (X) of the present invention As a method for producing the composition (X) of the present invention, there is a method in which polylactic acid (A), amorphous thermoplastic resin (B), acrylic compatibilizer (C), and flame retardant (D) are melt-kneaded. Can be mentioned. Any of the method of mixing these simultaneously and the method of mixing in order may be sufficient. Even when the aromatic carbodiimide compound (E) is contained, it may be added simultaneously with the polylactic acid (A), the amorphous thermoplastic resin (B), the acrylic compatibilizer (C), and the flame retardant (D). The polylactic acid (A), the amorphous thermoplastic resin (B), the acrylic compatibilizing agent (C), and the flame retardant (D) are first melt-kneaded and then added and kneaded later. Good.
- the composition (X) of the present invention can be formed into various molded bodies by a molding method such as injection molding, blow molding, extrusion molding, inflation molding, and vacuum molding, pressure molding, and vacuum / pressure molding after sheet processing. .
- the composition (X) of the present invention is particularly suitable for an injection molding method, and can be used for gas injection molding, injection press molding and the like in addition to general injection molding.
- the injection molding conditions are appropriately selected according to the type and content ratio of the thermoplastic resin, but the cylinder temperature is preferably 180 to 260 ° C, more preferably 190 to 250 ° C.
- the mold temperature is preferably 100 ° C. or lower, more preferably 80 ° C. or lower in consideration of operability.
- the mold temperature is preferably relatively high, and 80 to 120 ° C. is particularly preferable. If the molding temperature (mold temperature) is too low, a part of the molded body is lost, and a problem of forming an incompletely molded body tends to occur. On the other hand, when the molding temperature is too high, the composition (X) is likely to be decomposed, and there may be a problem that the strength of the resulting molded product is reduced or colored.
- the molded product of the present invention is formed by molding the composition (X) of the present invention. And what was made into various molded objects by shaping
- the molded body of the present invention include injection molded products, extrusion molded products, blow molded products, films, fibers, and sheets.
- an injection molded product can be thinned. Since these molded products have excellent performance in flame retardancy, heat resistance, and impact resistance, they can be used in various applications such as electrical / electronic parts, machine parts, optical equipment, building members, automobile parts, and daily necessities. In particular, it can be suitably used as a casing for electronic devices (cases for notebook computers, projectors, copying machines, printers, etc.).
- Evaluation item (1) MFR According to JIS standard K-7210 (Test condition 4), the measurement was performed at 190 ° C. and a load of 21.2 N.
- (3) Intrinsic viscosity The intrinsic viscosity was measured under the conditions of a concentration of 1 g / dl and a temperature of 25 ° C. using 1,1,2,2-tetrachloroethane as a measurement solvent.
- Heat resistance heat distortion temperature
- ISO standards 75-1 and 2 the heat distortion temperature was measured with a load of 0.45 MPa using the obtained test piece.
- Impact strength Charpy impact strength
- 179-1eA Charpy impact strength was measured using the obtained test piece (with a V-shaped notch).
- Bending strength According to ISO standard 178, bending strength was measured at a deformation rate of 1 mm / min using the obtained test piece.
- Flame Retardancy According to the UL94 vertical combustion test method, the obtained test piece (thickness, approximately 1.6 mm) was used to perform a combustion test to evaluate flame retardancy.
- the flame retardancy is preferably V-1 or V-0 for practical use.
- thermoplastic resin having bisphenol group> (B-1) Polycarbonate resin / PC 200-13 manufactured by Sumitomo Dow, intrinsic viscosity 0.49 (B-2) Polyarylate resin, PAR Unita, Powder L, intrinsic viscosity 0.54
- ⁇ (C) Acrylic compatibilizer> (Acrylic compatibilizer having an epoxy group) ⁇ EA-1 Metablene S-2200 manufactured by Mitsubishi Rayon Co., Ltd. ⁇ EA-2 ARUFON UG-40 manufactured by Toa Gosei Co., Ltd. ⁇ EA-3 Modiper A4200 manufactured by NOF Corporation (Acrylic compatibilizer without epoxy group) ⁇ A-1 Metablene C-223A manufactured by Mitsubishi Rayon Co., Ltd. ⁇ A-2 Acrypet VH-001 (polymethyl methacrylate resin) manufactured by Mitsubishi Rayon Co., Ltd. ⁇ Styrene compatibilizer> ⁇ S-TPE Tough Tech H1041 (Styrene-ethylene / butylene-styrene block copolymer) manufactured by Asahi Kasei Chemicals
- Example 1 Using a twin screw extruder (TEM-37BS manufactured by Toshiba Machine Co., Ltd.), 30 parts by mass of PLA-1 as polylactic acid (A) and 41 parts by mass of PC as amorphous thermoplastic resin (B) are used as the top feeder. 7 parts by weight of EA-1 as an acrylic compatibilizer (C), 5 parts by weight of FR-1 as a phosphate ester flame retardant (D-1), and a phosphinic acid metal salt flame retardant (D-2) ) 15 parts by weight of FR-4, 1 part by weight of HMCD as aromatic monocarbodiimide (E-1), and 1 part by weight of HPCD as aromatic polycarbodiimide (E-2), and melt-kneaded at 230 ° C.
- EA-1 an acrylic compatibilizer
- D-1 phosphate ester flame retardant
- D-2 a phosphinic acid metal salt flame retardant
- composition (X) was dried with a hot air dryer at 80 ° C. for 5 hours, and then molded with an injection molding machine (IS-80G type manufactured by Toshiba Machine), which was suitable for various performance evaluations. A size specimen was obtained. When obtaining any of the test pieces, it is melted at a cylinder set temperature (injection temperature) of 220 ° C., and filled in a mold of 80 ° C. (mold temperature) at an injection pressure of 100 MPa and an injection time of 15 seconds, for 30 seconds. After holding, it was taken out.
- injection temperature injection temperature
- mold temperature 80 ° C.
- Examples 2 to 41, Comparative Examples 1 to 25 Various test pieces were prepared in the same manner as in Example 1 except that the types and amounts of the components constituting the composition (X) and the production conditions (melt kneading temperature, injection temperature) were changed as shown in Tables 1 to 3. Got.
- Tables 1 to 3 show the compositions and characteristic values of the compositions (X) obtained in the examples and comparative examples.
- compositions (X) obtained in Examples 1 to 41 are excellent in flame retardancy, impact resistance, and heat resistance, and use polylactic acid derived from natural products. The dependence on the environment was low and the global environment was taken into consideration.
- polylactic acid (A) contains a specific D form. Since it was a large amount or a crosslinked structure was introduced, it was excellent in heat resistance (heat deformation temperature) and flame retardancy.
- the compositions (X) obtained in Examples 18 to 19 and 37 to 38 are excellent in flame retardancy because the phosphinic acid metal salt flame retardant (D-2) has a small average particle size. It became a thing.
- compositions (X) obtained in Examples 1 to 24 and 27 to 39 contained the aromatic carbodiimide compound (E), they were excellent in heat and heat resistance. Among them, since the compositions (X) obtained in Examples 1 to 23 and 27 to 39 used both the aromatic monocarbodiimide (E-1) and the aromatic polyvalent carbodiimide (E-2), was significantly better.
- the composition (X) obtained in Comparative Examples 1 to 2 and 24 has a polylactic acid (A) content larger than the amount specified in the present invention, and an amorphous thermoplastic resin ( Since the content of B) was less than the amount specified in the present invention, the effects of the amorphous thermoplastic resin (B) were not sufficiently exhibited, and the flame retardancy, heat resistance and impact resistance were all inferior. It was.
- the content of the amorphous thermoplastic resin (B) was less than the amount specified in the present invention, so the effect of the amorphous thermoplastic resin (B). Was not fully exhibited, and it was inferior to all of flame retardancy, heat resistance and impact resistance.
- composition (X) obtained in Comparative Examples 4 and 5 had an acrylic compatibilizer (C) content less than the amount specified in the present invention, polylactic acid (A) and an amorphous thermoplastic resin (B) was not sufficiently compatible, and was inferior in impact resistance, heat resistance and flame retardancy, and also had low bending strength.
- composition (X) obtained in Comparative Example 6 had a content of the acrylic compatibilizer (C) that was greater than the amount specified in the present invention, the heat resistance, bending strength, and flame retardancy were reduced.
- composition (X) obtained in Comparative Examples 7 and 8 used a styrene type as a compatibilizing agent, the effect of the acrylic compatibilizing agent (C) was not recognized, and the heat resistance, It was inferior in impact and flame retardancy.
- the mass ratio of the phosphate ester flame retardant (D-1) and the phosphinic acid metal salt flame retardant (D-2) is within the range specified by the present invention. Is not satisfied, so the flame retardancy is poor. Furthermore, when the mass ratio of the phosphate ester flame retardant (D-1) was too high, the heat resistance was also lowered.
- compositions (X) obtained in Comparative Examples 13 and 14 contained only the phosphate ester flame retardant (D-1), they were inferior in flame retardancy.
- the compositions (X) obtained in Comparative Examples 15 to 16 and 21 were inferior in flame retardancy because they were a combination of the phosphate ester flame retardant (D-1) and the phosphorus flame retardant. It was.
- the compositions (X) obtained in Comparative Examples 17 to 18 and 22 were a combination of the phosphinic acid metal salt flame retardant (D-2) and the phosphorus flame retardant, they were inferior in flame retardancy. there were.
- the compositions (X) obtained in Comparative Examples 19 to 20 and 23 contained only the phosphorus flame retardant, they were inferior in flame retardancy.
Abstract
Description
しかしながら、ポリ乳酸は、難燃性が低く、容易に燃焼してしまうという問題や、また、耐衝撃性能が低く、衝撃により製品が簡単に割れてしまうという欠点があった。 In recent years, biomass raw material resins such as polylactic acid have attracted attention from the viewpoint of environmental conservation. Polylactic acid is inexpensive because it can be mass-produced, and since it has high heat resistance among biomass-derived resins, its use in various fields including automobile parts and machine parts is being studied.
However, polylactic acid has a problem that it has low flame retardancy and easily burns, and has a drawback that the impact resistance is low and the product is easily cracked by impact.
しかしながら、フッ素系化合物を添加することなしには、未だV-1の難燃性能を達成できていなかった。また、フッ素系化合物を添加すると、成形加工時や焼却時に、有毒ガスが発生するという問題があることも知られている。 In order to improve flame retardancy, it is known that it is effective to add a fluorine-based compound to the resin composition. For example, in Patent Document 1, V-1 flame retardancy is achieved by adding a fluorine compound to a resin composition comprising polylactic acid, polycarbonate, styrene compatibilizer, monocarbodiimide, polyvalent carbodiimide, and a flame retardant. Has been achieved.
However, the flame retardant performance of V-1 has not yet been achieved without adding a fluorine compound. In addition, it is also known that when a fluorine-based compound is added, a toxic gas is generated during molding or incineration.
しかしながら、上記のように自動車部品、電気・電子部品等に使用できることが記載されているものの、特許文献2に記載の樹脂組成物は、芳香族ポリエステルを用いたものであるため、耐衝撃性能が低く、十分な性能を有するものではなかった。また、ポリ乳酸自体の改質も行われておらず、耐熱性能も十分に満足できるものではなかった。 Patent Document 2 describes a resin composition that is made of polylactic acid and an aromatic polyester and has flame retardancy by having a flame retardant. Patent Document 2 shows that this resin composition can be used for automobile parts, electrical / electronic parts and the like, and that flame retardancy of V-1 and V-0 can be achieved.
However, although it is described that it can be used for automobile parts, electric / electronic parts and the like as described above, the resin composition described in Patent Document 2 uses an aromatic polyester, and therefore has an impact resistance performance. It was low and did not have sufficient performance. Further, polylactic acid itself was not modified, and the heat resistance performance was not sufficiently satisfactory.
(1)ポリ乳酸(A)、ビスフェノール基を有する非晶性熱可塑性樹脂(B)、アクリル系相溶化剤(C)および難燃剤(D)を含有する樹脂組成物であり、樹脂組成物中のポリ乳酸(A)の含有量が25~60質量%、ビスフェノール基を有する非晶性熱可塑性樹脂(B)の含有量が30~60質量%、アクリル系相溶化剤(C)の含有量が0.5~20質量%、難燃剤(D)の含有量が5~30質量%であり、難燃剤(D)が、リン酸エステル系難燃剤(D-1)とホスフィン酸金属塩系難燃剤(D-2)とを含み、リン酸エステル系難燃剤(D-1)とホスフィン酸金属塩系難燃剤(D-2)の質量比率〔(D-1)/(D-2)〕が、10/90~50/50であることを特徴とする熱可塑性樹脂組成物。
(2)ポリ乳酸(A)は、D体含有量が1.0モル%以下であるか、または99.0モル%以上であることを特徴とする(1)記載の熱可塑性樹脂組成物。
(3)ポリ乳酸(A)は、架橋構造が導入されたものであることを特徴とする(1)または(2)記載の熱可塑性樹脂組成物。
(4)ビスフェノール基を有する非晶性熱可塑性樹脂(B)が、ポリカーボネート樹脂(B-1)および/またはポリアリレート樹脂(B-2)であることを特徴とする(1)~(3)のいずれかに記載の熱可塑性樹脂組成物。
(5)リン酸エステル系難燃剤(D-1)が芳香族縮合リン酸エステルであり、かつホスフィン酸金属塩系難燃剤(D-2)がホスフィン酸アルミニウム塩であることを特徴とする(1)~(4)のいずれかに記載の熱可塑性樹脂組成物。
(6)さらに芳香族カルボジイミド化合物(E)を含有し、樹脂組成物中の芳香族カルボジイミド化合物(E)の含有量が0.1~5質量%であることを特徴とする(1)~(5)のいずれかに記載の熱可塑性樹脂組成物。
(7)芳香族カルボジイミド化合物(E)が、芳香族モノカルボジイミド(E-1)と芳香族多価カルボジイミド(E-2)とであり、芳香族モノカルボジイミド(E-1)と芳香族多価カルボジイミド(E-2)の質量比率〔(E-1)/(E-2)〕が、10/90~90/10であることを特徴とする(6)記載の熱可塑性樹脂組成物。
(8)上記(1)~(7)のいずれかに記載の熱可塑性樹脂組成物を成形してなる成形体。 That is, the gist of the present invention is as follows.
(1) A resin composition containing polylactic acid (A), an amorphous thermoplastic resin (B) having a bisphenol group, an acrylic compatibilizer (C) and a flame retardant (D), The content of the polylactic acid (A) is 25 to 60% by mass, the content of the amorphous thermoplastic resin (B) having a bisphenol group is 30 to 60% by mass, and the content of the acrylic compatibilizer (C) Is 0.5 to 20% by mass, the content of the flame retardant (D) is 5 to 30% by mass, and the flame retardant (D) is a phosphate ester flame retardant (D-1) and a phosphinic acid metal salt type. A flame retardant (D-2), and a mass ratio of the phosphate ester flame retardant (D-1) and the phosphinic acid metal salt flame retardant (D-2) [(D-1) / (D-2) ] Is a thermoplastic resin composition, characterized in that it is 10/90 to 50/50.
(2) The thermoplastic resin composition according to (1), wherein the polylactic acid (A) has a D-form content of 1.0 mol% or less, or 99.0 mol% or more.
(3) The thermoplastic resin composition according to (1) or (2), wherein the polylactic acid (A) has a cross-linked structure introduced therein.
(4) The amorphous thermoplastic resin (B) having a bisphenol group is a polycarbonate resin (B-1) and / or a polyarylate resin (B-2) (1) to (3) The thermoplastic resin composition according to any one of the above.
(5) The phosphate ester flame retardant (D-1) is an aromatic condensed phosphate ester, and the phosphinic acid metal salt flame retardant (D-2) is an aluminum phosphinate ( 1) The thermoplastic resin composition according to any one of (4).
(6) Further comprising an aromatic carbodiimide compound (E), wherein the content of the aromatic carbodiimide compound (E) in the resin composition is 0.1 to 5% by mass. 5) The thermoplastic resin composition according to any one of the above.
(7) The aromatic carbodiimide compound (E) is an aromatic monocarbodiimide (E-1) and an aromatic polyvalent carbodiimide (E-2), and the aromatic monocarbodiimide (E-1) and the aromatic polyvalent polyvalent The thermoplastic resin composition according to (6), wherein the mass ratio [(E-1) / (E-2)] of the carbodiimide (E-2) is 10/90 to 90/10.
(8) A molded product obtained by molding the thermoplastic resin composition according to any one of (1) to (7).
また、ポリ乳酸として、D体含有量が特定の範囲を満足するものを用いたり、また架橋構造が導入されたものを用いることにより、ポリ乳酸の耐熱性を向上させることができる。そして、樹脂組成物自体の耐熱性を向上させることが可能となるとともに、難燃性も向上させることが可能となる。
また、芳香族カルボジイミド化合物を含有させることにより、樹脂組成物の耐湿熱性も向上させることが可能となる。
以上のように、本発明の熱可塑性樹脂組成物は、難燃性、耐衝撃性、耐熱性、さらには耐湿熱性に顕著に優れており、かつ天然物由来の樹脂を利用しているので石油系製品への依存度が低く、地球環境にも配慮したものである。そして、本発明の熱可塑性樹脂組成物は射出成形等により各種成形体とすることができる。
本発明の成形体は、上記のような本発明の樹脂組成物を成形してなるものであるため、各種の機械部品、電気・電子部品、建築部材、自動車部品や日用品等の各種用途に好適に使用することができる。 The thermoplastic resin composition of the present invention contains a non-crystalline thermoplastic resin having a bisphenol group, which is excellent in flame retardancy and impact resistance, and polylactic acid. Improved low flame resistance and low impact resistance, and excellent in flame retardancy and impact resistance. And since the thermoplastic resin composition of the present invention contains an acrylic compatibilizing agent as a compatibilizing agent, the compatibility between the polylactic acid and the amorphous thermoplastic resin having a bisphenol group is greatly improved, The high flame resistance and impact resistance of the amorphous thermoplastic resin having a bisphenol group are sufficiently exhibited. Further, since a specific flame retardant is used in combination as a flame retardant, further excellent flame retardancy is imparted, and the resin composition can have flame retardancy of V-1 and V-0 levels.
Moreover, the heat resistance of polylactic acid can be improved by using a polylactic acid having a D-form content that satisfies a specific range or using a cross-linked structure. And it becomes possible to improve the heat resistance of resin composition itself, and also to improve a flame retardance.
Moreover, it becomes possible to improve the heat-and-moisture resistance of a resin composition by containing an aromatic carbodiimide compound.
As described above, the thermoplastic resin composition of the present invention is remarkably excellent in flame retardancy, impact resistance, heat resistance, and further heat and moisture resistance, and uses a natural product-derived resin. The dependence on the products is low and the global environment is taken into consideration. And the thermoplastic resin composition of this invention can be made into various molded objects by injection molding etc.
Since the molded article of the present invention is formed by molding the resin composition of the present invention as described above, it is suitable for various applications such as various machine parts, electrical / electronic parts, building members, automobile parts, daily necessities, etc. Can be used for
本発明の熱可塑性樹脂組成物〔以下、組成物(X)と略称することがある。〕は、ポリ乳酸(A)、ビスフェノール基を有する非晶性熱可塑性樹脂(B)、アクリル系相溶化剤(C)および難燃剤(D)を含有する。 Hereinafter, the present invention will be described in detail.
The thermoplastic resin composition of the present invention [hereinafter sometimes abbreviated as composition (X). ] Contains polylactic acid (A), an amorphous thermoplastic resin (B) having a bisphenol group, an acrylic compatibilizer (C), and a flame retardant (D).
ポリ乳酸(A)とは、ポリ(L-乳酸)、ポリ(D-乳酸)、これらの混合物または共重合体のことをいう。 First, polylactic acid (A) will be described.
The polylactic acid (A) refers to poly (L-lactic acid), poly (D-lactic acid), a mixture or a copolymer thereof.
D体含有量が上記の範囲を満足するポリ乳酸(A)は、結晶性に優れることにより、耐熱性が向上し、かつ結晶化速度も向上するので、成形サイクルが短くなり成形性にも優れるものとなる。 Polylactic acid has high heat resistance among aliphatic polyesters, but in order to further improve heat resistance, the D-form content of polylactic acid is 1.0 mol% or less, or 99.0. It is preferably at least mol%. Among them, the D-form content is preferably 0.1 to 0.6 mol% or 99.4 to 99.9 mol%.
The polylactic acid (A) having a D-form content satisfying the above range has excellent crystallinity, thereby improving heat resistance and crystallization speed, thereby shortening the molding cycle and excellent moldability. It will be a thing.
本発明においては、ポリ乳酸(A)のD体含有量は、ポリ乳酸(A)を分解して得られるL乳酸とD乳酸を全てメチルエステル化し、L乳酸のメチルエステルとD乳酸のメチルエステルとをガスクロマトグラフィー分析機で分析する方法により算出するものである。 The D-form content of polylactic acid (A) refers to the proportion (mol%) occupied by D lactic acid units in the total lactic acid units constituting polylactic acid (A). Therefore, for example, in the case of polylactic acid having a D-form content of 1.0 mol%, this polylactic acid has a ratio of D lactic acid units of 1.0 mol% and a ratio of L lactic acid units of 99.0. Mol%.
In the present invention, the D-form content of polylactic acid (A) is such that L lactic acid and D lactic acid obtained by decomposing polylactic acid (A) are all methyl esterified, and methyl ester of L lactic acid and methyl ester of D lactic acid are obtained. Is calculated by a method of analyzing with a gas chromatography analyzer.
ポリ乳酸(A)に架橋構造を導入する方法としては、電子線を照射する方法、多価イソシアネート化合物等の多官能性化合物を使用する方法、過酸化物を使用する方法等の公知の方法が挙げられる。架橋効率の点で、過酸化物を使用する方法が好ましい。 Moreover, it is also preferable to use what introduce | transduced the crosslinked structure as polylactic acid (A). As a form of crosslinking, polylactic acid molecules may be directly crosslinked, indirectly crosslinked via a crosslinking aid, or may be a mixture of direct crosslinking and indirect crosslinking. By introducing the crosslinked structure, the heat resistance of the polylactic acid (A) is improved.
As a method for introducing a crosslinked structure into polylactic acid (A), there are known methods such as a method of irradiating an electron beam, a method of using a polyfunctional compound such as a polyvalent isocyanate compound, and a method of using a peroxide. Can be mentioned. In view of crosslinking efficiency, a method using a peroxide is preferred.
過酸化物の使用量は、ポリ乳酸(A)100質量部に対して、0.1~20質量部とすることが好ましく、0.1~10質量部とすることがより好ましい。10質量部を超えても使用できるが、効果が飽和するばかりか、経済的でない。なお、過酸化物は、架橋する際に分解して消費されるため、ポリ乳酸(A)に添加されても、樹脂組成物中には残存しない場合がある。 Peroxides include benzoyl peroxide, bis (butylperoxy) trimethylcyclohexane, bis (butylperoxy) cyclododecane, butylbis (butylperoxy) valerate, dicumyl peroxide, butylperoxybenzoate, dibutyl peroxide, Examples thereof include bis (butylperoxy) diisopropylbenzene, dimethyldi (butylperoxy) hexane, dimethyldi (butylperoxy) hexyne, and butylperoxycumene.
The amount of the peroxide used is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polylactic acid (A). Although it can be used even if it exceeds 10 parts by mass, the effect is saturated and it is not economical. In addition, since a peroxide decomposes | disassembles and is consumed when bridge | crosslinking, even if it adds to polylactic acid (A), it may not remain in a resin composition.
(メタ)アクリル酸エステル化合物の具体的な化合物としては、例えば、グリシジル(メタ)アクリレート、グリセロールジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、アリロキシポリエチレングリコールモノ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、ポリプロピレングリコールジ(メタ)アクリレート、ポリテトラメチレングリコールジ(メタ)アクリレート、または、これらのアルキレングリコール部が異種のアルキレン基を有するアルキレングリコールの共重合体が挙げられる。 The (meth) acrylic acid ester compound includes a compound having two or more (meth) acrylic groups in the molecule, or one or more (meth) acrylic groups and one or more glycidyl groups or vinyl groups. preferable. These compounds have high reactivity with the biodegradable resin, the monomer hardly remains, and the resin is less colored.
Specific examples of the (meth) acrylic acid ester compound include, for example, glycidyl (meth) acrylate, glycerol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, allyloxy polyethylene glycol mono (meth) acrylate, and polyethylene. Examples include glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, or a copolymer of alkylene glycol in which these alkylene glycol portions have different alkylene groups.
可塑剤としては、例えば、脂肪族多価カルボン酸エステル誘導体、脂肪族多価アルコールエステル誘導体、脂肪族オキシエステル誘導体、脂肪族ポリエーテル誘導体、脂肪族ポリエーテル多価カルボン酸エステル誘導体等が挙げられる。
可塑剤の具体的な化合物としては、グリセリンジアセトモノラウレート、グリセリンジアセトモノカプレート、ポリグリセリン酢酸エステル、ポリグリセリン脂肪酸エステル、脂肪酸トリグリセライド、ジメチルアジペート、ジブチルアジペート、トリエチレングリコールジアセテート、アセチルリシノール酸メチル、アセチルトリブチルクエン酸、ポリエチレングリコール、ジブチルジグリコールサクシネート、ビス(ブチルジグリコール)アジペート、ビス(メチルジグリコール)アジペート等が挙げられる。
市販品としては、理研ビタミン社製PL-012、PL-019、PL-320、PL-710、アクターシリーズ(M-1、M-2、M-3、M-4、M-107FR)、田岡化学社製のATBC、大八化学社製のBXA、MXA、太陽化学社製のチラバゾールVR-01、VR-05、VR-10P、VR-10P改1、VR-623等が挙げられる。 The medium for dissolving or dispersing the peroxide and / or crosslinking aid is not particularly limited, but a plasticizer excellent in compatibility with the resin composition of the present invention is preferable.
Examples of the plasticizer include aliphatic polyvalent carboxylic acid ester derivatives, aliphatic polyhydric alcohol ester derivatives, aliphatic oxyester derivatives, aliphatic polyether derivatives, aliphatic polyether polyvalent carboxylic acid ester derivatives, and the like. .
Specific plasticizer compounds include glycerin diacetomonolaurate, glycerin diacetomonocaprate, polyglycerin acetate, polyglycerin fatty acid ester, fatty acid triglyceride, dimethyl adipate, dibutyl adipate, triethylene glycol diacetate, acetylricinoleic acid Examples include methyl, acetyltributyl citrate, polyethylene glycol, dibutyl diglycol succinate, bis (butyl diglycol) adipate, and bis (methyl diglycol) adipate.
Commercially available products include PL-012, PL-019, PL-320, PL-710, Actor series (M-1, M-2, M-3, M-4, M-107FR) manufactured by Riken Vitamin, Taoka Examples include ATBC manufactured by Kagaku Co., Ltd., BXA and MXA manufactured by Daihachi Chemical Co., Ltd., and Tyrabazole VR-01, VR-05, VR-10P, VR-10P Rev. 1 and VR-623 manufactured by Taiyo Kagaku.
そして、本発明の組成物(X)において、後述する特定の難燃剤(D)を使用し、かつ、このような結晶性に優れたポリ乳酸(A)を用いると、得られる成形体は、結晶性が向上すると同時に難燃性もより向上する。この理由は明らかではないが、ポリ乳酸の結晶性が向上して結晶構造が変化すると、組成物(X)中に含有されている特定の2種類の難燃剤(D-1)と(D-2)の働きが活性化され、十分に難燃性能が発揮される方向に働くものと想定される。
つまり、本発明において、ポリ乳酸(A)として、特定のD体含有量のものや、架橋構造が導入されたものを使用することにより、組成物(X)は、耐熱性が向上すると同時に難燃性も向上したものとなる。 Furthermore, since the polylactic acid (A) having a specific D-form content and the polylactic acid (A) having a crosslinked structure introduced are excellent in crystallinity, the composition (X) using such polylactic acid (A) (X) ) Is formed at a high temperature, or heat treatment is performed after the forming, whereby the crystallinity of the obtained formed body can be further improved.
And in the composition (X) of this invention, when using the specific flame retardant (D) mentioned later and using polylactic acid (A) which was excellent in such crystallinity, the molded object obtained will be, The crystallinity is improved and the flame retardancy is also improved. Although the reason for this is not clear, when the crystallinity of polylactic acid is improved and the crystal structure is changed, the two specific flame retardants (D-1) and (D-) contained in the composition (X) are changed. It is assumed that the function of 2) is activated and works in a direction in which the flame retardant performance is sufficiently exhibited.
That is, in the present invention, the poly (lactic acid) (A) having a specific D-form content or having a cross-linked structure introduced makes it difficult for the composition (X) to have improved heat resistance. The flammability is also improved.
非晶性熱可塑性樹脂とは、以下に示す融点の測定方法により、融点が観測されない熱可塑性樹脂をいう。
(融点の測定方法)
DSC(示差走査熱量測定)装置(パーキンエルマー社製Pyrisl DSC)を用いて、-100℃から300℃まで20℃/分で昇温し、次に-100℃まで50℃/分で降温し、続いて-100℃から300℃まで20℃/分で昇温する。2回目の昇温過程における融解ピークを融点とする。 Next, the amorphous thermoplastic resin (B) having a bisphenol group will be described.
An amorphous thermoplastic resin refers to a thermoplastic resin whose melting point is not observed by the melting point measurement method described below.
(Measuring method of melting point)
Using a DSC (Differential Scanning Calorimetry) device (Pyrisl DSC manufactured by PerkinElmer), the temperature was raised from −100 ° C. to 300 ° C. at 20 ° C./min, then to −100 ° C. at 50 ° C./min, Subsequently, the temperature is raised from −100 ° C. to 300 ° C. at a rate of 20 ° C./min. The melting peak in the second temperature raising process is defined as the melting point.
ポリカーボネート樹脂(B1)とは、ビスフェノール類残基とカーボネート残基からなる樹脂をいう。 The polycarbonate resin (B1) will be described.
The polycarbonate resin (B1) refers to a resin composed of bisphenol residues and carbonate residues.
ポリアリレート樹脂(B2)とは、芳香族ジカルボン酸残基とビスフェノール類残基からなる樹脂をいう。 The polyarylate resin (B2) will be described.
The polyarylate resin (B2) is a resin composed of an aromatic dicarboxylic acid residue and a bisphenol residue.
テレフタル酸とイソフタル酸を併用する場合、両者のモル比率は、特に限定されないが、90/10~10/90の範囲とすることが好ましく、70/30~30/70の範囲とすることがより好ましく、50/50とすることがさらに好ましい。両者のモル比率がこの範囲にあると、界面重合する場合、十分に重合度を上げることができる。 Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, 4,4′-dicarboxyphenyl, and the like. Among these, terephthalic acid and isophthalic acid are preferable from the viewpoint of melt processability and mechanical properties, and the combined use of both is more preferable.
When terephthalic acid and isophthalic acid are used in combination, the molar ratio of the two is not particularly limited, but is preferably in the range of 90/10 to 10/90, more preferably in the range of 70/30 to 30/70. Preferably, 50/50 is more preferable. When the molar ratio of both is in this range, the degree of polymerization can be sufficiently increased when interfacial polymerization is performed.
ポリカーボネート樹脂(B1)とポリアリレート樹脂(B2)の両者を含有した樹脂(B3)としては、ポリカーボネート樹脂(B1)とポリアリレート樹脂(B2)を混合した樹脂、ポリカーボネート樹脂(B1)とポリアリレート樹脂(B2)を共重合した樹脂を含むものである。 The resin (B3) containing both the polycarbonate resin (B1) and the polyarylate resin (B2) will be described.
As the resin (B3) containing both the polycarbonate resin (B1) and the polyarylate resin (B2), a resin obtained by mixing the polycarbonate resin (B1) and the polyarylate resin (B2), the polycarbonate resin (B1), and the polyarylate resin It contains a resin copolymerized with (B2).
本発明の組成物(X)においては、アクリル系相溶化剤(C)を含有させることで、ポリ乳酸(A)と非晶性熱可塑性樹脂(B)との相溶性が格段に向上する。そして相溶性が向上することで、組成物(X)の耐衝撃性や強度等が向上する。さらに、相溶性が向上することで、ポリ乳酸(A)よりも難燃性能が高い非晶性熱可塑性樹脂(B)の難燃性能が最大限に発揮される。このため、特定の難燃剤を添加することによる難燃性の向上効果と相まって、アクリル系相溶化剤ではない相溶化剤を用いた場合と比べると、組成物(X)の難燃性が飛躍的に向上する。 Next, the acrylic compatibilizer (C) will be described.
In the composition (X) of the present invention, the compatibility between the polylactic acid (A) and the amorphous thermoplastic resin (B) is remarkably improved by containing the acrylic compatibilizing agent (C). And by improving compatibility, the impact resistance, strength, etc. of the composition (X) are improved. Furthermore, by improving the compatibility, the flame retardant performance of the amorphous thermoplastic resin (B) having a higher flame retardant performance than the polylactic acid (A) is exhibited to the maximum. For this reason, the flame retardancy of the composition (X) is greatly improved in comparison with the case of using a compatibilizer that is not an acrylic compatibilizer, in combination with the effect of improving the flame retardancy by adding a specific flame retardant. Improve.
(メタ)アクリル系モノマーとしては、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ブチル、メタクリル酸2-エチルヘキシル、メタクリル酸イソボルニル等のアルキル基(シクロアルキル基を含む)の炭素数が1~18の(メタ)アクリル酸アルキルエステル系モノマー、メタクリル酸フェニル等の(メタ)アクリル酸アリールエステル系モノマー、メタクリル酸ベンジル等の(メタ)アクリル酸アラルキルエステル系モノマー等が挙げられる。 The (meth) acrylic copolymer is obtained by polymerizing a (meth) acrylic monomer alone or by copolymerizing two or more (meth) acrylic monomers.
As the (meth) acrylic monomer, alkyl groups (including cycloalkyl groups) such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and isobornyl methacrylate have 1 carbon atom. 18 (meth) acrylic acid alkyl ester monomers, (meth) acrylic acid aryl ester monomers such as phenyl methacrylate, and (meth) acrylic acid aralkyl ester monomers such as benzyl methacrylate.
スチレン系モノマーとしては、スチレン、α-メチルスチレン、o-メチルスチレン、m-メチルスチレン、p-メチルスチレン、ビニルキシレン、エチルスチレン、ジメチルスチレン、p-tert-ブチルスチレン、ビニルナフタレン、メトキシスチレン、モノブロムスチレン、ジブロムスチレン、フルオロスチレン、トリブロムスチレンのスチレン誘導体が挙げられる。中でも、スチレン、α―メチルスチレン等が好ましい。これらは単独で使用してもよく、2種以上を併用してもよい。 The copolymer of a styrene monomer and a (meth) acrylic monomer is obtained by copolymerizing a styrene monomer and a monomer constituting the (meth) acrylic copolymer.
Styrene monomers include styrene, α-methyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, vinyl xylene, ethyl styrene, dimethyl styrene, p-tert-butyl styrene, vinyl naphthalene, methoxy styrene, Examples thereof include styrene derivatives of monobromostyrene, dibromostyrene, fluorostyrene, and tribromostyrene. Of these, styrene, α-methylstyrene and the like are preferable. These may be used alone or in combination of two or more.
ゴム状重合体としては、ポリブタジエン、ポリイソプレン、ブタジエン・スチレン共重合体、イソプレン・スチレン共重合体、ブタジエン・アクリロニトリル共重合体、ブタジエン・イソプレン・スチレン共重合体、ポリクロロプレン等のジエン系ゴム、エチレン・プロピレン共重合体、エチレン・プロピレン・非共役ジエン共重合体、エチレン・ブテン・非共役ジエン共重合体等のエチレン-プロピレン系ゴム、ポリブチルアクリレート等のアクリル系ゴム、ポリオルガノシロキサン系ゴム等のシリコン系ゴム、これら2種以上のゴムからなる複合ゴム等が挙げられる。中でも、ジエン系ゴムまたはアクリル系ゴムが好ましい。これらは単独で使用してもよく、2種以上を併用してもよい。 The rubber-reinforced acrylic compound is obtained by copolymerizing a (meth) acrylic monomer in the presence of a rubbery polymer, or by copolymerizing two or more kinds of monomers.
Examples of rubber-like polymers include polybutadiene, polyisoprene, butadiene / styrene copolymers, isoprene / styrene copolymers, butadiene / acrylonitrile copolymers, butadiene / isoprene / styrene copolymers, diene rubbers such as polychloroprene, Ethylene / propylene copolymers, ethylene / propylene / nonconjugated diene copolymers, ethylene / propylene rubbers such as ethylene / butene / nonconjugated diene copolymers, acrylic rubbers such as polybutyl acrylate, polyorganosiloxane rubbers And silicon rubbers such as these, and composite rubbers composed of two or more of these rubbers. Among these, diene rubber or acrylic rubber is preferable. These may be used alone or in combination of two or more.
コアシェル構造の一例として、コア(内層)は、アクリル成分、シリコーン成分、スチレン成分、ニトリル成分、共役ジエン成分、ウレタン成分またはエチレンプロピレン成分等を重合させたゴム等から構成され、シェル(外層)はメタクリル酸メチル重合体等から構成されるものが挙げられる。
市販品としては、三菱レイヨン製メタブレン、鐘淵化学工業社製カネエース、呉羽化学工業社製パラロイド、ロームアンドハース社製アクリロイド、武田薬品工業社製スタフィロイドまたはクラレ社製パラペットSA等が挙げられる。これらは単独で使用してもよく、2種以上を併用してもよい。 The core-shell type acrylic compound is composed of a layer having a rubber layer as an inner layer and a (meth) acrylic resin as an outer layer.
As an example of the core-shell structure, the core (inner layer) is composed of rubber obtained by polymerizing an acrylic component, a silicone component, a styrene component, a nitrile component, a conjugated diene component, a urethane component or an ethylene propylene component, and the shell (outer layer) The thing comprised from a methyl methacrylate polymer etc. is mentioned.
Examples of commercially available products include METABRENE manufactured by Mitsubishi Rayon, Kaneace manufactured by Kaneka Chemical Co., Ltd., Paraloid manufactured by Kureha Chemical Co., Ltd., Acryloid manufactured by Rohm and Haas Co., Ltd., Staphyloid manufactured by Takeda Pharmaceutical Co., Ltd., and Parapet SA manufactured by Kuraray Co., Ltd. These may be used alone or in combination of two or more.
例えば、エポキシ基を有する(メタ)アクリル酸エステルモノマー同士の共重合体、エポキシ基を有する(メタ)アクリル酸エステルモノマーと(メタ)アクリル酸エステルモノマーの共重合体、エポキシ基を有する(メタ)アクリル酸エステルモノマーとスチレンモノマーの共重合体、エポキシ基を有する(メタ)アクリル酸エステル重合体がスチレン系共重合体にグラフト共重合された化合物、(メタ)アクリル酸エステル重合体がエチレン・グリシジルメタクリレート共重合体にグラフト共重合された化合物、または、コア(内層)がアクリル成分、シリコーン成分、スチレン成分、ニトリル成分、共役ジエン成分、ウレタン成分またはエチレンプロピレン成分等を重合させたゴム等から構成され、シェル(外層)がエポキシ基を有するメタクリル酸メチル共重合体等から構成されるコアシェル構造のもの等が挙げられる。
市販品としては、東亜合成社製ARUFON UG-4000シリーズ、東亞合成社製RESEDA、日本油脂社製モディパーA4200、三菱レイヨン社製メタブレンS-2200等が挙げられる。 An acrylic compound having an epoxy group is a compound having at least one epoxy group and one acrylic group in the molecule.
For example, copolymers of (meth) acrylic acid ester monomers having an epoxy group, copolymers of (meth) acrylic acid ester monomers having an epoxy group and (meth) acrylic acid ester monomers, (meth) having an epoxy group A copolymer of an acrylate monomer and a styrene monomer, a compound obtained by graft copolymerization of a (meth) acrylate polymer having an epoxy group to a styrene copolymer, and a (meth) acrylate polymer is ethylene / glycidyl A compound copolymerized with a methacrylate copolymer, or a core (inner layer) composed of a rubber obtained by polymerizing an acrylic component, a silicone component, a styrene component, a nitrile component, a conjugated diene component, a urethane component or an ethylene propylene component. The shell (outer layer) has an epoxy group Those such as core-shell structure composed of methyl methacrylate copolymer, and the like.
Examples of commercially available products include ARUFON UG-4000 series manufactured by Toagosei Co., Ltd., RESEDA manufactured by Toagosei Co., Ltd., Modiper A4200 manufactured by Nippon Oil & Fats Co., Ltd., and Metabrene S-2200 manufactured by Mitsubishi Rayon Co., Ltd.
一般に、高分子材料の燃焼現象は、燃焼によって燃焼ガスが発生し、その燃焼ガスがさらに燃えることで継続されるとされている。燃焼ガスの発生を効果的に抑制するには、樹脂に応じて難燃剤を選択することが好ましい。ポリ乳酸(A)に対してはホスフィン酸金属塩系難燃剤(D-2)が、また非晶性熱可塑性樹脂(B)に対してはリン酸エステル系難燃剤(D-1)が、それぞれ難燃剤として特に効果的である。さらに両難燃剤を特定の割合で併用することにより、得られる組成物(X)の難燃性を飛躍的に向上させることができる。 Next, the flame retardant (D) will be described.
In general, it is said that the combustion phenomenon of a polymer material is continued by generating combustion gas by combustion and further burning the combustion gas. In order to effectively suppress the generation of combustion gas, it is preferable to select a flame retardant according to the resin. Phosphinic acid metal salt flame retardant (D-2) for polylactic acid (A), and phosphate ester flame retardant (D-1) for amorphous thermoplastic resin (B), Each is particularly effective as a flame retardant. Furthermore, by using both flame retardants in a specific ratio, the flame retardance of the resulting composition (X) can be dramatically improved.
上記したようなリン酸エステル系難燃剤の市販品としては、大八化学工業社製TMP、TEP、TPP、TCP、TXP、CDP、PX-110等が挙げられ、縮合リン酸エステルや芳香族縮合リン酸エステルとしては、大八化学社製PX-200、PX-201、PX-202、CR-733S、CR-741、CR-747等が挙げられる。 Examples of the phosphate ester flame retardant (D-1) include trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl 2,6-xylenyl phosphate Examples include phosphoric acid esters, condensed phosphoric acid esters, and aromatic condensed phosphoric acid esters. Of these, condensed phosphates are preferable, and aromatic condensed phosphates are more preferable.
Commercially available products of the above-mentioned phosphate ester flame retardant include TMP, TEP, TPP, TCP, TXP, CDP, PX-110, etc. manufactured by Daihachi Chemical Industry Co., Ltd. Examples of phosphate esters include PX-200, PX-201, PX-202, CR-733S, CR-741, and CR-747 manufactured by Daihachi Chemical Co., Ltd.
ホスフィン酸金属塩の市販品としてはクラリアント社のOPシリーズ(OP930、OP935、OP1230、OP1312、OP1240等)等が挙げられる。 Examples of the phosphinic acid metal salt flame retardant (D-2) include calcium phosphinate, magnesium phosphinate, zinc phosphinate, aluminum phosphinate, and aluminum phosphinate is preferable.
Commercially available phosphinic acid metal salts include Clariant's OP series (OP930, OP935, OP1230, OP1312, OP1240, etc.).
したがって、リン酸エステル系難燃剤(D-1)とホスフィン酸金属塩系難燃剤(D-2)の質量比率〔(D-1)/(D-2)〕が上記範囲を満足しない場合は、難燃性の向上効果が不十分となる。リン酸エステル系難燃剤(D-1)の質量比率が高すぎる場合は、組成物(X)の耐熱性も低下する。 Further, the mass ratio of the phosphate ester flame retardant (D-1) and the phosphinic acid metal salt flame retardant (D-2) added to the composition (X) [(D-1) / (D-2) ] Needs to be 10/90 to 50/50, more preferably 20/80 to 40/60. That is, by using both of the phosphate ester flame retardant (D-1) and the phosphinic acid metal salt flame retardant (D-2) and using a specific mass ratio, the resulting composition (X) has difficulty. The flammability is dramatically improved. And it can suppress that the heat resistance of composition (X) falls by adding a flame retardant.
Therefore, when the mass ratio [(D-1) / (D-2)] of the phosphate ester flame retardant (D-1) and the phosphinic acid metal salt flame retardant (D-2) does not satisfy the above range. The flame retardancy improving effect is insufficient. When the mass ratio of the phosphate ester flame retardant (D-1) is too high, the heat resistance of the composition (X) also decreases.
熱安定剤や酸化防止剤としては、ヒンダードフェノール類、リン化合物、ヒンダードアミン、イオウ化合物、銅化合物、アルカリ金属のハロゲン化物、ビタミンE等が挙げられる。
充填材としては、機械的強度や耐熱性の向上を目的に、ガラス繊維、金属繊維、炭素繊維等の繊維状強化材を用いることが好ましく、中でも、ガラス繊維等を用いることが好ましい。
繊維状強化材以外の充填材としては、タルク、炭酸カルシウム、炭酸亜鉛、ワラストナイト、シリカ、アルミナ、酸化マグネシウム、ケイ酸カルシウム、アルミン酸ナトリウム、アルミン酸カルシウム、アルミノ珪酸ナトリウム、珪酸マグネシウム、ガラスバルーン、カーボンブラック、酸化亜鉛、三酸化アンチモン、ゼオライト、ハイドロタルサイト、金属ウイスカー、セラミックウイスカー、チタン酸カリウム、窒化ホウ素、グラファイト等の無機充填材、澱粉、セルロース微粒子、木粉、おから、モミ殻、フスマ等の天然に存在するポリマー等の有機充填材が挙げられる。 Furthermore, in the composition (X) of the present invention, the heat stabilizer, the antioxidant, the weathering agent, the light-proofing agent, the pigment, the plasticizer, the lubricant, the mold release agent, and the antistatic are within the range not greatly impairing the characteristics. An agent, a filler, a crystal nucleating agent and the like may be contained.
Examples of heat stabilizers and antioxidants include hindered phenols, phosphorus compounds, hindered amines, sulfur compounds, copper compounds, alkali metal halides, vitamin E, and the like.
As the filler, for the purpose of improving mechanical strength and heat resistance, it is preferable to use a fibrous reinforcing material such as glass fiber, metal fiber, or carbon fiber, and it is preferable to use glass fiber or the like.
As fillers other than fibrous reinforcement, talc, calcium carbonate, zinc carbonate, wollastonite, silica, alumina, magnesium oxide, calcium silicate, sodium aluminate, calcium aluminate, sodium aluminosilicate, magnesium silicate, glass Balloon, carbon black, zinc oxide, antimony trioxide, zeolite, hydrotalcite, metal whisker, ceramic whisker, potassium titanate, boron nitride, graphite and other inorganic fillers, starch, cellulose fine particles, wood powder, okara, fir Organic fillers such as naturally occurring polymers such as shells and bras.
本発明の組成物(X)の製造方法としては、ポリ乳酸(A)、非晶性熱可塑性樹脂(B)、アクリル系相溶化剤(C)、難燃剤(D)を溶融混練する方法が挙げられる。これらを同時に混合する方法、順に混合する方法のいずれであってもよい。芳香族カルボジイミド化合物(E)を含有する場合も、ポリ乳酸(A)、非晶性熱可塑性樹脂(B)、アクリル系相溶化剤(C)、難燃剤(D)とともに同時に添加してもよいし、ポリ乳酸(A)、非晶性熱可塑性樹脂(B)、アクリル系相溶化剤(C)、難燃剤(D)を先に溶融混練しておき、後から添加して混練してもよい。 Next, a method for producing the composition (X) of the present invention will be described.
As a method for producing the composition (X) of the present invention, there is a method in which polylactic acid (A), amorphous thermoplastic resin (B), acrylic compatibilizer (C), and flame retardant (D) are melt-kneaded. Can be mentioned. Any of the method of mixing these simultaneously and the method of mixing in order may be sufficient. Even when the aromatic carbodiimide compound (E) is contained, it may be added simultaneously with the polylactic acid (A), the amorphous thermoplastic resin (B), the acrylic compatibilizer (C), and the flame retardant (D). The polylactic acid (A), the amorphous thermoplastic resin (B), the acrylic compatibilizing agent (C), and the flame retardant (D) are first melt-kneaded and then added and kneaded later. Good.
本発明の組成物(X)は、特に、射出成形法に適しており、一般的な射出成形のほか、ガス射出成形、射出プレス成形等に用いることができる。射出成形条件は、熱可塑性樹脂の種類や含有比率によって適宜選択されるが、シリンダ温度は180~260℃が好ましく、190~250℃がより好ましい。金型温度は操業性を考慮すると、100℃以下が好ましく、80℃以下がより好ましい。
ただし、ポリ乳酸(A)として、D体含有量が1.0モル%以下であるか、または99.0モル%以上であるものを用いたり、架橋構造が導入されたものを用いる場合は、これらの優れた結晶性能を生かすために、金型温度は比較的高温とすることが好ましく、中でも80~120℃が好ましい。
成形温度(金型温度)が低すぎると成形体の一部が欠け、不完全な形状の成形体となるという問題が生じやすい。逆に成形温度が高すぎると、組成物(X)が分解しやすくなり、得られる成形体の強度が低下したり、着色したりする等の問題が発生する場合がある。 The composition (X) of the present invention can be formed into various molded bodies by a molding method such as injection molding, blow molding, extrusion molding, inflation molding, and vacuum molding, pressure molding, and vacuum / pressure molding after sheet processing. .
The composition (X) of the present invention is particularly suitable for an injection molding method, and can be used for gas injection molding, injection press molding and the like in addition to general injection molding. The injection molding conditions are appropriately selected according to the type and content ratio of the thermoplastic resin, but the cylinder temperature is preferably 180 to 260 ° C, more preferably 190 to 250 ° C. The mold temperature is preferably 100 ° C. or lower, more preferably 80 ° C. or lower in consideration of operability.
However, as polylactic acid (A), when D-form content is 1.0 mol% or less, or 99.0 mol% or more, or when a crosslinked structure is used, In order to take advantage of these excellent crystal performances, the mold temperature is preferably relatively high, and 80 to 120 ° C. is particularly preferable.
If the molding temperature (mold temperature) is too low, a part of the molded body is lost, and a problem of forming an incompletely molded body tends to occur. On the other hand, when the molding temperature is too high, the composition (X) is likely to be decomposed, and there may be a problem that the strength of the resulting molded product is reduced or colored.
1.評価項目
(1)MFR
JIS規格K-7210(試験条件4)にしたがい、190℃、荷重21.2Nで測定した。
(2)融点
DSC(示差走査熱量測定)装置(パーキンエルマー社製Pyrisl DSC)を用いて、-100℃から300℃まで20℃/分で昇温し、次に-100℃まで50℃/分で降温し、続いて-100℃から300℃まで20℃/分で昇温した。2回目の昇温過程における融解ピークを融点とした。
(3)極限粘度
1,1,2,2-テトラクロロエタンを測定溶媒として、濃度1g/dl、温度25℃の条件で測定した。 Hereinafter, the present invention will be described more specifically with reference to examples.
1. Evaluation item (1) MFR
According to JIS standard K-7210 (Test condition 4), the measurement was performed at 190 ° C. and a load of 21.2 N.
(2) Melting point Using a DSC (Differential Scanning Calorimetry) device (Pyrisl DSC manufactured by Perkin Elmer), the temperature was raised from −100 ° C. to 300 ° C. at 20 ° C./min, and then to −100 ° C. at 50 ° C./min. The temperature was then lowered from −100 ° C. to 300 ° C. at a rate of 20 ° C./min. The melting peak in the second temperature raising process was taken as the melting point.
(3) Intrinsic viscosity The intrinsic viscosity was measured under the conditions of a concentration of 1 g / dl and a temperature of 25 ° C. using 1,1,2,2-tetrachloroethane as a measurement solvent.
ISO規格75-1、2にしたがい、得られた試験片を用いて、荷重0.45MPaで熱変形温度を測定した。
(5)衝撃強度(シャルピー衝撃強度)
ISO規格179-1eAにしたがい、得られた試験片(V字型切込み付き)を用いて、シャルピー衝撃強度を測定した。
(6)曲げ強度
ISO規格178にしたがい、得られた試験片を用いて、変形速度1mm/分で曲げ強度を測定した。
(7)難燃性
UL94の垂直燃焼試験法にしたがい、得られた試験片(厚み、約1.6mm)を用いて、燃焼試験をおこない、難燃性を評価した。難燃性は、実用上、V-1、V-0が好ましい。
(8)耐湿熱性(強度保持率)
上記(6)同様、ISO規格178にしたがって得られた曲げ強度試験片を用い、温度65℃、湿度90%RHの環境下で500時間処理した後、曲げ強度を測定した。そして、未処理品の曲げ強度((6)で測定した曲げ強度)に対する強度保持率を下記の式で計算した。
強度保持率(%)=(処理後の曲げ強度/未処理品の曲げ強度)×100 (4) Heat resistance (heat distortion temperature)
According to ISO standards 75-1 and 2, the heat distortion temperature was measured with a load of 0.45 MPa using the obtained test piece.
(5) Impact strength (Charpy impact strength)
According to ISO standard 179-1eA, Charpy impact strength was measured using the obtained test piece (with a V-shaped notch).
(6) Bending strength According to ISO standard 178, bending strength was measured at a deformation rate of 1 mm / min using the obtained test piece.
(7) Flame Retardancy According to the UL94 vertical combustion test method, the obtained test piece (thickness, approximately 1.6 mm) was used to perform a combustion test to evaluate flame retardancy. The flame retardancy is preferably V-1 or V-0 for practical use.
(8) Moist heat resistance (strength retention)
Similarly to the above (6), a bending strength test piece obtained according to ISO standard 178 was used, and after bending for 500 hours in an environment of a temperature of 65 ° C. and a humidity of 90% RH, the bending strength was measured. And the strength retention with respect to the bending strength (bending strength measured by (6)) of the untreated product was calculated by the following formula.
Strength retention (%) = (Bending strength after treatment / Bending strength of untreated product) × 100
<(A)ポリ乳酸>
(1)ポリ乳酸(PLA)
・PLA-1 NatureWorks社製3001DK、MFR=10g/10分、融点=168℃、D体含有量=1.4モル%
・PLA-2 トヨタ自動車社製A-1、MFR=2g/10分、融点=172℃、D体含有量=0.6モル%
・PLA-3 トヨタ自動車社製S-12、MFR=8g/10分、融点=176℃、D体含有量=0.1モル%
(2)架橋ポリ乳酸(架橋PLA)
・架橋PLA-1
二軸押出機(東芝機械社製TEM-37BS)を使用し、そのトップフィーダーに、PLA-1を100質量部と、ポリエチレングリコールジメタアクリレート(日本油脂製)1.0質量部、ジ-t-ブチルパーオキサイド(日本油脂製)1.0質量部をグリセリンジアセトモノカプレート2.5質量部に溶解した溶液を注入し、190℃で混練した。吐出された樹脂をペレット状にカッティングして、架橋PLA-1(MFR=1.2g/10分、融点=172℃、D体含有量=1.4モル%)を得た。
・架橋PLA-2
PLA-3を用いた以外は、架橋PLA-1と同様の方法で架橋PLA-2(MFR=1.0g/10分、融点=176℃、D体含有量=0.1モル%)を得た。 2. Raw material <(A) Polylactic acid>
(1) Polylactic acid (PLA)
PLA-1 NatureWorks 3001DK, MFR = 10 g / 10 min, melting point = 168 ° C., D-form content = 1.4 mol%
PLA-2 Toyota Motor Corporation A-1, MFR = 2 g / 10 min, melting point = 172 ° C., D-form content = 0.6 mol%
PLA-3 Toyota Motor Corporation S-12, MFR = 8 g / 10 min, melting point = 176 ° C., D-form content = 0.1 mol%
(2) Crosslinked polylactic acid (crosslinked PLA)
・ Crosslinked PLA-1
Using a twin screw extruder (TEM-37BS manufactured by Toshiba Machine Co., Ltd.), 100 parts by mass of PLA-1 and 1.0 part by mass of polyethylene glycol dimethacrylate (manufactured by NOF Corporation), di-t -A solution prepared by dissolving 1.0 part by mass of butyl peroxide (manufactured by NOF Corporation) in 2.5 parts by mass of glycerin diacetomonocaprate was poured and kneaded at 190 ° C. The discharged resin was cut into pellets to obtain crosslinked PLA-1 (MFR = 1.2 g / 10 min, melting point = 172 ° C., D-form content = 1.4 mol%).
・ Cross-linked PLA-2
A crosslinked PLA-2 (MFR = 1.0 g / 10 min, melting point = 176 ° C., D-form content = 0.1 mol%) was obtained in the same manner as the crosslinked PLA-1, except that PLA-3 was used. It was.
(B-1)ポリカーボネート樹脂
・PC 住友ダウ社製200-13、極限粘度0.49
(B-2)ポリアリレート樹脂
・PAR ユニチカ社製PowderL、極限粘度0.54 <(B) Amorphous thermoplastic resin having bisphenol group>
(B-1) Polycarbonate resin / PC 200-13 manufactured by Sumitomo Dow, intrinsic viscosity 0.49
(B-2) Polyarylate resin, PAR Unita, Powder L, intrinsic viscosity 0.54
(エポキシ基を有するアクリル系相溶化剤)
・EA-1 三菱レイヨン社製メタブレンS-2200
・EA-2 東亜合成社製ARUFON UG-40
・EA-3 日本油脂社製モディパーA4200
(エポキシ基を有しないアクリル系相溶化剤)
・A-1 三菱レイヨン社製メタブレンC-223A
・A-2 三菱レイヨン社製アクリペットVH-001(ポリメタクリル酸メチル樹脂)
<スチレン系相溶化剤>
・S-TPE 旭化成ケミカルズ社製タフテックH1041(スチレン-エチレン/ブチレン-スチレンブロック共重合体) <(C) Acrylic compatibilizer>
(Acrylic compatibilizer having an epoxy group)
・ EA-1 Metablene S-2200 manufactured by Mitsubishi Rayon Co., Ltd.
・ EA-2 ARUFON UG-40 manufactured by Toa Gosei Co., Ltd.
・ EA-3 Modiper A4200 manufactured by NOF Corporation
(Acrylic compatibilizer without epoxy group)
・ A-1 Metablene C-223A manufactured by Mitsubishi Rayon Co., Ltd.
・ A-2 Acrypet VH-001 (polymethyl methacrylate resin) manufactured by Mitsubishi Rayon Co., Ltd.
<Styrene compatibilizer>
・ S-TPE Tough Tech H1041 (Styrene-ethylene / butylene-styrene block copolymer) manufactured by Asahi Kasei Chemicals
(D-1)リン酸エステル系難燃剤
・FR-1 大八化学工業社製PX-200(芳香族縮合リン酸エステル)
・FR-2 大八化学工業社製PX-202(芳香族縮合リン酸エステル)
・FR-3 大八化学工業社製TPP(トリフェニルフォスフェート)
(D-2)ホスフィン酸金属塩系難燃剤
・FR-4 クラリアント社製エクソリットOP1230(ホスフィン酸アルミニウム塩、平均粒径18μm)
・FR-5 クラリアント社製エクソリットOP935(ホスフィン酸アルミニウム塩、平均粒径2.5μm)
なお、FR-4とFR-5の平均粒径の測定は、レーザ回折/散乱式粒度分布測定装置LA-910(堀場製作所社製)を用いて行った。
(リン系難燃剤)
・FR-6 チバスペシャリティケミカルズ社製MELAPUR200/70(ポリリン酸メラミン) <(D) Flame retardant>
(D-1) Phosphate ester flame retardant FR-1 PX-200 (aromatic condensed phosphate ester) manufactured by Daihachi Chemical Industry Co., Ltd.
FR-2 PX-202 (aromatic condensed phosphate ester) manufactured by Daihachi Chemical Industry Co., Ltd.
・ FR-3 TPP (Triphenyl phosphate) manufactured by Daihachi Chemical Industry Co., Ltd.
(D-2) Phosphinic acid metal salt flame retardant / FR-4 Clariant Exolit OP1230 (phosphinic acid aluminum salt, average particle size 18 μm)
FR-5 Clariant Exolit OP935 (phosphinic acid aluminum salt, average particle size 2.5 μm)
The average particle diameters of FR-4 and FR-5 were measured using a laser diffraction / scattering particle size distribution analyzer LA-910 (manufactured by Horiba, Ltd.).
(Phosphorus flame retardant)
FR-6 Ciba Specialty Chemicals MELAPUR 200/70 (melamine polyphosphate)
(E-1)芳香族モノカルボジイミド
・HMCD ラインケミー社製スタバクゾールI(N,N′-ジ-2,6-ジイソプロピルフェニルカルボジイミド)
(E-2)芳香族ポリカルボジイミド
・HPCD ラインケミー社製スタバクゾールP(ポリ(1,3,5-トリイソプロピルベンゼン)カルボジイミド) <(E) Aromatic carbodiimide compound>
(E-1) Aromatic monocarbodiimide / HMCD Rhein Chemie's Starbuxol I (N, N'-di-2,6-diisopropylphenylcarbodiimide)
(E-2) Aromatic polycarbodiimide / HPCD Starbazole P (poly (1,3,5-triisopropylbenzene) carbodiimide) manufactured by Rhein Chemie
二軸押出機(東芝機械社製TEM-37BS)を使用し、そのトップフィーダーに、ポリ乳酸(A)としてPLA-1を30質量部、非晶性熱可塑性樹脂(B)としてPCを41質量部、アクリル系相溶化剤(C)としてEA-1を7質量部、リン酸エステル系難燃剤(D-1)としてFR-1を5質量部、ホスフィン酸金属塩系難燃剤(D-2)としてFR-4を15質量部、芳香族モノカルボジイミド(E-1)としてHMCDを1質量部、および芳香族ポリカルボジイミド(E-2)としてHPCDを1質量部供給し、230℃で溶融混練し、押出した。そして、押出された樹脂をペレット状にカッティングし、組成物(X)を得た。
得られた組成物(X)を、熱風乾燥機で、80℃で5時間乾燥処理した後、射出成形機(東芝機械製IS-80G型)を用いて成形し、各種の性能評価に適したサイズの試験片を得た。いずれの試験片を得る際にも、シリンダ設定温度(射出温度)220℃で溶融して、射出圧力100MPa、射出時間15秒で、80℃(金型温度)の金型に充填し、30秒間保持した後、取り出した。 Example 1
Using a twin screw extruder (TEM-37BS manufactured by Toshiba Machine Co., Ltd.), 30 parts by mass of PLA-1 as polylactic acid (A) and 41 parts by mass of PC as amorphous thermoplastic resin (B) are used as the top feeder. 7 parts by weight of EA-1 as an acrylic compatibilizer (C), 5 parts by weight of FR-1 as a phosphate ester flame retardant (D-1), and a phosphinic acid metal salt flame retardant (D-2) ) 15 parts by weight of FR-4, 1 part by weight of HMCD as aromatic monocarbodiimide (E-1), and 1 part by weight of HPCD as aromatic polycarbodiimide (E-2), and melt-kneaded at 230 ° C. And extruded. Then, the extruded resin was cut into pellets to obtain a composition (X).
The obtained composition (X) was dried with a hot air dryer at 80 ° C. for 5 hours, and then molded with an injection molding machine (IS-80G type manufactured by Toshiba Machine), which was suitable for various performance evaluations. A size specimen was obtained. When obtaining any of the test pieces, it is melted at a cylinder set temperature (injection temperature) of 220 ° C., and filled in a mold of 80 ° C. (mold temperature) at an injection pressure of 100 MPa and an injection time of 15 seconds, for 30 seconds. After holding, it was taken out.
組成物(X)を構成する成分の種類や量、および製造条件(溶融混練温度、射出温度)を表1~3に示すように変更した以外は、実施例1と同様にして各種の試験片を得た。 Examples 2 to 41, Comparative Examples 1 to 25
Various test pieces were prepared in the same manner as in Example 1 except that the types and amounts of the components constituting the composition (X) and the production conditions (melt kneading temperature, injection temperature) were changed as shown in Tables 1 to 3. Got.
特に、実施例2~5、17、19~22、26、28~34、36、38~39、41で得られた組成物(X)は、ポリ乳酸(A)が、特定のD体含有量のものであったり、架橋構造が導入されたものであったため、耐熱性(熱変形温度)と難燃性に優れるものであった。
また、実施例18~19、37~38で得られた組成物(X)は、ホスフィン酸金属塩系難燃剤(D-2)として平均粒径が小さいものを用いたため、難燃性に優れるものとなった。実施例1~24、27~39で得られた組成物(X)は、芳香族カルボジイミド化合物(E)を含有するものであったため、耐湿熱性に優れていた。中でも実施例1~23、27~39で得られた組成物(X)は、芳香族モノカルボジイミド(E-1)と芳香族多価カルボジイミド(E-2)とを併用していたため、耐湿熱性が顕著に優れていた。 The compositions (X) obtained in Examples 1 to 41 are excellent in flame retardancy, impact resistance, and heat resistance, and use polylactic acid derived from natural products. The dependence on the environment was low and the global environment was taken into consideration.
In particular, in the compositions (X) obtained in Examples 2 to 5, 17, 19 to 22, 26, 28 to 34, 36, 38 to 39, 41, polylactic acid (A) contains a specific D form. Since it was a large amount or a crosslinked structure was introduced, it was excellent in heat resistance (heat deformation temperature) and flame retardancy.
The compositions (X) obtained in Examples 18 to 19 and 37 to 38 are excellent in flame retardancy because the phosphinic acid metal salt flame retardant (D-2) has a small average particle size. It became a thing. Since the compositions (X) obtained in Examples 1 to 24 and 27 to 39 contained the aromatic carbodiimide compound (E), they were excellent in heat and heat resistance. Among them, since the compositions (X) obtained in Examples 1 to 23 and 27 to 39 used both the aromatic monocarbodiimide (E-1) and the aromatic polyvalent carbodiimide (E-2), Was significantly better.
比較例9~12で得られた組成物(X)は、リン酸エステル系難燃剤(D-1)とホスフィン酸金属塩系難燃剤(D-2)の質量比率が本発明で規定する範囲を満足しないため、難燃性に劣るものとなった。さらに、リン酸エステル系難燃剤(D-1)の質量比率が高すぎる場合は、耐熱性も低下した。比較例13、14で得られた組成物(X)は、リン酸エステル系難燃剤(D-1)のみを含有するものであったため、難燃性に劣るものであった。比較例15~16、21で得られた組成物(X)は、リン酸エステル系難燃剤(D-1)とリン系難燃剤を併用したものであったため、難燃性に劣るものであった。比較例17~18、22で得られた組成物(X)は、ホスフィン酸金属塩系難燃剤(D-2)とリン系難燃剤を併用したものであったため、難燃性に劣るものであった。比較例19~20、23で得られた組成物(X)は、リン系難燃剤のみを含有するものであったため、難燃性に劣るものであった。
On the other hand, the composition (X) obtained in Comparative Examples 1 to 2 and 24 has a polylactic acid (A) content larger than the amount specified in the present invention, and an amorphous thermoplastic resin ( Since the content of B) was less than the amount specified in the present invention, the effects of the amorphous thermoplastic resin (B) were not sufficiently exhibited, and the flame retardancy, heat resistance and impact resistance were all inferior. It was. In the compositions (X) obtained in Comparative Examples 3 and 25, the content of the amorphous thermoplastic resin (B) was less than the amount specified in the present invention, so the effect of the amorphous thermoplastic resin (B). Was not fully exhibited, and it was inferior to all of flame retardancy, heat resistance and impact resistance. Since the composition (X) obtained in Comparative Examples 4 and 5 had an acrylic compatibilizer (C) content less than the amount specified in the present invention, polylactic acid (A) and an amorphous thermoplastic resin (B) was not sufficiently compatible, and was inferior in impact resistance, heat resistance and flame retardancy, and also had low bending strength. In addition, since the composition (X) obtained in Comparative Example 6 had a content of the acrylic compatibilizer (C) that was greater than the amount specified in the present invention, the heat resistance, bending strength, and flame retardancy were reduced. Furthermore, since the composition (X) obtained in Comparative Examples 7 and 8 used a styrene type as a compatibilizing agent, the effect of the acrylic compatibilizing agent (C) was not recognized, and the heat resistance, It was inferior in impact and flame retardancy.
In the compositions (X) obtained in Comparative Examples 9 to 12, the mass ratio of the phosphate ester flame retardant (D-1) and the phosphinic acid metal salt flame retardant (D-2) is within the range specified by the present invention. Is not satisfied, so the flame retardancy is poor. Furthermore, when the mass ratio of the phosphate ester flame retardant (D-1) was too high, the heat resistance was also lowered. Since the compositions (X) obtained in Comparative Examples 13 and 14 contained only the phosphate ester flame retardant (D-1), they were inferior in flame retardancy. The compositions (X) obtained in Comparative Examples 15 to 16 and 21 were inferior in flame retardancy because they were a combination of the phosphate ester flame retardant (D-1) and the phosphorus flame retardant. It was. Since the compositions (X) obtained in Comparative Examples 17 to 18 and 22 were a combination of the phosphinic acid metal salt flame retardant (D-2) and the phosphorus flame retardant, they were inferior in flame retardancy. there were. Since the compositions (X) obtained in Comparative Examples 19 to 20 and 23 contained only the phosphorus flame retardant, they were inferior in flame retardancy.
Claims (8)
- ポリ乳酸(A)、ビスフェノール基を有する非晶性熱可塑性樹脂(B)、アクリル系相溶化剤(C)および難燃剤(D)を含有する樹脂組成物であり、樹脂組成物中のポリ乳酸(A)の含有量が25~60質量%、ビスフェノール基を有する非晶性熱可塑性樹脂(B)の含有量が30~60質量%、アクリル系相溶化剤(C)の含有量が0.5~20質量%、難燃剤(D)の含有量が5~30質量%であり、難燃剤(D)が、リン酸エステル系難燃剤(D-1)とホスフィン酸金属塩系難燃剤(D-2)とを含み、リン酸エステル系難燃剤(D-1)とホスフィン酸金属塩系難燃剤(D-2)の質量比率〔(D-1)/(D-2)〕が、10/90~50/50であることを特徴とする熱可塑性樹脂組成物。 A resin composition containing polylactic acid (A), an amorphous thermoplastic resin (B) having a bisphenol group, an acrylic compatibilizer (C) and a flame retardant (D), and the polylactic acid in the resin composition The content of (A) is 25 to 60% by mass, the content of the amorphous thermoplastic resin (B) having a bisphenol group is 30 to 60% by mass, and the content of the acrylic compatibilizer (C) is 0.00. 5 to 20% by mass, the content of the flame retardant (D) is 5 to 30% by mass, and the flame retardant (D) comprises a phosphate ester flame retardant (D-1) and a phosphinic acid metal salt flame retardant ( D-2), and the mass ratio [(D-1) / (D-2)] of the phosphate ester flame retardant (D-1) and the phosphinic acid metal salt flame retardant (D-2) is A thermoplastic resin composition characterized by being 10/90 to 50/50.
- ポリ乳酸(A)は、D体含有量が1.0モル%以下であるか、または99.0モル%以上であることを特徴とする請求項1記載の熱可塑性樹脂組成物。 2. The thermoplastic resin composition according to claim 1, wherein the polylactic acid (A) has a D-form content of 1.0 mol% or less or 99.0 mol% or more.
- ポリ乳酸(A)は、架橋構造が導入されたものであることを特徴とする請求項1または2記載の熱可塑性樹脂組成物。 3. The thermoplastic resin composition according to claim 1 or 2, wherein the polylactic acid (A) has a cross-linked structure introduced therein.
- ビスフェノール基を有する非晶性熱可塑性樹脂(B)が、ポリカーボネート樹脂(B-1)および/またはポリアリレート樹脂(B-2)であることを特徴とする請求項1~3のいずれかに記載の熱可塑性樹脂組成物。 4. The amorphous thermoplastic resin (B) having a bisphenol group is a polycarbonate resin (B-1) and / or a polyarylate resin (B-2). Thermoplastic resin composition.
- リン酸エステル系難燃剤(D-1)が芳香族縮合リン酸エステルであり、かつホスフィン酸金属塩系難燃剤(D-2)がホスフィン酸アルミニウム塩であることを特徴とする請求項1~4のいずれかに記載の熱可塑性樹脂組成物。 The phosphate ester flame retardant (D-1) is an aromatic condensed phosphate ester, and the phosphinic acid metal salt flame retardant (D-2) is an phosphinic acid aluminum salt. 5. The thermoplastic resin composition according to any one of 4 above.
- さらに芳香族カルボジイミド化合物(E)を含有し、樹脂組成物中の芳香族カルボジイミド化合物(E)の含有量が0.1~5質量%であることを特徴とする請求項1~5のいずれかに記載の熱可塑性樹脂組成物。 6. The method according to claim 1, further comprising an aromatic carbodiimide compound (E), wherein the content of the aromatic carbodiimide compound (E) in the resin composition is 0.1 to 5% by mass. The thermoplastic resin composition described in 1.
- 芳香族カルボジイミド化合物(E)が、芳香族モノカルボジイミド(E-1)と芳香族多価カルボジイミド(E-2)とであり、芳香族モノカルボジイミド(E-1)と芳香族多価カルボジイミド(E-2)の質量比率〔(E-1)/(E-2)〕が、10/90~90/10であることを特徴とする請求項6記載の熱可塑性樹脂組成物。 The aromatic carbodiimide compound (E) is an aromatic monocarbodiimide (E-1) and an aromatic polyvalent carbodiimide (E-2), and the aromatic monocarbodiimide (E-1) and the aromatic polyvalent carbodiimide (E) The thermoplastic resin composition according to claim 6, wherein the mass ratio of (-2) [(E-1) / (E-2)] is 10/90 to 90/10.
- 請求項1~7のいずれかに記載の熱可塑性樹脂組成物を成形してなる成形体。
A molded article formed by molding the thermoplastic resin composition according to any one of claims 1 to 7.
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JP2014055266A (en) * | 2012-09-13 | 2014-03-27 | Fuji Xerox Co Ltd | Cross-linked polylactic acid, resin composition, and molded article thereof |
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