WO2012176778A1 - Composition de résine thermoplastique et corps moulé - Google Patents

Composition de résine thermoplastique et corps moulé Download PDF

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Publication number
WO2012176778A1
WO2012176778A1 PCT/JP2012/065656 JP2012065656W WO2012176778A1 WO 2012176778 A1 WO2012176778 A1 WO 2012176778A1 JP 2012065656 W JP2012065656 W JP 2012065656W WO 2012176778 A1 WO2012176778 A1 WO 2012176778A1
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Prior art keywords
group
thermoplastic resin
resin composition
lignophenol
mass
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PCT/JP2012/065656
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English (en)
Japanese (ja)
Inventor
野寺　明夫
舩岡　正光
充 青▲柳▼
Original Assignee
出光興産株式会社
国立大学法人三重大学
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Application filed by 出光興産株式会社, 国立大学法人三重大学 filed Critical 出光興産株式会社
Priority to CN201280040012.6A priority Critical patent/CN103842443B/zh
Publication of WO2012176778A1 publication Critical patent/WO2012176778A1/fr

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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • 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

Definitions

  • the present invention relates to a thermoplastic resin composition and a molded body using the same. More specifically, the present invention relates to a thermoplastic resin composition that is excellent in environmental performance by using a biomass material, is excellent in heat resistance and flame retardancy, and is also excellent in molding appearance and moisture and heat resistance, and a molded body using the same.
  • biomass materials such as biodegradable polyester resins have attracted attention from the viewpoint of environmental protection.
  • a typical biodegradable polyester resin is polylactic acid.
  • biomass materials generally have lower mechanical strength than petroleum-based general-purpose plastics and are inferior in heat resistance, so that their use is limited to a very narrow range. Therefore, in order to expand the application range of biomass materials, by blending petroleum-based polymers such as aromatic polycarbonate resins with polylactic acid, or by blending plant fiber materials that have been delignified to biodegradable resins, Attempts have been made to increase the mechanical strength of resin molded bodies (see, for example, Patent Document 1 or 2).
  • the present invention provides a thermoplastic resin composition excellent in environmental performance, suppressing coloring during molding, excellent in fluidity, molding appearance, moisture and heat resistance, and extremely excellent in flame retardancy, and a molded body using the same.
  • the purpose is to do.
  • thermoplastic resin composition excellent in fluidity, molding appearance, moisture and heat resistance, and extremely excellent in flame retardancy and a molded body using the same can be obtained, and the present invention has been completed. That is, the present invention provides the following thermoplastic resin composition and molded article.
  • thermoplastic resin composition comprising a part.
  • R 1 and R 4 represent an alkyl group, an aryl group, an alkoxy group, an aralkyl group or a phenoxy group
  • R 2 represents a hydroxyaryl group or an alkyl-substituted hydroxyaryl group
  • R 3 represents a hydroxyalkyl group or an alkyl group.
  • Group, an aryl group, an alkyl-substituted aryl group or —OR 5 R 5 represents a hydrogen atom, an alkyl group or an aryl group
  • R 1 to R 5 other than a hydrogen atom may have a substituent.
  • p and q are integers from 0 to 4.
  • thermoplastic resin composition as described in 1 above wherein the thermoplastic resin as component (A) comprises 40 to 100% by mass of a polycarbonate resin and 60 to 0% by mass of a thermoplastic resin other than the polycarbonate resin.
  • thermoplastic resin composition according to 1 or 2 above wherein the phosphorus-based flame retardant as a component does not contain a halogen. 4).
  • thermoplastic resin composition by using lignophenol and a phosphorus-based flame retardant, which are environmentally friendly biomass materials, coloring during molding is suppressed and fluidity, molding appearance, moisture and heat resistance are excellent, and flame retardancy is extremely high.
  • An excellent thermoplastic resin composition and a molded body using the same can be obtained.
  • a polycarbonate resin is used as the thermoplastic resin, excellent heat resistance and impact resistance can be obtained, and the polycarbonate resin has good affinity with lignophenol, so that the molded product such as an incompatible polymer alloy can be used. No surface peeling or poor appearance is observed.
  • the biomass degree vegetable degree
  • thermoplastic resin composition of the present invention is a thermoplastic resin composition comprising (A) a thermoplastic resin, (B) lignophenol having a specific structure, and (C) a phosphorus flame retardant.
  • A a thermoplastic resin
  • B lignophenol having a specific structure
  • C a phosphorus flame retardant
  • thermoplastic resin (A) examples include polycarbonate resin, styrene resin, polyethylene resin, polypropylene resin, polymethyl methacrylate resin, polyvinyl chloride resin, cellulose acetate resin, polyamide resin, polyester resin (PET, PBT).
  • polylactic acid and / or a copolymer containing polylactic acid polyacrylonitrile resin, acrylonitrile-butadiene-styrene resin (ABS resin), polyphenylene oxide resin (PPO), polyketone resin, polysulfone resin, polyphenylene sulfide resin (PPS) , Fluororesins, silicon resins, polyimide resins, polybenzimidazole resins, polyamide elastomers, and the like, and copolymers of these with other monomers.
  • ABS resin acrylonitrile resin
  • PPO polyphenylene oxide resin
  • PPS polyketone resin
  • PES polysulfone resin
  • PPS polyphenylene sulfide resin
  • Fluororesins silicon resins, polyimide resins, polybenzimidazole resins, polyamide elastomers, and the like, and copolymers of these with other monomers.
  • thermoplastic resin used in the present invention a thermoplastic resin having an aromatic group in the molecular structure from the viewpoint of affinity with lignophenol as the component (B), for example, an aromatic polycarbonate resin, Styrenic resins, aromatic polyamide resins, aromatic polyester resins and the like are preferable.
  • a polycarbonate resin as the thermoplastic resin (A)
  • the excellent impact resistance and heat resistance of the polycarbonate resin can be imparted to the resulting composition. Therefore, it is preferable to use a polycarbonate resin or a mixture of a polycarbonate resin and another thermoplastic resin as the thermoplastic resin.
  • a polycarbonate resin preferable as the thermoplastic resin will be described.
  • the polycarbonate resin as the thermoplastic resin may be an aromatic polycarbonate resin or an aliphatic polycarbonate resin, but as described above, from the viewpoint of affinity with the component (B) and impact resistance, It is preferable to use an aromatic polycarbonate resin from the viewpoint of heat resistance.
  • an aromatic polycarbonate resin As the aromatic polycarbonate resin, an aromatic polycarbonate resin usually produced by a reaction between a dihydric phenol and a carbonate precursor can be used.
  • the aromatic polycarbonate resin can be a main component of the resin composition because it has better heat resistance, flame retardancy, and impact resistance than other thermoplastic resins.
  • Dihydric phenols include 4,4′-dihydroxydiphenyl; 1,1-bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-hydroxy).
  • Bis (4-hydroxyphenyl) alkane such as phenyl) propane [bisphenol A]; bis (4-hydroxyphenyl) cycloalkane; bis (4-hydroxyphenyl) oxide; bis (4-hydroxyphenyl) sulfide; Hydroxyphenyl) sulfone; bis (4-hydroxyphenyl) sulfoxide; bis (4-hydroxyphenyl) ketone and the like. Of these, bisphenol A is preferred.
  • the dihydric phenol may be a homopolymer using one of these dihydric phenols or a copolymer using two or more. Further, it may be a thermoplastic random branched polycarbonate resin obtained by using a polyfunctional aromatic compound in combination with a dihydric phenol.
  • the carbonate precursor include carbonyl halide, haloformate, carbonate ester and the like, and specifically, phosgene, dihaloformate of dihydric phenol, diphenyl carbonate, dimethyl carbonate, diethyl carbonate and the like.
  • a terminal terminator can be used as necessary, and examples thereof include a monohydric phenol compound represented by the following general formula (II).
  • R 10 represents an alkyl group having 1 to 35 carbon atoms, and a represents an integer of 0 to 5
  • a para-substituted product is preferable.
  • monohydric phenol compounds include phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, p-nonylphenol, and p-tert-amylphenol. it can. These monohydric phenols may be used alone or in combination of two or more.
  • the aromatic polycarbonate resin used in the present invention may have a branched structure.
  • a branching agent may be used.
  • the viscosity average molecular weight of the aromatic polycarbonate resin used in the present invention is preferably 10,000 to 40,000, more preferably 13,000 to 30,000, from the viewpoint of physical properties of the resin composition.
  • the aromatic polycarbonate resin is an aromatic polycarbonate-polyorganosiloxane copolymer or contains an aromatic polycarbonate-polyorganosiloxane copolymer
  • flame retardancy and resistance at low temperatures are used.
  • the impact property can be further improved.
  • the polyorganosiloxane constituting the copolymer is more preferably polydimethylsiloxane from the viewpoint of flame retardancy.
  • thermoplastic resin preferably an aromatic polycarbonate resin
  • the mechanical strength by using the polycarbonate resin to be 40% by mass or more, preferably 50% by mass
  • Impact resistance, heat resistance, etc. can be maintained.
  • the other thermoplastic resin used by mixing with the polycarbonate resin, preferably the aromatic polycarbonate resin is arbitrarily selected from the above-mentioned (A) thermoplastic resins, but is polyester from the viewpoint of compatibility with the polycarbonate resin.
  • a resin (PET, PBT, etc.), polylactic acid and / or a copolymer containing polylactic acid, and a styrene resin such as acrylonitrile-butadiene-styrene resin are preferable.
  • (B) lignophenol has a structure represented by the following general formula (I).
  • R 1 and R 4 are alkyl groups (preferably alkyl groups having 1 to 4 carbon atoms, specifically methyl group, ethyl group, propyl group, etc.), aryl groups (preferably carbon atoms).
  • an alkoxy group preferably an alkoxy group having 1 to 4 carbon atoms, specifically a methoxy group, an ethoxy group, a propoxy group, etc.
  • An aralkyl group preferably an aralkyl group having 12 to 20 carbon atoms, specifically a benzyl group or the like) or a phenoxy group is shown.
  • R 2 is a hydroxyaryl group (preferably a hydroxyaryl group having 6 to 14 carbon atoms, specifically 2-hydroxyphenyl group, 3-hydroxyphenyl group, 4-hydroxyphenyl group, etc.) or alkyl-substituted hydroxyaryl Group (preferably a hydroxyaryl group having 7 to 18 carbon atoms, specifically 2-hydroxy-5-methylphenyl group, 3-hydroxy-5-methylphenyl group, 4-hydroxy-5-methylphenyl group, etc.
  • R 3 represents a hydroxyalkyl group (preferably a hydroxyalkyl group having 1 to 4 carbon atoms, specifically hydroxymethyl group, hydroxyethyl group, etc.), an alkyl group (preferably having 1 to 4 carbon atoms).
  • An alkyl group specifically a methyl group, an ethyl group, a propyl group, or the like) or an aryl group (preferably having 6 to 1 carbon atoms)
  • R 5 represents a hydrogen atom, an alkyl group, preferably an alkyl group having 1 to 10 carbon atoms or an aryl group, preferably an aryl group having 6 to 10 carbon atoms).
  • R 1 to R 5 other than a hydrogen atom may each have a substituent, and p and q each represents an integer of 0 to 4. However, when p is 2 or more, the plurality of R 1 may be the same or different, and when q is 2 or more, the plurality of R 4 are the same or different. May be.
  • the structure represented by the general formula (I) is preferably a naturally derived structure.
  • R 1 and R 4 in the above general formula (I) are determined by the tree species, the substituent represented by R 1 and R 4 is a methoxy group, and p and q are each 1 or 2
  • R 1 and R 4 are determined by the tree species
  • the substituent represented by R 1 and R 4 is a methoxy group
  • p and q are each 1 or 2
  • softwood is a 3-substituted product with one methoxy group
  • broad-leaved trees and herbs are 1: 1 with a 3-substituted product with one methoxy group and two 3,5-substituted products with two methoxy groups.
  • a structure that does not have a part of the substituent that is a methoxy group may be included.
  • R 3 is a hydroxymethyl group in the naturally derived structure.
  • R 2 is a hydroxyaryl group (preferably a hydroxyaryl group having 6 to 14 carbon atoms, specifically 2-hydroxyphenyl group, 3-hydroxyphenyl group, 4 -Hydroxyphenyl group or the like) or alkyl-substituted hydroxyaryl group (preferably a hydroxyaryl group having 7 to 18 carbon atoms, specifically 2-hydroxy-5-methylphenyl group, 3-hydroxy-5-methylphenyl group) , 4-hydroxy-5-methylphenyl group and the like.
  • the variation as (B) lignophenol can be increased by freely controlling R 2 of the naturally derived structure.
  • the weight average molecular weight of the lignophenol represented by the general formula (I) is preferably 1,000 to 200,000, more preferably 3,000 to 100,000, in terms of polystyrene. And it is desirable that both terminal groups of the lignophenol represented by the general formula (I) are phenolic hydroxyl groups.
  • the lignocresol structure represented, for example by following formula (III) is mentioned.
  • Lignophenol is a compound derived from lignin contained in timber, paper, etc., and lignin, for example, acts as an intercellular adhesion substance filled in the gaps of carbohydrates that form the cytoskeleton of trees. is there. Since the structure of lignin is very complex and difficult to use as it is, it is useful to convert it to lignophenol.
  • the component (B) of the present invention can be obtained by adding a phenol derivative to a lignocellulosic material such as wood or paper and then hydrolyzing it with an acid to separate it into lignophenol and a carbohydrate.
  • the component (B) includes an alkali-treated derivative of the above lignophenol, or a derivative in which the hydroxyl group in the above-mentioned lignophenol or the above-mentioned alkali-treated derivative of lignophenol is protected.
  • lignocellulosic substances include wooded materials, various materials mainly wood, such as wood flour, chips, waste materials, and mill ends. Moreover, as wood to be used, any kind of wood such as conifers and hardwoods can be used. Furthermore, various herbaceous plants and related samples such as agricultural wastes can be used. When lignophenol is separated using these materials, those obtained without heating and pressurization in the separation process are preferably used.
  • a monovalent phenol derivative a divalent phenol derivative, a trivalent phenol derivative, or the like
  • the monovalent phenol derivative include phenol, naphthol, anthrol, anthroquinoneol and the like, and each may have one or more substituents.
  • the divalent phenol derivative include resorcinol, hydroquinone and the like, each of which may have one or more substituents.
  • the trivalent phenol derivative include pyrogallol and the like, which may have one or more substituents.
  • those including those other than those mentioned above such as hydroxyanthracene, methoxyphenol (mono-di-tri), methylcatechol, biphenyl, dimethylhydroxyaryl, trimethylhydroxyaryl, etc. can also be used as the phenol derivative.
  • the type of substituent that the phenol derivative may have is not particularly limited, and may have any substituent, but is preferably a group other than an electron-withdrawing group (such as a halogen atom),
  • an alkyl group methyl group, ethyl group, propyl group, etc.
  • an alkoxy group methoxy group, ethoxy group, propoxy group, etc.
  • an aryl group phenyl group etc.
  • Particularly preferred examples of phenol derivatives are cresol, in particular m-cresol or p-cresol.
  • an acid having swelling property with respect to cellulose is preferable.
  • the acid include sulfuric acid having a concentration of 65% by mass or more (for example, 72% by mass sulfuric acid), 85% by mass or more of phosphoric acid, 38% by mass or more of hydrochloric acid, p-toluenesulfonic acid, trifluoroacetic acid, Examples thereof include trichloroacetic acid and formic acid.
  • Examples of the method for extracting and separating lignophenol obtained as described above include the following two methods.
  • the first method is the method described in Japanese Patent No. 2895087. Specifically, lignin is solvated into a phenol derivative by infiltrating a lignocellulosic material such as wood flour, and then concentrated acid is added to dissolve the lignocellulosic material. At this time, the cation at the side chain ⁇ -position of the lignin basic structural unit is attacked by the phenol derivative, and lignophenol in which the phenol derivative is introduced at the benzyl position is generated in the phenol derivative phase. And it is the method of extracting lignophenol from a phenol derivative phase.
  • the precipitate obtained by adding the phenol derivative phase to a large excess of ethyl ether is collected and dissolved in acetone.
  • the acetone insoluble part is removed by centrifugation, and the acetone soluble part is concentrated.
  • the acetone soluble part is dropped into a large excess of ethyl ether, and the precipitate section is collected.
  • the crude lignophenol can be obtained by simply removing the phenol derivative phase by distillation under reduced pressure.
  • an acetone soluble part can also be used for a derivatization process (alkali process) as a lignophenol solution as it is.
  • the second method is a method described in Japanese Patent Laid-Open No. 2001-64494. Specifically, a lignocellulosic material is infiltrated with a solvent in which a solid or liquid phenol derivative is dissolved, and then the solvent is distilled off (phenol derivative sorption step). Next, a concentrated acid is added to this lignocellulosic material to dissolve the cellulose component, and lignophenol is produced in the phenol derivative phase and the lignophenol is extracted as in the first method. Extraction of lignophenol can be performed in the same manner as in the first method. Alternatively, as another extraction method, the entire reaction solution after the concentrated acid treatment is put into excess water, insoluble sections are collected by centrifugation, deoxidized and dried. Acetone or alcohol is added to the dried product to extract lignophenol. Further, as in the first method, this soluble segment is dropped into excess ethyl ether or the like to obtain lignophenol as an insoluble segment.
  • the second method is the latter extraction method, in particular, the method of extracting and separating lignophenol with acetone or alcohol, the amount of phenol derivative used is It is economical because it requires less. Moreover, since this method can process many lignocellulosic materials with a small amount of a phenol derivative, it is suitable for large-scale synthesis of lignophenol.
  • the component (B) of the present invention obtained by the above method generally has the following characteristics.
  • the characteristics of the component (B) used in the present invention are not limited to the following.
  • the weight average molecular weight is about 1,000 to 200,000.
  • a diphenylmethane type structure is formed by the aromatic nucleus of the lignin constituent unit and the aromatic nucleus of the phenol derivative grafted at the side chain ⁇ -position, and self-condensation is suppressed.
  • (6) easily dissolved in various solvents such as methanol, ethanol, acetone, dioxane, pyridine, THF (tetrahydrofuran), DMF (dimethylformamide) and the like.
  • the component (B) obtained by the above method can be used after being derivatized by further alkali treatment.
  • Lignophenol obtained from natural lignin by a phase separation process is stable as a whole because the ⁇ -position of the activated carbon is blocked with a phenol derivative.
  • the phenolic hydroxyl group readily dissociates under alkaline conditions, and the resulting phenoxide ion attacks the ⁇ -position of the adjacent carbon when it is sterically possible.
  • the ⁇ -position aryl ether bond is cleaved, the lignophenol is reduced in molecular weight, and the phenolic hydroxyl group in the introduced phenol nucleus moves to the lignin matrix.
  • the alkali-treated derivative is expected to have improved hydrophobicity compared to lignophenol before the alkali treatment.
  • the alkoxide ion present in the carbon at the ⁇ -position or the carbanion of the lignin aromatic nucleus is also expected to attack the ⁇ -position, but this requires much higher energy than the phenoxide ion. Therefore, the adjacent group effect of the phenolic hydroxyl group of the introduced phenol nucleus preferentially appears under mild alkaline conditions, and further reaction occurs under more severe conditions, and the phenolic hydroxyl group of the once etherified cresol nucleus is regenerated. As a result, it is expected that lignophenol is further reduced in molecular weight and hydrophilicity is increased by increasing the number of hydroxyl groups.
  • lignophenol and lignophenol derivatives obtained by alkali treatment thereof have various characteristics due to the presence of phenolic and alcoholic hydroxyl groups.
  • a derivative having different characteristics can be obtained.
  • the method for protecting the hydroxyl group include protecting the hydroxyl group with a protecting group such as an acyl group (for example, an acetyl group, a propionyl group, a benzyl group, and preferably an acyl group).
  • an acyl group for example, an acetyl group, a propionyl group, a benzyl group, and preferably an acyl group.
  • the phosphorus flame retardant (C) is preferably a phosphorus flame retardant containing no halogen. If halogen is contained, harmful gases may be generated during molding, mold corrosion may occur, and harmful substances may be discharged during incineration of molded products, which is not preferable from the viewpoint of environmental pollution and safety.
  • the phosphorus-based flame retardant containing no halogen include a halogen-free organic phosphorus-based flame retardant.
  • the organic phosphorus flame retardant any organic compound having a phosphorus atom and not containing a halogen can be used without particular limitation. Of these, phosphate ester compounds having at least one ester oxygen atom directly bonded to a phosphorus atom are preferably used.
  • halogen-free phosphorus flame retardants other than organic phosphorus compounds include red phosphorus.
  • the phosphate ester compound is not particularly limited, and preferably does not contain halogen.
  • the following general formula (IV) is not particularly limited, and preferably does not contain halogen.
  • R 11 , R 12 , R 13 and R 14 each independently represents a hydrogen atom or an organic group
  • X represents a divalent or higher valent organic group
  • m is 0 or 1
  • n Is an integer of 1 or more
  • r represents an integer of 0 or more.
  • the organic group is an alkyl group, a cycloalkyl group, an aryl group or the like, which may or may not be substituted. Examples of the substituent when substituted include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, and an arylthio group.
  • an arylalkoxyalkyl group that is a combination of these substituents, or an arylsulfonylaryl group that is a combination of these substituents bonded by an oxygen atom, nitrogen atom, sulfur atom, or the like is used as a substituent.
  • the divalent or higher organic group X means a divalent or higher valent group formed by removing one or more hydrogen atoms bonded to a carbon atom from the above organic group.
  • it is derived from an alkylene group, a (substituted) phenylene group, or a bisphenol that is a polynuclear phenol.
  • Preferable examples include bisphenol A, hydroquinone, resorcinol, diphenylmethane, dihydroxydiphenyl and dihydroxynaphthalene.
  • the phosphate ester compound may be a monomer, dimer, oligomer, polymer or a mixture thereof. Specifically, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, tris (2-ethylhexyl) phosphate, diisopropyl Phenyl phosphate, trixylenyl phosphate, tris (isopropylphenyl) phosphate, trinaphthyl phosphate, bisphenol A bisphosphate, hydroquinone bisphosphate, resorcin bisphosphate, resorcinol-diphenyl phosphate, trioxybenzene triphosphate, cresyl diphenyl phosphate, or
  • halogen-free phosphate ester compounds for example, TPP [triphenyl phosphate], TXP [trixylenyl phosphate], CR-733S [resorcinol bis (diphenyl phosphate) manufactured by Daihachi Chemical Industry Co., Ltd.
  • a blending ratio of (A) thermoplastic resin, (B) lignophenol and (C) phosphorus flame retardant is 1 to 40 parts by mass of component (B) with respect to 100 parts by mass of component (A).
  • Component (C) is 0.5 to 30 parts by mass.
  • the component (B) is less than 1 part by mass, the effect of improving the flame retardancy cannot be obtained, and when it exceeds 40 parts by mass, the effect of suppressing coloring during molding is undesirably reduced.
  • the component (B) is 2 to 30 parts by mass.
  • component (C) when the component (C) is less than 0.5 parts by mass, the effect of suppressing coloring during molding is lowered, silver is likely to occur in the molded product, which is not preferable, and flame retardancy is further enhanced. I can't. And when (C) component exceeds 30 mass parts, since heat resistance, impact resistance, etc. fall, it is unpreferable. Preferably, the component (C) is 2 to 20 parts by mass.
  • the thermoplastic resin composition of the present invention may contain an additive component as necessary together with the component (A), the component (B) and the component (C).
  • an additive component for example, phenol-based, phosphorus-based, sulfur-based antioxidants, antistatic agents, polyamide polyether block copolymers (permanent antistatic performance imparted), benzotriazole-based or benzophenone-based UV absorbers, hindered amine-based light stabilizers (Weathering agent), antibacterial agent, compatibilizer, colorant (dye, pigment) and the like.
  • the compounding amount of the additive component is not particularly limited as long as the characteristics of the thermoplastic resin composition of the present invention are maintained.
  • thermoplastic resin composition of the present invention the above-mentioned components (A), (B) and (C) are blended in the proportions described above, and additive components used as necessary are blended in an appropriate proportion, and kneaded. Can be obtained. Mixing and kneading at this time are premixed with a commonly used equipment such as a ribbon blender, a drum tumbler, etc., then a Henschel mixer, a Banbury mixer, a single screw extruder, a twin screw extruder, a multi screw extruder. This method can be performed by a method using a machine and a conider.
  • the heating temperature at the time of kneading is appropriately selected in the range of usually 200 to 350 ° C. depending on the type of the thermoplastic resin, but when the polycarbonate resin is used as the thermoplastic resin, it is selected in the range of 240 to 300 ° C.
  • the thermoplastic resin composition of the present invention is obtained by using the above-described melt-kneading molding machine or the obtained pellets as an injection molding method, injection compression molding method, extrusion molding method, blow molding method, press molding method, vacuum molding method.
  • Various molded products can be manufactured by the method and the foam molding method.
  • a pellet-shaped molding raw material can be produced, and then this pellet can be used suitably for the production of an injection molded product by injection molding or injection compression molding.
  • the present invention also provides a molded article obtained by molding the above-described thermoplastic resin composition of the present invention.
  • a molded article formed by molding the thermoplastic resin composition of the present invention, preferably an injection molded article (including injection compression) is a copier, fax machine, television, radio, tape recorder, video deck, personal computer, printer, telephone, Used for OA equipment such as information terminals, refrigerators, microwave ovens, home appliances, housings and various parts of electrical / electronic equipment.
  • Moisture and heat resistance The moisture and heat resistance was determined by visually observing the presence or absence of surface deformation after leaving a flat test piece (80 mm ⁇ 80 mm ⁇ 1 mm) in an environment of 60 ° C. and 80% humidity for 300 hours. ⁇ indicates no deformation of the surface. In x, surface swelling and deformation are recognized.
  • each component used in each example is as follows.
  • Polylactic acid Trade name Lacia H100, manufactured by Mitsui Chemicals, Inc.
  • ABS Amorphous styrene resin (acrylonitrile-styrene-butadiene copolymer, trade name: AT-05, manufactured by Nippon A & L Co., Ltd.)
  • the precipitate in the container was dried, acetone was added thereto to extract lignocresol having the structure of formula (III), and then acetone was distilled off. Specifically, it was performed in the same manner as in Example 1 of JP-A-2001-64494.
  • Examples 1 to 7 and Comparative Examples 1 to 9 The above components were blended at the ratio shown in Table 1, supplied to an extruder (model name: VS40, manufactured by Tanabe Plastic Machinery Co., Ltd.), melt-kneaded at 240 ° C., and pelletized.
  • 0.2 parts by mass of Irganox 1076 manufactured by BASF
  • Adekastab C manufactured by ADEKA
  • the obtained pellets were dried at 120 ° C.
  • Table 1 shows the following. Examples 1 to 7 (A) When (B) lignophenol and (C) phosphorus flame retardant are added to a polycarbonate resin which is a thermoplastic resin, YI and flame retardancy can be improved, and the molded appearance and moisture heat resistance are also excellent. Comparative examples 1 to 9 When (B) lignophenol and (C) phosphorus flame retardant are not used in combination, YI decreases (Comparative Example 1, Comparative Example 3, Comparative Example 5, Comparative Example 7, Comparative Example 9), or high flame retardancy. May not be obtained (Comparative Example 1, Comparative Example 2, Comparative Example 4), heat resistance may be reduced (Comparative Example 4, Comparative Example 6, Comparative Example 8), and molding appearance and wet heat resistance may not be sufficient. (Comparative Example 1, Comparative Example 3, Comparative Example 4, Comparative Example 7).
  • thermoplastic resin composition of the present invention can prevent coloring at the time of molding processing that occurs when using lignophenol by using lignophenol and a phosphorus-based flame retardant, which are environmentally friendly biomass materials, and is excellent. It has flame resistance and heat resistance. And it is excellent also in a shaping

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)

Abstract

L'invention concerne une composition de résine thermoplastique contenant, dans (A) 100 parties en masse d'une résine thermoplastique, (B) 1-40 parties en masse d'un lignophénol ayant une structure spécifique et (C) 0,5-30 parties en masse d'un retardateur de flamme à base de phosphore. L'invention concerne également un corps moulé fait par moulage de la composition de résine thermoplastique.
PCT/JP2012/065656 2011-06-22 2012-06-19 Composition de résine thermoplastique et corps moulé WO2012176778A1 (fr)

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JP5942451B2 (ja) * 2012-02-06 2016-06-29 富士ゼロックス株式会社 リグノフェノール誘導体、樹脂組成物、樹脂成形体
US9346922B2 (en) 2013-11-26 2016-05-24 International Business Machines Corporation Flame retardant block copolymers from renewable feeds
US9284414B2 (en) 2013-11-26 2016-03-15 Globalfoundries Inc. Flame retardant polymers containing renewable content
CN107735445A (zh) * 2015-07-29 2018-02-23 出光狮王塑料株式会社 高反射阻燃热塑性树脂组合物、成形体和照明机器用反射板
JP2020176213A (ja) * 2019-04-18 2020-10-29 清水建設株式会社 難燃性樹脂組成物、成形体及び樹脂繊維
CN113897023A (zh) * 2021-09-18 2022-01-07 北京嘉诚瑞鑫科技有限公司 一种非金属汽车车身环保覆盖件及其制作方法

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JP2008050446A (ja) * 2006-08-23 2008-03-06 Fuji Xerox Co Ltd 樹脂組成物、樹脂成形体及び筐体、並びに樹脂成形体の製造方法及びリサイクル方法
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CN103842443B (zh) 2016-04-20

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