WO2013179726A1 - ポリブチレンテレフタレート樹脂組成物、及び耐加水分解性向上剤 - Google Patents
ポリブチレンテレフタレート樹脂組成物、及び耐加水分解性向上剤 Download PDFInfo
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- WO2013179726A1 WO2013179726A1 PCT/JP2013/057290 JP2013057290W WO2013179726A1 WO 2013179726 A1 WO2013179726 A1 WO 2013179726A1 JP 2013057290 W JP2013057290 W JP 2013057290W WO 2013179726 A1 WO2013179726 A1 WO 2013179726A1
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- polybutylene terephthalate
- terephthalate resin
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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
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
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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
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
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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
Definitions
- the present invention relates to a polybutylene terephthalate resin composition excellent in hydrolysis resistance and fluidity, and a hydrolysis resistance improver that improves the hydrolysis resistance of the polybutylene terephthalate resin composition.
- Polybutylene terephthalate resin has excellent mechanical properties, electrical properties, heat resistance, weather resistance, water resistance, chemical resistance, and solvent resistance, so it can be used as an engineering plastic for automotive parts, electrical / electronic parts, etc. It is widely used for applications.
- polybutylene terephthalate resin has a problem in hydrolysis resistance and does not always have sufficient durability when used in a high temperature and high humidity environment.
- Patent Document 1 discloses a polybutylene terephthalate resin composition in which a carbodiimide compound and a fibrous filler are blended with a polybutylene terephthalate resin.
- the resin composition described in Patent Document 1 has high strength and excellent heat shock resistance, and excellent tensile strength retention (pressure resistance to hydrolysis) after the pressure cooker test. Yes.
- an increase in viscosity due to the reaction between the polybutylene terephthalate resin and the carbodiimide compound is a problem.
- some fluidity improvement effect is seen by using fatty acid ester together, hydrolysis resistance is impaired.
- Patent Document 2 discloses a polybutylene terephthalate resin composition excellent in fluidity in which a polybutylene terephthalate resin is blended with a glycerin fatty acid ester.
- a technique for improving hydrolysis resistance is disclosed. Has not been found.
- the present invention has been made in order to solve the above problems, and its purpose is to obtain a polybutylene terephthalate resin composition having both excellent hydrolysis resistance and high fluidity at the time of melting. Is to provide.
- a polybutylene terephthalate resin composition containing a carbodiimide compound and a specific polyhydric hydroxyl group-containing compound can improve the fluidity of the resin composition and also improve the hydrolysis resistance of the resin composition.
- the present invention has been completed. More specifically, the present invention provides the following.
- Polybutylene terephthalate containing (A) a polybutylene terephthalate resin having a terminal carboxyl group amount of 30 meq / kg or less, (B) a carbodiimide compound, and (C) a polyhydric hydroxyl group-containing compound having a hydroxyl value of 200 or more. Resin composition.
- the content of the (B) carbodiimide compound is such that when the terminal carboxyl group amount of the (A) polybutylene terephthalate resin in the polybutylene terephthalate resin composition is 1 equivalent, the carbodiimide functional group amount is 0.5.
- the content of the (C) polyvalent hydroxyl group-containing compound is 0.05 to 5 parts by mass with respect to 100 parts by mass of (A) polybutylene terephthalate resin, and any one of (1) to (4) The polybutylene terephthalate resin composition described in 1.
- Hydrolysis resistance which is blended with polybutylene terephthalate resin together with carbodiimide compound, or blended with polybutylene terephthalate resin before carbodiimide compound is blended to improve hydrolysis resistance of polybutylene terephthalate resin composition
- a hydrolysis resistance improver comprising a polyhydric hydroxyl group-containing compound having a hydroxyl value of 200 or more.
- a polybutylene terephthalate resin composition having both excellent hydrolysis resistance and high fluidity upon melting can be obtained.
- FIG. 1 is a diagram illustrating an example of an approximate curve created for each example and each comparative example, where the results of the examples and comparative examples are represented on a graph in which the vertical axis represents TS retention and the horizontal axis represents processing time. .
- the polybutylene terephthalate resin composition of the present invention contains (A) a polybutylene terephthalate resin, (B) a carbodiimide compound, and (C) a polyhydric hydroxyl group-containing compound.
- the (C) polyvalent hydroxyl group-containing compound is the hydrolysis resistance improver of the present invention.
- the polybutylene terephthalate resin includes at least a polymerization component of terephthalic acid (terephthalic acid or an ester-forming derivative thereof) and alkylene glycol (1,4-butanediol) having 4 carbon atoms or an ester-forming derivative thereof. It is a thermoplastic resin. Moreover, (A) polybutylene terephthalate resin is resin whose terminal carboxyl group amount is 30 meq / kg or less, as will be described later.
- polybutylene terephthalate resin PBT resin
- a homopolyester polybutylene terephthalate
- a copolyester a butylene terephthalate copolymer or a polybutylene terephthalate copolyester having repeating units derived from possible monomers in the proportions described below.
- copolymerizable monomer in the copolyester examples include dicarboxylic acid components excluding terephthalic acid, 1,4-butane Examples include diols other than diols, oxycarboxylic acid components, and lactone components.
- the copolymerizable monomers can be used alone or in combination of two or more.
- Dicarboxylic acids include aliphatic dicarboxylic acids (for example, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, hexadecandioyl carboxylic acid, C 4 ⁇ 40 dicarboxylic acids such as dimer acid, preferably C 4 ⁇ 14 dicarboxylic acids), alicyclic dicarboxylic acid component (e.g., hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, hymic C 8 ⁇ 12 dicarboxylic acids such as acid), an aromatic dicarboxylic acid component other than terephthalic acid (e.g., phthalic acid, isophthalic acid, naphthalene di
- polyvalent carboxylic acids such as trimellitic acid and a pyromellitic acid, or its ester formation derivative (alcohol ester etc.) etc. as needed.
- a polyfunctional compound such as trimellitic acid and a pyromellitic acid, or its ester formation derivative (alcohol ester etc.) etc.
- a branched polybutylene terephthalate resin can also be obtained.
- Diols include, for example, aliphatic alkanediols excluding 1,4-butanediol [for example, alkanediols (for example, ethylene glycol, trimethylene glycol, propylene glycol, neopentyl glycol, hexanediol ( 1,6-hexanediol, etc.), octanediol (1,3-octanediol, 1,8-octanediol, etc.), lower alkane diols, such as decanediol, preferably a straight chain or branched chain C 2 ⁇ 12 alkane Diols, more preferably linear or branched C 2-10 alkane diols, etc.); (poly) oxyalkylene glycols (eg glycols having a plurality of oxy C 2-4 alkylene units, eg di
- a polyol such as glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, or an ester-forming derivative thereof may be used in combination.
- a polyfunctional compound such as glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, or an ester-forming derivative thereof may be used in combination.
- a branched polybutylene terephthalate resin can also be obtained.
- Bisphenols include bis (4-hydroxyphenyl) methane (bisphenol F), 1,1-bis (4-hydroxyphenyl) ethane (bisphenol AD), 1,1-bis (4-hydroxyphenyl) propane, 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 Bis (hydroxyaryl) C 1 such as (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) hexane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, etc.
- alkanes 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxy) Shifeniru) bis (hydroxyaryl such cyclohexane) C 4 ⁇ 10 cycloalkanes, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulphide, 4,4'-dihydroxydiphenyl Examples thereof include ketones and their alkylene oxide adducts.
- alkylene oxide adduct bisphenol (e.g., bisphenol A, bisphenol AD, bisphenol F) C 2 ⁇ 3 alkylene oxide adduct of, for example, 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.
- Alkylene oxide addition mole number of (ethylene oxide, C 2 ⁇ 3 alkylene oxide such as propylene oxide) is from 1 to 10 moles for each hydroxy group, preferably 1 to 5 moles.
- oxycarboxylic acid examples include oxycarboxylic acids such as oxybenzoic acid, oxynaphthoic acid, hydroxyphenylacetic acid, glycolic acid, oxycaproic acid, and derivatives thereof.
- oxycarboxylic acids such as oxybenzoic acid, oxynaphthoic acid, hydroxyphenylacetic acid, glycolic acid, oxycaproic acid, and derivatives thereof.
- diols preferably diols [C 2 ⁇ 6 alkylene glycol (ethylene glycol, trimethylene glycol, propylene glycol, a linear or branched alkylene glycols such as hexanediol and the like), the number of repetitions polyoxy C 2-4 alkylene glycol having 2 to about 4 oxyalkylene units (diethylene glycol), bisphenol (bisphenol compound, or an alkylene oxide adduct)], dicarboxylic acids [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, 1,4-cyclohexanedimethanol, etc.].
- diols preferably diols [C 2 ⁇ 6 alkylene glycol (ethylene glycol, trimethylene glycol, prop
- the polybutylene terephthalate resin is preferably a homopolyester (polybutylene terephthalate) and / or a copolymer (polybutylene terephthalate copolyester).
- the proportion (modification amount) of the copolymerizable monomer is usually 45 mol% or less (for example, about 0 mol% or more and 45 mol% or less), preferably 35 mol% or less (for example, It may be a copolyester of 0 mol% or more and 35 mol% or less, more preferably 30 mol% or less (for example, about 0 mol% or more and 30 mol% or less).
- the proportion of the copolymerizable monomer can be selected, for example, from the range of about 0.01 mol% to 30 mol%, and is usually about 1 mol% to 30 mol%, preferably 3 mol. % Or more and about 25 mol% or less, more preferably about 5 to 20 mol%.
- the proportion of the homopolyester and the copolyester is such that the proportion of the copolymerizable monomer is relative to the total monomers.
- the range is from 0.1 mol% to 30 mol% (preferably about 1 mol% to 25 mol%, more preferably about 5 mol% to 25 mol%).
- the former / the latter 99 / It can be selected from the range of 1 to 1/99 (mass ratio), preferably 95/5 to 5/95 (mass ratio), more preferably 90/10 to 10/90 (weight ratio).
- the amount of terminal carboxyl groups of the polybutylene terephthalate resin is 30 meq / kg or less.
- a more preferred terminal carboxyl group amount is 25 meq / kg or less.
- the hydrolysis resistance of the polybutylene terephthalate resin composition can be improved by using (B) a carbodiimide compound or (C) a polyhydric hydroxyl group-containing compound, but the terminal carboxyl group amount of the polybutylene terephthalate resin is increased.
- the terminal carboxyl group amount of (A) polybutylene terephthalate resin needs to be 30 meq / kg or less.
- the intrinsic viscosity (IV) of the polybutylene terephthalate resin is preferably 0.6 dL / g or more, and more preferably 0.7 dL / g or more.
- the intrinsic viscosity is preferably 1.3 dL / g or less, and more preferably 1.2 dL / g or less.
- the intrinsic viscosity (IV) can be measured in o-chlorophenol at a temperature of 35 ° C.
- a polybutylene terephthalate resin having an intrinsic viscosity in such a range is used, it is easy to efficiently provide sufficient hydrolysis resistance and reduce melt viscosity. If the intrinsic viscosity is too small, there is a possibility that sufficient effect of improving hydrolysis resistance may not be obtained. If the intrinsic viscosity is too large, the melt viscosity at the time of molding becomes high, and in some cases, the resin in the molding die There is a possibility of causing poor flow and poor filling.
- (A) polybutylene terephthalate resin a commercially available product may be used.
- the (B) carbodiimide compound used in the present invention is a compound having a carbodiimide group (—N ⁇ C ⁇ N—) in the molecule.
- the carbodiimide compound any of an aliphatic carbodiimide compound having an aliphatic main chain, an alicyclic carbodiimide compound having an alicyclic main chain, and an aromatic carbodiimide compound having an aromatic main chain can be used. In view of the above, it is preferable to use an aromatic carbodiimide compound.
- Aliphatic carbodiimide compounds include diisopropyl carbodiimide, dioctyl decyl carbodiimide, di-tert-butyl carbodiimide, 1-ethyl-3-tert-butyl carbodiimide, 1- (2-butyl) -3-ethyl carbodiimide, 1,3-di -(2-butyl) carbodiimide, poly (diisopropylcarbodiimide) and the like.
- Examples of the alicyclic carbodiimide compound include dicyclohexylcarbodiimide and poly (diisopropylcarbodiimide).
- Aromatic carbodiimide compounds include diphenylcarbodiimide, di-2,6-dimethylphenylcarbodiimide, di-2,6-diethylphenylcarbodiimide, di-2,6-diisopropylphenylcarbodiimide, di-2,6-ditert-butyl.
- Two or more of the above carbodiimide compounds can be used in combination.
- di-2,6-dimethylphenylcarbodiimide, poly (4,4'-diphenylmethanecarbodiimide), poly (phenylenecarbodiimide) and poly (triisopropylphenylenecarbodiimide) are particularly preferably used.
- the “carbodiimide compound” (alicyclic carbodiimide compound, aromatic carbodiimide compound, etc.) in the present invention is a compound having a carbodiimide group in the cyclic structure, that is, a compound having a “carbodiimide ring” (“cyclic carbodiimide compound”). (Also called) is not included.
- the (B) carbodiimide compound it is preferable to use a compound having a number average molecular weight of 2000 or more.
- a compound having a number average molecular weight of 2000 or more it is possible to improve the hydrolysis resistance of the polybutylene terephthalate resin composition over a long period of time. Furthermore, it is advantageous in that the generation of gas and odor can be reduced even when the polybutylene terephthalate resin composition has a long residence time during melt kneading and molding.
- the blending amount of the (B) carbodiimide compound in the polybutylene terephthalate resin composition is such that when the terminal carboxyl group amount of the (A) polybutylene terephthalate resin is 1 equivalent, the carbodiimide functional group amount is 0.5 to 10 equivalents. An amount is preferred. (B) If the compounding quantity of a carbodiimide compound exists in the said range, the hydrolysis resistance of a polybutylene terephthalate resin composition can fully be improved.
- the blending amount of the carbodiimide compound is too small, the hydrolysis resistance improving effect intended by the present invention may not be sufficiently obtained.
- the blending amount of the (B) carbodiimide compound is too large, the fluidity of the resin composition is lowered, the gel component during compounding or molding, the formation of carbides, discoloration under high temperature environment, mechanical properties There is a risk of a decrease.
- a more preferable blending amount is such that when the terminal carboxyl group amount of the (A) polybutylene terephthalate resin is 1 equivalent, the amount of the carbodiimide functional group is 0.8 to 5 equivalents, most preferably 1 to 3 equivalents. Is the amount.
- a polybutylene terephthalate resin composition having excellent fluidity during molding and mechanical properties after molding can be obtained. Furthermore, when the amount of the carbodiimide functional group is 1 to 3 equivalents, in addition to excellent fluidity during molding and mechanical properties after molding, polybutylene has reduced discoloration in a high temperature environment. A terephthalate resin composition is obtained.
- a polyhydric hydroxyl group-containing compound is a compound having two or more hydroxyl groups in one molecule. Moreover, the (C) polyvalent hydroxyl group-containing compound has a hydroxyl value of 200 or more, as will be described later.
- the polyhydric hydroxyl group-containing compound serves as a hydrolysis resistance improver for improving the hydrolysis resistance of the polybutylene terephthalate resin composition in the polybutylene terephthalate resin composition in which the (B) carbodiimide compound is blended.
- the polyhydric hydroxyl group-containing compound also improves the fluidity of the polybutylene terephthalate resin composition. Usually, by adding a component that enhances fluidity to (A) polybutylene terephthalate resin, even if the fluidity can be improved, avoid deterioration of properties such as mechanical strength and toughness of (A) polybutylene terephthalate resin itself. I can't. However, by using the (C) polyhydric hydroxyl group-containing compound, the fluidity at the time of melting of the polybutylene terephthalate resin composition can be efficiently improved while maintaining the characteristics of the (A) polybutylene terephthalate resin at a high level.
- the (C) polyhydric hydroxyl group-containing compound is contained in the polybutylene terephthalate resin composition, thereby making use of the characteristics of the polybutylene terephthalate resin and improving the fluidity of the polybutylene terephthalate resin composition.
- the hydrolysis resistance of the product can also be improved.
- the melt viscosity measured at a furnace temperature of 260 ° C., a capillary ⁇ 1 mm ⁇ 20 mmL, and a shear rate of 1000 sec ⁇ 1 is 350 Pa ⁇ s or less in accordance with ISO11443. It is preferably 300 Pa ⁇ s or less, more preferably 250 Pa ⁇ s or less (for example, 200 Pa ⁇ s or less).
- the polyhydric hydroxyl group-containing compound one produced by a conventionally known method may be used, or a commercially available product may be purchased and used.
- the hydroxyl value of the polyvalent hydroxyl group-containing compound is 200 or more. Moreover, a preferable hydroxyl value is 250 or more. If the said hydroxyl value is 200 or more, in addition to the tendency for the said fluid improvement effect to increase more, the effect which improves hydrolysis resistance is acquired. On the other hand, when the hydroxyl value is too large, the reaction with (A) polybutylene terephthalate proceeds excessively, the molecular weight of (A) polybutylene terephthalate resin is lowered, and excellent mechanical properties, heat resistance, chemical resistance, etc. May damage the characteristics.
- the preferred hydroxyl value is 1000 or less, and more preferably 500 or less.
- the content of the (C) polyhydric hydroxyl group-containing compound in the polybutylene terephthalate resin composition is preferably 0.05 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the (A) polybutylene terephthalate resin. . More preferably, it is 0.1 to 3 parts by mass. More preferably, they are 0.5 mass part or more and 2 mass parts or less. If the content of the polyvalent hydroxyl group-containing compound is 0.05 parts by mass or more, the effect of improving the fluidity tends to be obtained sufficiently, and if it is 5 parts by mass or less, molding by gas generation during molding is preferable. This is preferable because there is almost no risk of appearance defects and mold contamination.
- the glycerin fatty acid ester is an ester composed of glycerin and / or a dehydration condensate thereof and a fatty acid.
- glycerin fatty acid esters those obtained using fatty acids having 12 or more carbon atoms are preferred.
- the fatty acid having 12 or more carbon atoms include lauric acid, oleic acid, palmitic acid, stearic acid, 12-hydroxystearic acid, behenic acid, and montanic acid.
- Fatty acids having 12 to 32 carbon atoms are preferred, and fatty acids having 12 to 22 carbon atoms are particularly preferred.
- lauric acid, stearic acid, 12-hydroxystearic acid or behenic acid is particularly preferable.
- It is preferable to use a fatty acid having 12 or more carbon atoms because the heat resistance of the resin tends to be sufficiently maintained.
- a carbon number of 32 or less is preferable because the effect of improving the fluidity is high.
- Examples of preferred glycerin fatty acid esters include glycerin monostearate, glycerin monobehenate, diglycerin monostearate, triglycerin monostearate, triglycerin stearic acid partial ester, tetraglycerin stearic acid partial ester, decaglycerin lauric acid partial ester Glycerin mono-12-hydroxystearate and the like.
- the ether obtained by addition polymerization of alkylene oxide to diglycerin is obtained by, for example, polyoxypropylene diglyceryl ether obtained by addition polymerization of propylene oxide to diglycerin or addition polymerization of ethylene oxide to diglycerin.
- Polyoxyethylene diglyceryl ether is mentioned. In the present invention, among these ethers, use of polyoxyethylene diglyceryl ether is particularly preferable.
- the polybutylene terephthalate resin composition of the present invention preferably contains an inorganic filler. By blending the inorganic filler, physical properties such as mechanical strength of the obtained molded product can be further enhanced.
- any of a fibrous filler, a granular filler, a plate filler and the like can be used.
- the fibrous filler include glass fiber, asbestos fiber, silica fiber, silica / alumina fiber, alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, stainless steel, aluminum, titanium Inorganic fibrous materials such as metallic fibrous materials such as copper and brass.
- silica silica, quartz powder, glass beads, milled glass fiber, glass balloon, glass powder, calcium silicate, aluminum silicate, kaolin, talc, clay, diatomaceous earth, silicates such as wollastonite, iron oxide, Metal oxides such as titanium oxide, zinc oxide, antimony trioxide, and alumina, carbonates of metals such as calcium carbonate and magnesium carbonate, sulfates of metals such as calcium sulfate and barium sulfate, other ferrites, silicon carbide, silicon nitride , Boron nitride, various metal powders, and the like.
- the plate-like filler include mica, glass flakes, various metal foils and the like.
- the usage-amount of an inorganic filler is 10 mass parts or more and 200 mass parts or less with respect to 100 mass parts of (A) polybutylene terephthalate resin, for example.
- the resin composition of the present invention includes other resins, reinforcing fillers, flame retardants, antioxidants, heat stabilizers, ultraviolet absorbers, antistatic agents, dyes and pigments as long as the effects of the present invention are not impaired.
- a conventionally known additive such as a colorant such as a lubricant, a plasticizer, and a crystal nucleating agent can be contained.
- the reaction between (A) the polybutylene terephthalate resin and (C) the polyhydric hydroxyl group-containing compound is promoted.
- the reaction between the (A) polybutylene terephthalate resin and the (C) polyhydric hydroxyl group-containing compound is slow and it takes time to reach the desired fluidity, the transesterification reaction catalyst can be used to quickly The desired fluidity can be realized.
- the transesterification reaction catalyst is not particularly limited, and for example, a metal compound can be used as the transesterification catalyst.
- a metal compound can be used as the transesterification catalyst.
- titanium compounds, tin compounds, and antimony compounds are preferably used.
- Specific examples of the titanium compound include inorganic titanium compounds such as titanium oxide, titanium alcoholates such as tetramethyl titanate, tetraisopropyl titanate, and tetrabutyl titanate, titanium phenolates such as tetraphenyl titanate, and the like.
- tin compounds include dibutyltin oxide, hexaethylditin oxide, didodecyltin oxide, triethyltin hydroxide, tributyltin acetate, dibutyltin diacetate, diphenyltin dilaurate, monobutyltin trichloride, methylstannic acid, ethylstannon Examples thereof include acid and butylstannic acid.
- antimony compound include antimony trioxide. Of these, tetrabutyl titanate, tributyltin acetate, and antimony trioxide are particularly preferable.
- the transesterification reaction proceeds excessively, the physical properties of a molded article formed by molding the resin composition may be lowered.
- the desired fluidity can be adjusted without causing problems such as deterioration of physical properties.
- a phosphorus compound can be preferably used as the transesterification reaction terminator.
- the kind and amount of the phosphorus compound are not particularly limited and can be appropriately adjusted according to conditions such as the kind of the compound contained in the composition of the present invention.
- the phosphorus compound that can be used is not particularly limited, and phosphine, phosphinite, phosphonite, phosphite, phosphinas amide, phosphonas diamide, phosphorous triamide, phosphoramidite, phosphorodiamidite, phosphine
- Examples include phosphorus compounds of oxide, phosphinate, phosphonate, phosphate, phosphinic amide, phosphonodiamidate, phosphoramide, phosphoramidate, phosphorodiamidate, phosphine imide, and phosphine sulfide. it can.
- phosphorus compounds include those formed with salts with metals.
- the method for preparing the polybutylene terephthalate resin composition of the present invention is not particularly limited, and generally known equipment and methods can be used as a method for preparing the resin composition.
- necessary components can be mixed and kneaded using a single or twin screw extruder or other melt kneader to prepare pellets for molding.
- a plurality of extruders or other melt kneaders may be used.
- all the components may be charged simultaneously from the hopper, or some components may be charged from the side feed port.
- the extruder cylinder temperature is preferably set so that the resin temperature in the extruder is 240 to 300 ° C.
- the temperature is lower than 240 ° C.
- the reaction between (A) polybutylene terephthalate resin and (B) carbodiimide compound becomes insufficient, and the hydrolysis resistance of the resin composition is insufficient, or the viscosity of the melt is high.
- a resin composition having uniform characteristics cannot be obtained without being sufficiently kneaded.
- it exceeds 300 degreeC decomposition
- (B) a carbodiimide compound may be added after (A) polybutylene terephthalate resin and (C) a polyhydric hydroxyl group-containing compound are first melt-kneaded. .
- the (B) carbodiimide compound is added in a state where the melt viscosity of the (A) polybutylene terephthalate resin is reduced, uniform melt kneading can be performed efficiently.
- (B) a carbodiimide compound and (D) an inorganic filler if (D) the inorganic filler is added first, the interfacial adhesion between (A) the polybutylene terephthalate resin and (D) the inorganic filler becomes stronger. Therefore, it is preferable.
- the (B) carbodiimide compound can be blended as a master batch using a resin as a matrix, and it is often easy to use the master batch from the viewpoint of actual handling.
- a masterbatch made of polybutylene terephthalate resin is preferably used, but a masterbatch prepared with another resin may be used. What is necessary is just to adjust so that it may become in the range of a predetermined compounding quantity in the case of the masterbatch by polybutylene terephthalate resin.
- Terminal amount of carboxyl group (CEG) The terminal amount of the carboxyl group was determined by dissolving a pulverized sample of the resin composition pellet of the present invention in benzyl alcohol at 215 ° C. for 10 minutes and titrating with a 0.01N aqueous sodium hydroxide solution. The results are shown in Table 1.
- PCT Pressure Cooker Test
- TS retention (unit:%) (TS after processing for a predetermined time / TS before processing) ⁇ 100
- Example 5 where the equivalent ratio was “4.0”, a slight discoloration was observed in the test piece after the PCT treatment. However, the melt viscosity characteristics and TS retention of Example 5 were sufficiently excellent.
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Abstract
Description
(A)ポリブチレンテレフタレート樹脂とは、テレフタル酸(テレフタル酸又はそのエステル形成誘導体)と、炭素数4のアルキレングリコール(1,4-ブタンジオール)又はそのエステル形成誘導体とを、少なくとも重合成分とする熱可塑性樹脂である。また、(A)ポリブチレンテレフタレート樹脂は、後述する通り、末端カルボキシル基量が30meq/kg以下の樹脂である。
本発明で用いられる(B)カルボジイミド化合物とは、分子中にカルボジイミド基(-N=C=N-)を有する化合物である。カルボジイミド化合物としては、主鎖が脂肪族の脂肪族カルボジイミド化合物、主鎖が脂環族の脂環族カルボジイミド化合物、主鎖が芳香族の芳香族カルボジイミド化合物のいずれも使用できるが、耐加水分解性の点で芳香族カルボジイミド化合物の使用が好ましい。
(C)多価水酸基含有化合物は、一分子中に水酸基を2個以上有する化合物である。また、(C)多価水酸基含有化合物は、後述する通り、水酸基価が200以上である。
本発明のポリブチレンテレフタレート樹脂組成物には、無機充填材を配合することが好ましい。無機充填材が配合されることで、得られる成形品の機械的強度等の物性をさらに高めることができる。
本発明の樹脂組成物には、本発明の効果を害さない範囲で、他の樹脂や強化用充填材、難燃剤、酸化防止剤、耐熱安定剤、紫外線吸収剤、帯電防止剤、染料や顔料等の着色剤、潤滑剤、可塑剤、結晶核剤等の従来公知の添加剤を含有させることができる。本発明においては、他の成分として、エステル交換反応触媒、エステル交換反応停止剤を含有させることが好ましい場合がある。
本発明のポリブチレンテレフタレート樹脂組成物の調製法は特に限定されるものではなく、一般に樹脂組成物の調製法として公知の設備と方法を用いることができる。例えば、必要な成分を混合し、1軸又は2軸の押出機又はその他の溶融混練装置を使用して混練し、成形用ペレットとして調製することができる。また、押出機又はその他の溶融混練装置は複数使用してもよい。また、全ての成分をホッパから同時に投入してもよいし、一部の成分はサイドフィード口から投入してもよい。ここで押出機中での樹脂温度は、240~300℃となるように押出機シリンダー温度を設定することが好ましい。さらに好ましくは250~270℃である。240℃より低い場合は、(A)ポリブチレンテレフタレート樹脂と(B)カルボジイミド化合物との反応が不十分になり、樹脂組成物の耐加水分解性が不足したり、溶融物の粘度が高いことで十分に混練されず、均一な特性を有する樹脂組成物が得られないおそれがある。一方、300℃を超える場合は樹脂の分解が生じやすくなり、樹脂組成物の機械物性や耐加水分解性が不足するおそれがある。
さらに、(B)カルボジイミド化合物と(D)無機充填材は、(D)無機充填材を先に添加すれば(A)ポリブチレンテレフタレート樹脂と(D)無機充填材の界面密着がより強固となるため好ましい。
<材料>
(A)ポリブチレンテレフタレート樹脂
A-1:ポリブチレンテレフタレート樹脂(固有粘度=0.68dL/g、カルボキシル基末端量=27meq/kg、ウィンテックポリマー株式会社製)
A-2:ポリブチレンテレフタレート樹脂(固有粘度=0.87dL/g、カルボキシル基末端量=16meq/kg、ウィンテックポリマー株式会社製)
A-3:ポリブチレンテレフタレート樹脂(固有粘度=1.14dL/g、カルボキシル基末端量=12meq/kg、ウィンテックポリマー株式会社製)
(B)カルボジイミド化合物
B-1:ラインケミージャパン株式会社製、スタバックゾールP400
(C)多価水酸基含有化合物
C-1:トリグリセリンステアリン酸部分エステル(水酸基価280、理研ビタミン株式会社製、「リケマールAF-70」)
C-2:ペンタエリスリトールテトラステアレート(水酸基価11、コグニスジャパン株式会社製、「ロキシオールVPG861」)
(A)ポリブチレンテレフタレート樹脂、(B)カルボジイミド化合物、(C)多価水酸基含有化合物を、表1に示す配合組成で秤量後ドライブレンドし、二軸押出機(株式会社日本製鋼所製TEX-30)にて、シリンダー温度を260℃、スクリュー回転数を130rpm、押出量を12kg/hとして、溶融混練を行い、吐出されたストランド状の溶融樹脂を冷却し、ペレタイザーによりカッティングすることにより、樹脂組成物のペレット状サンプルを得た。次いで、このペレットを用いて以下の各種評価を行った。
カルボキシル基末端量は、本発明の樹脂組成物ペレットの粉砕試料をベンジルアルコール中215℃で10分間溶解後、0.01Nの水酸化ナトリウム水溶液にて滴定することにより求めた。結果を表1に示す。
本発明の樹脂組成物のペレットを140℃で3時間乾燥後、ISO11443に準拠し、キャピログラフ1B(東洋精機製作所社製)を用いて、炉体温度260℃、キャピラリーφ1mm×20mmL、剪断速度1000sec-1にて測定した。結果を表1に示す。
本発明の樹脂組成物のペレットを140℃で3時間乾燥後、樹脂温度260℃、金型温度80℃、射出時間15秒、冷却時間15秒で、ISO3167引張り試験片を射出成形し、ISO527-1,2に準拠し引張り強さを測定した。結果を表1に示す。
引張り強さ試験に用いた試験片を、プレッシャークッカー試験機で121℃、100%RHの条件で処理し、処理後の引張り強さを測定し、処理前後での保持率を求めた。処理時間及び試験結果を表1に示す。また、実施例及び比較例の結果を、縦軸がTS保持率、横軸が処理時間のグラフ上に表し、実測した結果を表すドットに基づいて、各実施例及び各比較例について近似曲線を作成した。各近似曲線において、TS保持率が80%になる処理時間を表1に示した。なお、図1には、PBTとして(A-2)を使用した実施例(実施例2)及び比較例(比較例2、5、8、10)についての上記近似曲線を示す。また、グラフ内の矢印は、TS保持率が80%になる処理時間を示す。
なお、TS保持率は、下式に基づいて算出した。
TS保持率(単位:%)=(所定時間処理後のTS/処理前のTS)×100
Claims (7)
- (A)末端カルボキシル基量が30meq/kg以下のポリブチレンテレフタレート樹脂と、(B)カルボジイミド化合物、(C)水酸基価が200以上の多価水酸基含有化合物とを含有するポリブチレンテレフタレート樹脂組成物。
- 前記(A)ポリブチレンテレフタレート樹脂の固有粘度が0.6dL/g以上である請求項1に記載のポリブチレンテレフタレート樹脂組成物。
- 前記(C)カルボジイミド化合物の含有量は、前記ポリブチレンテレフタレート樹脂組成物における、(A)ポリブチレンテレフタレート樹脂の末端カルボキシル基量を1当量とした場合、カルボジイミド官能基量が0.5~10当量となる量である請求項1又は2に記載のポリブチレンテレフタレート樹脂組成物。
- 前記(C)多価水酸基含有化合物が、炭素数12以上の脂肪酸とからなるエステル結合を有する、請求項1から3のいずれかに記載のポリブチレンテレフタレート樹脂組成物。
- 前記(C)多価水酸基含有化合物の含有量は、(A)ポリブチレンテレフタレート樹脂100質量部に対し、0.05~5質量部である、請求項1から4のいずれかに記載のポリブチレンテレフタレート樹脂組成物。
- さらに(D)無機充填材を含む、請求項1から5のいずれかに記載のポリブチレンテレフタレート樹脂組成物。
- カルボジイミド化合物とともにポリブチレンテレフタレート樹脂に添加されるか、又はカルボジイミド化合物が配合される前にポリブチレンテレフタレート樹脂に添加され、ポリブチレンテレフタレート樹脂組成物の耐加水分解性を向上させる耐加水分解性向上剤であって、
水酸基価が200以上の多価水酸基含有化合物から構成される耐加水分解性向上剤。
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JP2018123239A (ja) * | 2017-02-01 | 2018-08-09 | 矢崎総業株式会社 | 自動車用高温耐油性成形部品 |
WO2020203436A1 (ja) * | 2019-04-01 | 2020-10-08 | ポリプラスチックス株式会社 | 熱可塑性樹脂の耐アルカリ溶液性向上方法 |
WO2021065094A1 (ja) * | 2019-09-30 | 2021-04-08 | ポリプラスチックス株式会社 | ポリブチレンテレフタレート樹脂組成物 |
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CN111154240B (zh) * | 2020-01-20 | 2022-02-01 | 湖北工业大学 | 一种光缆护套用高性能和耐水解的聚对苯二甲酸丁二醇酯树脂的改性方法 |
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US20150126658A1 (en) | 2015-05-07 |
TW201402643A (zh) | 2014-01-16 |
JP5916853B2 (ja) | 2016-05-11 |
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CN104379670A (zh) | 2015-02-25 |
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