Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
• • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/32—Phosphorus-containing compounds
• • 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
• • 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
  • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
• • 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
  • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
  • C08K5/5333—Esters of phosphonic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • 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
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
  • C09J183/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
  • C09J7/22—Plastics; Metallised plastics
  • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds

Definitions

• the present invention relates to a polybutylene terephthalate resin composition, and a molded article and a composite using the same.
• Polybutylene terephthalate resin is excellent in various properties such as mechanical properties, electrical properties, heat resistance, chemical resistance and solvent resistance. It is widely used in various applications. However, when a molded product obtained by molding PBT resin is exposed to an alkaline solution for a long time, the strength may be reduced, or a so-called stress crack may be generated due to external stress or residual stress due to molding processing. There are times when Therefore, when using the molded article using PBT resin as components which contact alkaline solutions, such as a detergent and a snow melting agent, improving alkali-proof solution resistance is calculated
• Patent Documents 1 and 2 JP, 2010-144154, A International Publication No. 2000/078867 pamphlet
• the viscosity may be increased and the fluidity may be reduced.
• the formability is unfavorably reduced.
• the resin composition in which the epoxy resin and the silicone compound are added to the PBT resin is particularly deteriorated in fluidity when it is retained in a molten state for a long time in a molten state at injection molding. It turned out that the formability is further lowered and it is not preferable.
• An object of the present invention is to provide a polybutylene terephthalate resin composition excellent in alkali solution resistance and hydrolysis resistance and excellent in flowability, and a molded article and a composite using the same.
• One aspect of the present invention is as follows. [1] 100 parts by mass of (A) polybutylene terephthalate resin, (B) an amount of epoxy groups of 0.5 to 1.5 when the amount of terminal carboxyl groups of (A) polybutylene terephthalate resin is 1 A polybutylene terephthalate resin composition comprising an epoxy resin, (C) 0.5 to 5 parts by mass of a silicone compound, and (D) 0.05 to 0.5 parts by mass of a phosphorus compound.
• the phosphorus compound is one or two selected from an alkali metal phosphate, an alkaline earth metal phosphate, an organic phosphate compound, an organic phosphite compound, an organic phosphonate compound, and an organic phosphonite compound
• the (D) phosphorus compound contains one or more selected from an alkali metal phosphate, an alkaline earth metal phosphate and an organic phosphite compound.
• the polybutylene terephthalate resin composition as described in 2].
• Polybutylene terephthalate resin composition The present inventor can not only suppress the increase in viscosity of the polybutylene terephthalate resin composition due to the addition of the epoxy resin by adding the phosphorus compound to the polybutylene terephthalate resin composition containing the epoxy resin and the silicone compound. Rather, it has been found that the flowability can be further enhanced, and the flowability can be prevented from being excessively lowered even when being retained in the cylinder in the molten state for a long time in the injection molding or the like.
• the polybutylene terephthalate resin composition (hereinafter, also referred to as “PBT resin composition”) according to the present embodiment includes (A) polybutylene terephthalate resin, (B) epoxy resin, (C) silicone compound, and D) Contains a phosphorus-based compound.
• PBT resin composition includes (A) polybutylene terephthalate resin, (B) epoxy resin, (C) silicone compound, and D) Contains a phosphorus-based compound.
• butylene terephthalate resin As polybutylene terephthalate resin (hereinafter, also simply referred to as "PBT resin"), butylene terephthalate is a main component (for example, 50% by mass to 100% by mass, preferably 60% by mass to 100% by mass, more preferably 75% Homopolyester (polybutylene terephthalate) or copolyester (butylene terephthalate-based copolymer or polybutylene terephthalate copolyester) or the like.
• PBT resin polybutylene terephthalate resin
• PBT resin polybutylene terephthalate resin
• butylene terephthalate is a main component (for example, 50% by mass to 100% by mass, preferably 60% by mass to 100% by mass, more preferably 75% Homopolyester (polybutylene terephthalate) or copolyester (butylene terephthalate-based copolymer or polybutylene ter
• copolymerizable monomers in the copolyester examples include dicarboxylic acids other than terephthalic acid, diols other than 1,4-butanediol, oxycarboxylic acids, lactones, and the like. .
• the copolymerizable monomers can be used alone or in combination of two or more.
• dicarboxylic acids examples include aliphatic dicarboxylic acids (eg, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, hexadecanedicarboxylic acid, dimer acid, etc.
• aliphatic dicarboxylic acids eg, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, hexadecanedicarboxylic acid, dimer acid, etc.
• C 4-40 dicarboxylic acids preferably C 4-14 dicarboxylic acids
• alicyclic dicarboxylic acids e.g., hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, C 8-12 dicarboxylic such himic acid
• aromatic dicarboxylic acids other than terephthalic acid eg, phthalic acid, isophthalic acid; naphthalene dicarboxylic acids such as 2,6-naphthalene dicarboxylic acid; 4,4'-diphenyl dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid 4,4'-diphenylmethane dical Phosphate, 4,4'-diphenyl ketone C 8-16 diphenyl dicarboxylic acid such as dicarboxylic acids), or reactive derivatives thereof [for example, lower alkyl esters of phthalic acid such as (di
• diols examples include aliphatic alkylene glycols other than 1,4-butanediol (eg, ethylene glycol, trimethylene glycol, propylene glycol, neopentyl glycol, hexanediol, octanediol, decanediol, etc.) Linear C 2-12 aliphatic glycol, preferably linear or branched C 2-10 aliphatic glycol), (poly) oxyalkylene glycol (glycol having a plurality of oxy C 2-4 alkylene units, for example, Diethylene glycol, dipropylene glycol, ditetramethylene glycol, triethylene glycol, tripropylene glycol, polytetramethylene glycol etc., alicyclic diols (eg, 1,4-cyclohexanediol, 1,4-cyclohexene) Nji methanol, hydrogenated bisphenol A, etc.), aromatic diol (e
• bisphenols examples include bis (4-hydroxyphenyl) methane (bisphenol F), 1,1-bis (4-hydroxyphenyl) ethane (bisphenol AD), 1,1-bis (4-hydroxyphenyl) propane, 2 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2- Bis (hydroxyaryl) C 1 such as bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) hexane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane and the like -6 alkanes; 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydrate Bis (hydroxyaryl) C 4-10 cycloalkanes such as oxyphenyl) cyclohexane; 4,4'-dihydroxydiphenyl ether; 4,4'-dihydroxydiphenyl
• alkylene oxide adducts C 2-3 alkylene oxide adducts of bisphenols (eg, bisphenol A, bisphenol AD, bisphenol F, etc.), eg, 2,2-bis- [4- (2-hydroxyethoxy) phenyl Propane, diethoxylated bisphenol A (EBPA), 2,2-bis- [4- (2-hydroxypropoxy) phenyl] propane, dipropoxylated bisphenol A and the like.
• the addition mole number of the alkylene oxide C2-3 alkylene oxide such as ethylene oxide or propylene oxide
• the oxycarboxylic acids include, for example, oxybenzoic acids, oxynaphthoic acids, hydroxyphenylacetic acids, glycolic acids, oxycarboxylic acids such as oxycaproic acid, or derivatives thereof.
• the lactones include C 3-12 lactones such as propiolactone, butyrolactone, valerolactone, caprolactone (eg, ⁇ -caprolactone etc.) and the like.
• Preferred copolymerizable monomers include diols or dicarboxylic acids.
• diols include C 2-6 alkylene glycols (linear or branched alkylene glycols such as ethylene glycol, trimethylene glycol, propylene glycol, hexanediol, etc.), and oxyalkylene units having a repeating number of about 2 to 4 Polyoxy C 2-4 alkylene glycols (such as diethylene glycol), bisphenols (such as bisphenols or alkylene oxide adducts thereof), and the like.
• dicarboxylic acids examples include C 6-12 aliphatic dicarboxylic acids (adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, etc.), asymmetric aromatic dicarboxylic acids in which the carboxyl group is substituted at the asymmetric position of the arene ring, 1,1 4-cyclohexanedimethanol and the like.
• aromatic compounds such as alkylene oxide adducts of bisphenols (especially bisphenol A) and asymmetric aromatic dicarboxylic acids [phthalic acid, isophthalic acid, and reactive derivatives thereof (dimethyl isophthalic acid (DMI) Etc.) and the like are preferable.
• the polybutylene terephthalate resin is preferably homopolyester (polybutylene terephthalate) and / or copolymer (polybutylene terephthalate copolyester), and the proportion (modification amount) of the copolymerizable monomer is usually 45 mol% or less (e.g. 0 to 40 mol%), preferably 35 mol% or less (eg, about 0 to 35 mol%), and may be 30 mol% or less (0 to 30 mol%).
• the proportion of the copolymerizable monomer in the copolymer can be selected, for example, from the range of about 0.01 to 30 mol%, usually 1 to 30 mol%, preferably 3 to 25 mol%.
• the proportion of the copolymerizable monomer in the copolymer can be selected, for example, from the range of about 0.1 to 45 mol%, and is usually 1 to 40 mol% (for example, 5 to 40 mol %, Preferably about 10 to 35 mol%.
• the proportion of the homopolyester to the copolyester is such that the proportion of the copolymerizable monomer is from 0.1 to It is in the range of about 30 mol% (preferably 1 to 25 mol%, more preferably 5 to 25 mol%), and usually the weight ratio of homopolyester / copolyester is 99/1 to 1/99, preferably It can be selected from the range of about 95/5 to 5/95, more preferably about 90/10 to 10/90.
• Polybutylene terephthalate resin is copolymerized with terephthalic acid or a reactive derivative thereof and a monomer which is optionally copolymerized with 1,4-butanediol by a conventional method such as transesterification, direct esterification method and the like. It can be manufactured by
• the content of the polybutylene terephthalate resin is 50% by mass or more in the entire PBT resin composition in that the various properties such as mechanical properties, electrical properties, heat resistance, chemical resistance and solvent resistance are sufficiently exhibited.
• it can be 60% by mass or more, more preferably 65% by mass or more.
• the amount of terminal carboxyl groups of the polybutylene terephthalate resin is preferably 50 meq / kg or less, and particularly preferably 35 meq / kg or less, in terms of further enhancing the alkali solution resistance.
• the lower limit of the amount of terminal carboxyl groups of the polybutylene terephthalate resin is not particularly limited, but when the amount of terminal carboxyl groups of the polybutylene terephthalate resin is extremely low, (B) epoxy resin, and optionally for the purpose of improving mechanical characteristics. 1 meq / kg or more, preferably 5 meq or more, in that the reaction with the surface treatment agent of the inorganic filler such as glass fiber to be added may be insufficient, and it may be difficult to obtain alkali solution resistance and mechanical properties.
• the amount of terminal carboxyl group of polybutylene terephthalate resin is determined by dissolving a crushed sample of polybutylene terephthalate resin in benzyl alcohol at 215 ° C. for 10 minutes and then titrating with a 0.01 N aqueous solution of sodium hydroxide to measure.
• the intrinsic viscosity of the polybutylene terephthalate resin is not particularly limited as long as the object of the present invention is not impaired, but it is preferably 0.60 dL / g to 1.2 dL / g, more preferably 0.65 dL / g to 0. .9 dL / g or less.
• the PBT resin composition obtained will be particularly excellent in moldability.
• the intrinsic viscosity can also be adjusted by blending polybutylene terephthalate resins having different intrinsic viscosities.
• a polybutylene terephthalate resin having an inherent viscosity of 0.9 dL / g is prepared by blending a polybutylene terephthalate resin having an inherent viscosity of 1.0 dL / g and a polybutylene terephthalate resin having an inherent viscosity of 0.7 dL / g.
• the intrinsic viscosity (IV) of the polybutylene terephthalate resin can be measured, for example, in o-chlorophenol at a temperature of 35 ° C.
• epoxy resin examples include polyfunctional epoxy resins and vinyl copolymers having a glycidyl group.
• the epoxy resins can be used alone or in combination of two or more.
• glycidyl ether type epoxy resin for example, glycidyl ether type epoxy resin, glycidyl ester type epoxy resin (diglycidyl phthalate, diglycidyl tetrahydro phthalate, diglycidyl hexahydrophthalate, dimethyl glycidyl phthalate, dimethyl glycidyl hexahydro phthalate, dimer acid glycidyl ester , Aromatic diglycidyl ester, cycloaliphatic diglycidyl ester, etc., glycidyl amine type epoxy resin (tetraglycidyl diaminodiphenylmethane, triglycidyl para aminophenol, triglycidyl meta amino phenol, diglycidyl toluidine, tetraglycidyl toxylylene di Amine, diglycidyl tribromoaniline, tetraglycidyl bisaminomethyl Cyclo
• glycidyl ether type epoxy resins include glycidyl ethers of polyhydroxy compounds [bisphenol type epoxy resins (for example, bisphenol A type (Bis-A type), bisphenol AD type, bisphenol F type epoxy resin, etc.), resorcinol type epoxy resins, etc. Glycidyl ethers of aromatic polyhydroxy compounds; aliphatic epoxy resins (such as alkylene glycols and glycidyl ethers of polyoxyalkylene glycols); novolac epoxy resins (such as phenol nopolac type and cresol novolac epoxy resins); Be
• the vinyl copolymer having a glycidyl group is composed of a copolymer of a polymerizable monomer having a glycidyl group (such as a vinyl monomer having a glycidyl group) and another copolymerizable monomer. Ru.
• the polymerizable monomer having a glycidyl group has, along with the glycidyl group, at least one polymerizable group (such as an ethylenically unsaturated bond (such as a vinyl group) or an acetylene bond).
• at least one polymerizable group such as an ethylenically unsaturated bond (such as a vinyl group) or an acetylene bond.
• glycidyl ethers such as allyl glycidyl ether, vinyl glycidyl ether, chalcone glycidyl ether, 2-cyclohexene-1-glycidyl ether; glycidyl (meth) acrylate, glycidyl maleate, glycidyl itaconate, vinyl benzoic acid Acid glycidyl ester, allyl benzoate glycidyl ester, cinnamic acid glycidyl ester, cinnamylidene glycidyl ester, dimer acid glycidyl ester, epoxidized ester of stearyl alcohol and acrylic acid or methacrylic acid, alicyclic glycidyl ester (cyclohexene-4, Glycidyl or epoxy esters such as 5-diglycidyl carboxylate etc.
• Epoxidized unsaturated linear or cyclic olefins such as epoxyhexene and limonene oxide; N- [4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl] acrylamide and the like.
• vinyl monomers having a glycidyl group for example, glycidyl esters of ⁇ , ⁇ -unsaturated carboxylic acids are preferred.
• These glycidyl group-containing polymerizable monomers can be used alone or in combination of two or more.
• Examples of the other copolymerizable monomers copolymerizable with the polymerizable monomer having a glycidyl group include olefin monomers (eg, ⁇ -olefins such as ethylene, propylene, butene, and hexene), diene-based monomers, etc.
• olefin monomers eg, ⁇ -olefins such as ethylene, propylene, butene, and hexene
• diene-based monomers etc.
• Monomers such as conjugated dienes such as butadiene and isoprene
• aromatic vinyl monomers such as styrene monomers such as styrene, ⁇ -methylstyrene and vinyl toluene
• acrylic monomers ((meth) acrylics Acids, (meth) acrylic acid alkyl esters such as methyl methacrylate, acrylonitrile and the like), vinyl esters (vinyl acetate, vinyl propionate and the like), vinyl ethers and the like can be mentioned.
• the copolymerizable monomer is preferably a monomer having an ⁇ , ⁇ -unsaturated double bond. These copolymerizable monomers can be used alone or in combination of two or more.
• olefin monomers acrylic monomers ((meth) acrylic acid, (meth) acrylic acid ester, etc.) and the like are preferable.
• the addition amount of the epoxy resin is an amount such that the amount of epoxy groups is 0.5 to 1.5 when the amount of terminal carboxyl groups of (A) polybutylene terephthalate resin in the polybutylene terephthalate resin composition is 1. Preferably in an amount of 0.8 to 1.2.
• the amount of epoxy groups is a value calculated
• the PBT resin composition contains a silicone compound at a point of further improving the alkali solution resistance.
• the alkali solution resistance is improved more in the case of adding the epoxy resin and the silicone compound than in the case of adding only the epoxy resin to the PBT resin, but such PBT resin composition is particularly good. It was found that when the substance was allowed to stay in the molten state for a long time, the increase in viscosity became remarkable and the fluidity further decreased.
• the polybutylene terephthalate resin composition according to the present embodiment even in the case of containing an epoxy resin and a silicone compound, a PBT resin composition having both excellent flowability and resistance to alkaline solution can be obtained. Can.
• the liquid organopolysiloxane which has a siloxane bond in a principal chain can be mentioned, The kind in particular is not limited.
• R 3 SiO [R 2 SiO] n SiR 3 (1) (Wherein R is a substituted or unsubstituted monovalent hydrocarbon group or a hydroxyl group, and n is an integer).
• R represents an alkyl group such as methyl, ethyl or propyl; an alkenyl group such as vinyl or allyl; an aralkyl group such as cycloalkyl or ⁇ -phenylethyl; 3,3,3-tri It is a substituted or unsubstituted monovalent hydrocarbon group exemplified by fluoropropyl group, 3-mercaptopropyl group, 3-aminopropyl group, 3-glycidoxypropyl group and the like.
• silicone compounds include: pure silicone resins such as dimethylpolysiloxane, methylphenylpolysiloxane and diphenylpolysiloxane generally used as silicone oils; pure silicone resins; alkyd resins; polyester resins; acrylic resins; A modified silicone reacted with a modifying resin such as a resin may, for example, be mentioned. One or more selected from these can be used.
• the content of the silicone compound is preferably 0.5 to 5 parts by mass, more preferably 0. 5 parts by mass with respect to 100 parts by mass of the (A) polybutylene terephthalate resin, from the viewpoint of further enhancing the alkali solution resistance.
• the amount is 8 to 2.5 parts by mass, more preferably 0.8 to 2 parts by mass.
• the molecular weight of the silicone compound is not particularly limited, but it is preferable that the silicone compound is liquid, and in particular, one having a kinematic viscosity at 25 ° C. of 100 to 200,000 cSt is preferable. More preferably, it is in the range of 1000 to 60000 cSt, especially 3000 to 10000 cSt.
• the phosphorus-based compound includes at least one selected from organic phosphorus-based compounds and inorganic phosphorus-based compounds.
• organic phosphorus compounds include organic phosphate compounds, organic phosphite compounds, organic phosphonate compounds, organic phosphonite compounds and the like.
• inorganic phosphorus compounds include alkali metal phosphates and alkaline earth metal phosphates.
• the phosphorus-based compound may be liquid or solid.
• organic phosphate compounds include mono to trialkyl esters of phosphoric acid (for example, mono to di C 6-24 alkyl esters such as monostearyl acid phosphate, distearyl acid phosphate, etc.), mono to triaryl esters of phosphoric acid (mono Or mono- or di-C 6-10 aryl esters such as diphenyl phosphate etc.) and the like.
• mono to trialkyl esters of phosphoric acid for example, mono to di C 6-24 alkyl esters such as monostearyl acid phosphate, distearyl acid phosphate, etc.
• mono to triaryl esters of phosphoric acid mono Or mono- or di-C 6-10 aryl esters such as diphenyl phosphate etc.
• organic phosphite compound for example, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butyl-4-methylphenyl) penta Erythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite and the like.
• organic phosphonate compound mono- or dialkyl phosphonates (C 6-24 alkyl phosphonate etc.) such as distearyl phosphonate; and aryl phosphonates which may have a substituent on the aryl group such as diphenyl phosphonate or di (nonylphenyl) phosphonate (C 6-10 aryl phosphonates, etc.); mono- or di-aralkyl phosphonates such as dibenzyl phosphonate ((C 6-10 aryl -C 1-6 alkyl) phosphonate and the like) and the like.
• organic phosphonite compound examples include tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene phosphonite and the like.
• alkali metal phosphates include phosphates or corresponding hydrogen phosphates (eg, potassium phosphate, sodium phosphate [(monosodium phosphate (sodium dihydrogenphosphate), disodium phosphate (hydrogen phosphate) And alkali metal salts such as sodium, sodium monohydrogenphosphate, disodium hydrogenphosphate etc.) and the like.
• phosphates or corresponding hydrogen phosphates eg, potassium phosphate, sodium phosphate [(monosodium phosphate (sodium dihydrogenphosphate), disodium phosphate (hydrogen phosphate) And alkali metal salts such as sodium, sodium monohydrogenphosphate, disodium hydrogenphosphate etc.
• alkaline earth metal phosphate calcium phosphate (calcium phosphate (calcium dihydrogen phosphate, calcium bis (dihydrogen phosphate) monohydrate etc.), dibasic calcium phosphate (calcium hydrogen phosphate, calcium hydrogen phosphate) Dihydrate etc. and the like], alkaline earth metal salts such as magnesium phosphate (magnesium hydrogen phosphate, magnesium dihydrogen phosphate etc.) and the like.
• the alkali metal salt or alkaline earth metal salt may be either anhydrous or hydrous.
• the PBT resin composition when used for a molded article application to be bonded to another member using a silicone adhesive, it contains an alkali metal phosphate and / or a metal alkaline earth salt in terms of enhancing the adhesive strength. Is preferable, and it is more preferable to contain sodium dihydrogen phosphate.
• the content of the (D) phosphorus-based compound is 0.05 to 0.5 parts by mass, preferably 0.05 to 0.3 parts by mass with respect to 100 parts by mass of the (A) polybutylene terephthalate resin. More preferably, it is 0.08 to 0.2 parts by mass.
• the polybutylene terephthalate resin composition of one embodiment of the present invention can contain other components as needed.
• Other components include, for example, inorganic fillers, antioxidants, weathering stabilizers, molecular weight modifiers, UV absorbers, antistatic agents, dyes, pigments, lubricants, crystallization accelerators, crystal nucleating agents, near infrared rays
• an absorbent, a flame retardant, a flame retardant auxiliary, an organic filler, a coloring agent etc. are mentioned, it is not limited to these.
• a fibrous, particulate or plate-like inorganic filler for example, a fibrous, particulate or plate-like inorganic filler can be used.
• fibrous inorganic fillers include glass fibers, asbestos fibers, silica fibers, silica / alumina fibers, alumina fibers, zirconia fibers, boron nitride fibers, silicon nitride fibers, boron fibers, potassium titanate fibers, and further stainless steel, aluminum, titanium And fibrous materials of metals such as copper and brass.
• cuttle-fish, glass flakes, various metal foil etc. can be illustrated.
• the size of the inorganic filler is not particularly limited as long as the effect of the present invention is not impaired.
• the content of the inorganic filler is not particularly limited, but is preferably 40 to 100 parts by mass, and more preferably 45 to 80 parts by mass with respect to 100 parts by mass of (A) PBT resin.
• the content of the inorganic filler is in the above-mentioned range, the strength of the molded article can be further enhanced.
• antioxidants examples include hindered phenol-based, thioether-based and hindered amine-based antioxidants, and one or more selected from these may be used.
• the content of the antioxidant is not particularly limited, and is determined according to the purpose. For example, it can be 0.01 to 5 parts by mass with respect to 100 parts by mass of PBT resin.
• the colorant is not particularly limited, and examples thereof include inorganic pigments, organic pigments, dyes and the like.
• examples of the inorganic pigment include black pigments such as carbon black and carbon nanotubes, red pigments such as iron oxide red, orange pigments such as molybdate orange, and white pigments such as titanium oxide.
• examples of organic pigments include yellow pigments, orange pigments, red pigments, blue pigments, green pigments and the like.
• These coloring agents B can be used alone or in combination of two or more.
• the coloring agent B may be one whose surface is treated with an acid or the like.
• the content of the colorant can be, for example, 0.01 to 5 parts by mass with respect to 100 parts by mass of the PBT resin composition.
• the polybutylene terephthalate resin composition according to an embodiment of the present invention may contain other crystalline resin such as PET resin, as long as the effects of the present invention are not impaired.
• Polycarbonate resin (PC resin) polytrile Amorphous resins such as methylene terephthalate resin (PTT resin), polycyclohexylene dimethylene terephthalate resin (PCT resin), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-styrene-butadiene copolymer (ABS resin) May be included.
• PC resin polycarbonate resin
• PCT resin polytrile Amorphous resins
• AS resin acrylonitrile-styrene copolymer
• ABS resin acrylonitrile-styrene-butadiene copolymer
• the transesterification with (A) PBT resin may affect the moldability and mechanical properties, so the polybutylene terephthalate resin composition of the present invention Is preferably substantially free of polyester resins other than PBT resin.
• the phrase "does not substantially contain" means that the content of the polyester-based resin other than the PBT resin is 10% by mass or less of the entire polybutylene terephthalate resin composition, and preferably 5% by mass or less. It is.
• the polybutylene terephthalate resin composition of one embodiment of the present invention may contain a thermoplastic elastomer in order to improve impact resistance.
• the type of the thermoplastic elastomer is not particularly limited, and examples thereof include olefin elastomers, styrene elastomers, polyester elastomers, polyamide elastomers and urethane elastomers.
• olefin elastomer are copolymers having ethylene and / or propylene as the main component, and specifically, ethylene-propylene copolymers, ethylene-butene copolymers, ethylene-octene copolymers, ethylene -Propylene-butene copolymer, ethylene-propylene-diene copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-vinyl acetate copolymer, ethylene-glycidyl methacrylate copolymer, etc. Although it is mentioned, it is not limited to this.
• styrenic elastomers include block copolymers comprising a polymer block mainly composed of a vinyl aromatic compound such as styrene and a polymer block mainly composed of a nonhydrogenated and / or hydrogenated conjugated diene compound. .
• polyester elastomers examples include aromatic polyesters such as polyethylene terephthalate and polybutylene terephthalate as hard segments, polyethers such as polyethylene glycol and polytetramethylene glycol, or aliphatic polyesters such as polyethylene adipate, polybutylene adipate, and polycaprolactone as soft.
• aromatic polyesters such as polyethylene terephthalate and polybutylene terephthalate as hard segments
• polyethers such as polyethylene glycol and polytetramethylene glycol
• aliphatic polyesters such as polyethylene adipate, polybutylene adipate, and polycaprolactone as soft.
• polyamide-based elastomers include, but are not limited to, block copolymers in which nylon 6, nylon 66, nylon 11, nylon 12 or the like is a hard segment and polyether or aliphatic polyester is a soft segment. It is not a thing.
• urethane elastomers include reaction of diisocyanates such as 4,4'-diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, tolylene diisocyanate and hexamethylene diisocyanate with glycols such as ethylene glycol and tetramethylene glycol.
• a polyether or polyethylene adipate such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol or an aliphatic polyester such as polybutylene adipate or polycaprolactone as a soft segment
• the content of the thermoplastic elastomer is preferably 10 to 30 parts by mass, more preferably 12 to 20 parts by mass with respect to 100 parts by mass of (A) PBT resin.
• the polybutylene terephthalate resin composition is MFR of a melt flow rate (MFR) after staying for 60 minutes at 260 ° C. in a melt flow rate tester defined in ISO 1133, after staying for 7 minutes at 260 ° C.
• MFR melt flow rate
• Ratio to MFR is preferably 0.8 to 5, more preferably 0.9 to 4, and particularly preferably 1 to 3. is there.
• the increase in viscosity is suppressed even when the PBT resin composition stays in the cylinder at a high temperature for a long time at the time of molding
• the viscosity suitable for the above can be maintained, and a decrease in mechanical physical properties can be suppressed by setting the viscosity to 5 or less.
• the form of the polybutylene terephthalate resin composition may be a powder mixture, or may be a melt mixture (melt-kneaded product) such as pellets.
• the method for producing the polybutylene terephthalate resin composition is not particularly limited, and can be produced using equipment and methods known in the art. For example, necessary components can be mixed and kneaded using a single- or twin-screw extruder or other melt-kneading apparatus to prepare molding pellets. A plurality of extruders or other melt kneading apparatuses may be used. Moreover, all the components may be simultaneously fed from the hopper, or some components may be fed from the side feed port.
• the application of the polybutylene terephthalate resin composition is not particularly limited, and can be widely used in various applications such as automotive parts and electric / electronic parts.
• this polybutylene terephthalate resin composition is excellent in alkali solution resistance, it can be suitably used for a molded article to be in contact with an alkaline solution such as a detergent or a snow melting agent.
• an alkaline solution such as a detergent or a snow melting agent.
• a molded product having a thin-walled portion generally, in order to ensure the fluidity for filling the resin in the thin-walled portion of the mold, it is necessary to increase the molding temperature.
• polybutylene terephthalate resin compositions to which an epoxy resin and a silicone compound have been added to impart alkaline solution properties, a dilemma occurs in which, when staying in the molten state, the increase in viscosity becomes remarkable and the flowability decreases.
• the polybutylene terephthalate resin composition of the present embodiment is excellent in moldability because the decrease in fluidity is suppressed even when staying at a high temperature. Therefore, this polybutylene terephthalate resin composition can be suitably used for a molded article having a thin-walled portion having a thickness of 1 mm or less at least partially.
• the injection amount of the resin composition per mold is small as in the production of small parts, the time for which the resin composition stays in the molding machine becomes long, and the resin composition Things are often heated for a long time.
• the conventional PBT resin containing an epoxy resin and a silicone compound tends to further increase the viscosity of the resin composition when the heating time becomes long.
• the polybutylene terephthalate resin composition according to the present embodiment is excellent in fluidity even when heated for a long time. Therefore, this PBT resin composition can be suitably used also for molded articles used as small parts having a volume of molded articles of 20 cm 3 or less.
• the polybutylene terephthalate resin composition when used for a case of an automobile sensor, an ECU case, and the like, adhesion and potting may be performed with an addition type silicone adhesive or the like.
• the phosphorus compound may be a substance inhibiting the effect of the silicone adhesive, but when it contains an alkali metal phosphate and / or an alkaline earth metal phosphate, there are very few cases that cause curing inhibition.
• a molded article using the PBT resin composition is excellent in adhesive strength with other parts by a silicone adhesive. Therefore, it can be suitably used for a molded article to be laminated with another member via a silicone adhesive layer, or for a molded article having a silicone adhesive layer on at least one surface.
• the molded article according to the present embodiment is a molded article molded using the above-described polybutylene terephthalate resin composition.
• the molding method of the molded article is not particularly limited, and can be formed by, for example, conventionally known injection molding, extrusion molding, blow molding (various hollow molded articles), vacuum molding, compression molding or the like.
• the molded article may have a thickness of at least 1 mm in at least a part of the portion containing the polybutylene terephthalate resin composition.
• the molded article may be used as a small part having a volume of 20 cm 3 or less.
• a molding is made to be laminated with another member via a silicone adhesive layer.
• the article may be a molded article having a silicone adhesive layer on at least one surface.
• the composite according to the present embodiment includes a molded article molded using the above PBT resin composition containing an alkali metal phosphate and / or an alkaline earth metal phosphate and at least one surface of the molded article. And having a silicone adhesive layer formed thereon.
• a conventionally known silicone adhesive can be used as the silicone adhesive constituting the silicone adhesive layer.
• the silicone adhesive is an adhesive that cures at room temperature or by heating, and conventionally known ones can be used. For example, mention is made of an addition reaction type silicone adhesive whose effect is promoted by an addition reaction with a platinum-based catalyst. Can.
• a composite is obtained by bonding a molded article formed using the above PBT resin composition containing an alkali metal phosphate and / or an alkaline earth metal phosphate with another member with a silicone adhesive. May be.
• the composite in this case has a configuration in which a molded product molded using a PBT resin composition and other members are laminated via a silicone adhesive layer. Examples of other members include molded articles of metals, alloys, inorganic solids or resins.
• the metal, alloy or inorganic solid is not particularly limited and can be selected according to the purpose.
• the resin is preferably one that does not inhibit the curing of the silicone-based adhesive, and in terms of having alkali solution resistance, it is preferable to use the above PBT resin composition.
• Epoxy group amount The amount of epoxy groups derived from the epoxy resin when the amount of terminal carboxyl groups of the polybutylene terephthalate resin was 1 was determined as follows.
• (Epoxy resin derived epoxy resin content in PBT resin composition) ⁇ (carboxyl content derived from PBT resin in PBT resin composition) (content of epoxy resin in PBT resin composition [kg] kg epoxy concerned Epoxy equivalent of resin [kg / meq]) (Content of PBT resin in PBT resin composition [kg] x amount of terminal carboxyl groups of PBT resin [meq / kg])
• Examples 1 to 4 and Comparative Examples 1 to 12 The components shown in Table 1 are dry-blended according to the composition (parts by mass) shown in Table 1, supplied from a hopper to a twin-screw extruder (made by Japan Steel Works Ltd.) having a 30 mm ⁇ screw and melt-kneaded at 260 ° C. The pellet-like PBT resin composition was obtained.
• MFR MFR for 7 minutes
• MFR g / 10 min
• MELT INDEXER L202 manufactured by Takara Co., Ltd., Thermistor.
• MFR for 60 minutes A MFR (g / 10 min) immediately after holding at a load of 2160 g at 260 ° C. for 60 minutes was measured using MELT INDEXER L202 manufactured by Takara Co., Ltd. Thermistor.
• the pellets of the PBT resin composition are dried at 140 ° C. for 3 hours, and then the test piece molding die (80 mm long, horizontal) with a cylinder temperature of 250 ° C., a mold temperature of 70 ° C., an injection time of 20 seconds and a cooling time of 10 seconds.
• a pin of 2 mm in width ⁇ 1 mm in thickness provided at the side center of one side of the flat plate by installing a pin at a position corresponding to the approximate center of one main surface of the flat plate.
• the other cut tensile test pieces were overlapped so as to be a combination of molded articles before cutting, fixed by clips, and heat-treated at 120 ° C. for 1 hour. After the heat treatment, the clip was removed to confirm the cured state of the adhesive. Adhesiveness was evaluated by setting “1” for which the adhesive was cured and the test pieces could be bonded and “2” for those in which the test pieces were not able to be bonded due to curing inhibition.
• the PBT resin compositions of Examples 1 to 4 are excellent in alkali resistance and hydrolysis resistance, and are retained for 7 minutes at 260 ° C. and for 60 minutes. Both are excellent in liquidity.
• the MFR for 60 minutes retention / the value of MFR for 7 minutes of retention was 0.8 or more, and it was possible to suppress the decrease in fluidity even when staying in the molten state for a long time.

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• 2017
  • 2017-08-30 JP JP2017165299A patent/JP6506806B2/ja active Active
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