WO2015072216A1 - 熱可塑性ポリエステル樹脂組成物および成形品 - Google Patents
熱可塑性ポリエステル樹脂組成物および成形品 Download PDFInfo
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- WO2015072216A1 WO2015072216A1 PCT/JP2014/073326 JP2014073326W WO2015072216A1 WO 2015072216 A1 WO2015072216 A1 WO 2015072216A1 JP 2014073326 W JP2014073326 W JP 2014073326W WO 2015072216 A1 WO2015072216 A1 WO 2015072216A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- 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
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
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- 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
- C08G59/20—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 epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3218—Carbocyclic compounds
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- 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
- C08G59/68—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 catalysts used
- C08G59/686—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 catalysts used containing nitrogen
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- 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
- C08G59/68—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 catalysts used
- C08G59/688—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 catalysts used containing phosphorus
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- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
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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
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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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
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/04—Epoxynovolacs
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/05—Polymer mixtures characterised by other features containing polymer components which can react with one another
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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
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/66—Substances characterised by their function in the composition
- C08L2666/78—Stabilisers against oxidation, heat, light or ozone
- C08L2666/82—Phosphorus-containing stabilizers
Definitions
- the present invention relates to a thermoplastic polyester resin composition and a molded product obtained by molding it.
- Thermoplastic polyester resins are used in a wide range of fields such as mechanical mechanism parts, electrical / electronic parts, and automobile parts, taking advantage of their excellent properties such as injection moldability and mechanical properties.
- the thermoplastic polyester resin is easily degraded by hydrolysis, it has general chemical and physical properties for use as industrial materials such as mechanical mechanism parts, electrical parts, electronic parts, and automobile parts. In addition to balance, it is required to have hydrolysis resistance in the long term.
- thinner and lighter molded products as well as smaller molded products.
- burrs and shorts can be formed during molding. Since molding defects such as shots occur, there is a demand for a material that has little change in viscosity during melt residence and has excellent residence stability.
- thermoplastic polyester resin As a method of imparting hydrolysis resistance to a thermoplastic polyester resin, a method of blending an epoxy resin with a thermoplastic polyester resin is known.
- a resin composition a thermoplastic composition containing a thermoplastic polyester resin, an epoxy resin having an average epoxy equivalent of 80 to 1000, and a curing accelerator used in the epoxy resin (see Patent Document 1) ), A thermoplastic polyester resin is blended with an aromatic vinyl resin having a weight average molecular weight of 1000 to 10,000, an amide compound having a molecular weight of 1000 or less, a polyhydric alcohol compound having three or more hydroxyl groups, an epoxy compound, and a fibrous filler.
- the polyester resin composition formed (refer patent document 2) is proposed, there existed a subject that hydrolysis resistance was still inadequate also by these techniques.
- a flame retardant resin composition obtained by blending a thermoplastic polyester resin with polyphenylene sulfide, an epoxy resin, a flame retardant and a flame retardant aid
- a flame retardant resin composition (see Patent Document 4) containing a phosphorus-based flame retardant and an epoxy resin having a specific structure has been proposed for a plastic resin.
- the present invention provides a thermoplastic polyester resin composition having excellent residence stability, excellent mechanical properties and heat resistance, and capable of obtaining a molded product having excellent long-term hydrolysis resistance, and a molded product thereof.
- the task is to do.
- the present inventors have formulated the above-described problems by blending (A) a thermoplastic polyester resin with a specific amount of (B) a novolac type epoxy resin having a specific structure.
- the present invention has been found. That is, the present invention has the following configuration.
- thermoplastic polyester resin composition comprising (B) 0.1 to 10 parts by weight of a novolac type epoxy resin represented by the following general formula (1) with respect to 100 parts by weight of a thermoplastic polyester resin;
- X represents a divalent group represented by the general formula (2) or (3); in the general formulas (1) and (2), each of R 1 to R 4 represents Each independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms, and may be the same or different; R 5 represents hydrogen, an alkyl group having 1 to 8 carbon atoms or 6 to 6 carbon atoms; 10 represents an aryl group; in the above general formula (1), n represents a value greater than 0 and 10 or less; in the above general formulas (1) and (2), a, c and d each independently represent 0 to 4 represents a value, and b represents a value of 0 to 3.
- the present invention includes a molded product obtained by melt-molding the above thermoplastic polyester resin composition.
- thermoplastic polyester resin composition of the present invention is excellent in retention stability. According to the thermoplastic polyester resin composition of the present invention, it is possible to obtain a molded article having excellent mechanical properties and heat resistance, and further excellent long-term hydrolysis resistance.
- thermoplastic polyester resin composition of the present invention will be described in detail.
- (A) Although the thermoplastic polyester resin is excellent in injection moldability and mechanical properties, the ester bond is easily decomposed by hydrolysis. When the ester bond is broken, the carboxyl end group concentration increases. As the carboxyl end group concentration increases, the molecular weight reduction of the (A) thermoplastic polyester resin is promoted, and the mechanical properties deteriorate.
- thermoplastic polyester resin is blended with (B) the novolac type epoxy resin represented by the general formula (1), and (A) the carboxyl terminal of the thermoplastic polyester resin produced by hydrolysis.
- the group and (B) the novolac-type epoxy resin represented by the general formula (1) react to suppress an increase in the carboxyl end group concentration, and (A) the high mechanical properties of the thermoplastic polyester resin are maintained. Can do.
- the thermoplastic polyester resin comprises (1) a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof, (2) a hydroxycarboxylic acid or an ester-forming derivative thereof, and (3) a lactone. It is a polymer or copolymer having at least one residue selected from the group as a main structural unit.
- the “main structural unit” means having 50 mol% or more of at least one residue selected from the group consisting of (1) to (3) in all the structural units. Is preferably 80 mol% or more.
- dicarboxylic acid or its ester-forming derivative examples include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, and anthracene.
- Aromatic dicarboxylic acids such as dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 5-tetrabutylphosphonium isophthalic acid, 5-sodium sulfoisophthalic acid; oxalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedione Aliphatic dicarboxylic acids such as acid, malonic acid, glutaric acid and dimer acid; alicyclic dicarboxylic acids such as 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, and ester-forming derivatives thereof . Two or more of these may be used.
- diol or its ester-forming derivative examples include ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol.
- Aliphatic or cycloaliphatic glycols having 2 to 20 carbon atoms such as cyclohexanedimethanol, cyclohexanediol and dimerdiol; long molecular weights of 200 to 100,000 such as polyethylene glycol, poly-1,3-propylene glycol and polytetramethylene glycol Chain glycol; aromatic dioxy compounds such as 4,4′-dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, bisphenol A, bisphenol S, bisphenol F, and the like Etc. Le forming derivatives thereof. Two or more of these may be used.
- polystyrene resin examples include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate.
- Polyhexylene terephthalate polyethylene isophthalate, polypropylene isophthalate, polybutylene isophthalate, polycyclohexanedimethylene isophthalate, polyhexylene isophthalate, polyethylene naphthalate, polypropylene naphthalate, polybutylene naphthalate, polyethylene isophthalate / terephthalate , Polypropylene isophthalate / terephthalate, polybutylene isophthalate / terephthalate Talate, polyethylene terephthalate / naphthalate, polypropylene terephthalate / naphthalate, polybutylene terephthalate / naphthalate, polybutylene terephthalate / decane dicarboxylate, polyethylene terephthalate / cyclohexanedimethylene terephthalate, polyethylene terephthalate / 5-sodium sulfoisophthalate,
- Examples of the hydroxycarboxylic acid or ester-forming derivative thereof include glycolic acid, lactic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy- Examples include 2-naphthoic acid and ester-forming derivatives thereof. Two or more of these may be used.
- Examples of the polymer or copolymer having these residues as structural units include polyglycolic acid, polylactic acid, polyglycolic acid / lactic acid, and polyhydroxybutyric acid / ⁇ -hydroxybutyric acid / ⁇ -hydroxyvaleric acid. And aliphatic polyester resins.
- lactones examples include caprolactone, valerolactone, propiolactone, undecalactone, and 1,5-oxepan-2-one. Two or more of these may be used.
- the polymer or copolymer having these residues as structural units include polycaprolactone, polyvalerolactone, polypropiolactone, and polycaprolactone / valerolactone.
- thermoplastic polyester resin a polymer or copolymer having as main structural units a residue of a dicarboxylic acid or an ester-forming derivative thereof and a residue of a diol or an ester-forming derivative thereof.
- a polymer or copolymer having a main structural unit composed of a residue of an aromatic dicarboxylic acid or its ester-forming derivative and a residue of an aliphatic diol or its ester-forming derivative More preferably, the residue of an aromatic dicarboxylic acid selected from terephthalic acid and naphthalenedicarboxylic acid or an ester-forming derivative thereof and an aliphatic diol selected from ethylene glycol, propylene glycol, butanediol, and cyclohexanedimethanol, or an ester-forming property thereof Derivative residues main structure Position to the polymer or copolymer is more preferred.
- the ratio of the residue of terephthalic acid or its ester-forming derivative to the total dicarboxylic acid residue in the polymer or copolymer is preferably 30 mol% or more, more preferably 40 mol% or more. .
- thermoplastic polyester resin a liquid crystalline polyester resin capable of forming anisotropy when melted can also be used.
- the structural unit of the liquid crystalline polyester resin include aromatic oxycarbonyl units, aromatic dioxy units, aromatic and / or aliphatic dicarbonyl units, alkylene dioxy units, and aromatic iminooxy units.
- the amount of carboxyl end groups of the thermoplastic polyester resin is preferably 50 eq / t or less, more preferably 30 eq / t or less, in terms of fluidity, hydrolysis resistance and heat resistance.
- the lower limit of the amount of carboxyl end groups is 0 eq / t.
- the amount of carboxyl end groups of the thermoplastic polyester resin is a value measured by dissolving (A) the thermoplastic polyester resin in o-cresol / chloroform solvent and titrating with ethanolic potassium hydroxide. is there.
- the amount of hydroxyl terminal groups of the thermoplastic polyester resin is preferably 50 eq / t or more, more preferably 80 eq / t or more, and still more preferably 100 eq / t or more in terms of moldability and fluidity. And particularly preferably 120 eq / t or more.
- the upper limit of the amount of hydroxy end groups is preferably 180 eq / t.
- thermoplastic polyester resin preferably has an intrinsic viscosity in the range of 0.50 to 1.50 dl / g when an o-chlorophenol solution is measured at a temperature of 25 ° C.
- the molecular weight of the thermoplastic polyester resin is such that the weight average molecular weight (Mw) is in the range of more than 8000 and less than 500,000, more preferably more than 8,000 and less than or equal to 300,000 in terms of further improving heat resistance. It is a range, More preferably, it is the range of more than 8000 and 250,000 or less.
- Mw of the thermoplastic polyester resin is a value in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent.
- thermoplastic polyester resin can be produced by a known polycondensation method or ring-opening polymerization method.
- the production method may be either batch polymerization or continuous polymerization, and any of transesterification and direct polymerization can be applied.
- Continuous polymerization is preferred in that the amount of carboxyl end groups can be reduced and the effect of improving fluidity is increased, and direct polymerization is preferably used in terms of cost.
- thermoplastic polyester resin is a polymer or copolymer having the main structural unit as the residue of dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative
- dicarboxylic acid or its An ester-forming derivative and a diol or an ester-forming derivative thereof can be produced by an esterification reaction or a transesterification reaction and then a polycondensation reaction.
- the polymerization reaction catalyst include titanic acid methyl ester, tetra-n-propyl ester, tetra-n-butyl ester, tetraisopropyl ester, tetraisobutyl ester, tetra-tert-butyl ester, cyclohexyl ester, phenyl ester, Organic titanium compounds such as benzyl ester, tolyl ester, or mixed esters thereof; dibutyltin oxide, methylphenyltin oxide, tetraethyltin, hexaethylditin oxide, cyclohexahexyldistin oxide, didodecyltin oxide, triethyltin hydroxide , Triphenyltin hydroxide, triisobuty
- organic titanium compounds and tin compounds are preferable, tetra-n-propyl ester, tetra-n-butyl ester and tetraisopropyl ester of titanic acid are more preferable, and tetra-n-butyl ester of titanic acid. Is particularly preferably used. Two or more of these may be used in combination.
- the addition amount of the polymerization reaction catalyst is preferably in the range of 0.005 to 0.5 parts by weight, more preferably 0.01 to 100 parts by weight of the thermoplastic polyester resin in terms of mechanical properties, moldability and color tone. It is in the range of ⁇ 0.2 parts by weight.
- thermoplastic polyester resin composition of the present invention is characterized in that (B) a novolac type epoxy resin represented by the following general formula (1) is blended with (A) a thermoplastic polyester resin.
- thermoplastic polyester resins tend to be deteriorated by hydrolysis.
- X represents a divalent group represented by the general formula (2) or (3).
- R 1 to R 4 each independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms, and may be the same or different.
- R 5 represents hydrogen, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 10 carbon atoms.
- n represents a value greater than 0 and 10 or less.
- a, c and d each independently represent a value of 0 to 4, and b represents a value of 0 to 3.
- X in the general formula (1) is preferably a divalent group represented by the general formula (2).
- Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and tert-butyl group. Among these, a methyl group is preferable in terms of reactivity.
- Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a methylphenyl group, a dimethylphenyl group, and a naphthyl group. Among these, a phenyl group is preferable in terms of reactivity.
- a, b, c and d are preferably 0 to 1 in terms of reactivity.
- the blending amount of the (B) novolac type epoxy resin represented by the general formula (1) is 0.1 to 10 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin.
- the amount is preferably 8 parts by weight or less, and more preferably 5 parts by weight or less.
- a preferable range of the blending amount of the novolac type epoxy resin represented by the general formula (1) can be set according to the epoxy equivalent.
- the ratio of the epoxy group compounding concentration (eq / g) derived from the novolak type epoxy resin (epoxy group compounding concentration / carboxyl terminal group compounding concentration) is preferably 1-8.
- the epoxy group blending concentration / carboxyl terminal group blending concentration is 1 or more, the long-term hydrolysis resistance can be further improved.
- the epoxy group concentration / carboxyl terminal group concentration is more preferably 2 or more.
- the epoxy group blending concentration / carboxyl terminal group blending concentration is 8 or less, suppression of bleed out, heat resistance and mechanical properties can be balanced at a higher level. 7 or less is preferable and 5 or less is more preferable.
- the carboxyl end group-derived concentration derived from the thermoplastic polyester resin in the thermoplastic polyester resin composition refers to the carboxyl group end concentration of the component (A) as a raw material and the thermoplastic polyester resin composition. It is the calculated value of the carboxyl end group concentration calculated from the blending ratio of the component (A) in the whole product.
- the carboxyl end group concentration of the thermoplastic polyester resin was determined by using a solution obtained by dissolving (A) a thermoplastic polyester resin in a mixed solution of o-cresol / chloroform (2/1 vol) using 1% bromophenol blue as an indicator. It can be calculated by titrating with 0.05 mol / L ethanolic potassium hydroxide.
- the (B) epoxy group compound concentration derived from the novolac type epoxy resin represented by the general formula (1) in the thermoplastic polyester resin composition is the same as the epoxy group concentration of the component (B) used as a raw material, and the thermoplasticity. It is the calculated value of the epoxy group concentration calculated from the blending ratio of the component (B) in the entire polyester resin composition.
- the epoxy group concentration of the novolak type epoxy resin represented by the general formula (1) is in accordance with JISK7236: 2001.
- the novolak type epoxy resin represented by the general formula (1) is dissolved in chloroform. The solution can be calculated by adding an acetic acid and triethylammonium bromide / acetic acid solution to the solution and potentiometrically titrating with 0.1 mol / L acetic acid perchlorate.
- thermoplastic polyester resin As a first factor for achieving hydrolysis resistance, (B) a novolac type epoxy resin represented by the general formula (1) is blended, and (A) a thermoplastic polyester resin. It is considered important to reduce the carboxyl end groups originally present in the reaction. From this viewpoint, the carboxyl end group concentration relative to (A) the thermoplastic polyester resin in the thermoplastic polyester resin composition after melt-kneading is preferably as low as possible, preferably 20 eq / t or less, and more preferably 15 eq / t.
- the carboxyl end group concentration relative to the thermoplastic polyester resin is determined by measuring the carboxyl end group concentration relative to the entire thermoplastic polyester resin composition, and then dividing the concentration by the blending ratio of the (A) thermoplastic polyester resin. It is the value obtained by returning.
- the thermoplastic polyester resin in the thermoplastic polyester resin composition includes (A) a reaction product of the thermoplastic polyester resin and the epoxy compound. The carboxyl end group concentration with respect to the thermoplastic polyester resin (A) in the thermoplastic polyester resin composition was determined by dissolving a solution obtained by dissolving the thermoplastic polyester resin composition in an o-cresol / chloroform (2/1 vol) mixed solution.
- the concentration is (A) the thermoplastic polyester. Obtained by dividing by the compounding ratio of the resin.
- the epoxy group concentration in the thermoplastic polyester resin composition after melt-kneading is preferably 5 eq / t or more, more preferably 10 eq / t or more, and particularly preferably 20 eq / t or more.
- the epoxy group concentration in the thermoplastic polyester resin composition after melt-kneading is preferably 260 eq / t or less.
- the epoxy group concentration in the thermoplastic polyester composition was determined by adding the acetic acid and triethylammonium bromide / acetic acid solution after dissolving the thermoplastic polyester resin composition in a mixed solution of o-cresol / chloroform (2/1 vol). It can be calculated by potentiometric titration with 0.1 mol / L perchloric acid acetic acid.
- the thermoplastic polyester resin composition of the present invention preferably further comprises (C) a phosphorus stabilizer.
- the novolak-type epoxy resin represented by the general formula (1) tends to generate phenoxy radicals and quinones that cause yellowing of the color tone of the molded product in the thermoplastic polyester resin composition.
- B) By blending (C) a phosphorus stabilizer together with the novolac epoxy resin represented by the general formula (1), (B) derived from the novolac epoxy resin represented by the general formula (1) Yellowing of the molded product due to the structure can be suppressed and the color tone can be improved.
- the phosphorus stabilizer is a structure represented by the following structural formula (4) or (5), that is, a structure in which two or more oxygen atoms are bonded to a phosphorus atom having an unshared electron pair. It is a compound containing. By having such a structure, it can be coordinated with a phenoxy radical or quinone which is a cause of coloring derived from a novolak type epoxy, and can be decomposed or colorless. Note that in a general phosphorus compound, the upper limit of oxygen atoms that can be bonded to a phosphorus atom having a lone pair from the valence of the phosphorus atom is three.
- Phosphorus stabilizers include phosphonite compounds as compounds containing a structure in which two oxygen atoms are bonded to a phosphorus atom having an unshared electron pair, and three oxygen atoms to a phosphorus atom having an unshared electron pair.
- a phosphite compound etc. can be mentioned as a compound containing the structure where the atom has couple
- Examples of the phosphonite compound include phosphonous acid compounds such as phenylphosphonous acid and 4,4′-biphenyl diphosphonous acid, aliphatic alcohols having 4 to 25 carbon atoms and / or 2,6-di-t- Examples thereof include condensates with phenol compounds such as butylphenol and 2,4-di-t-butyl-5-methylphenol.
- tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4′-biphenylenediphosphonite tetrakis (2) from the viewpoint of the heat stability of the phosphorus stabilizer (C).
- 4-Di-t-butylphenyl) -4,4′-biphenylenediphosphonite is preferred.
- phosphite compound examples include phosphorous acid, aliphatic alcohols having 4 to 25 carbon atoms, polyhydric alcohols such as glycerol and pentaerythritol, and / or 2,6-di-t-butylphenol and 2,4-dithiol. Examples thereof include condensates with phenol compounds such as -t-butylphenol.
- triisodecyl phosphite trisnonylphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 4 , 4'-butylidenebis (3-methyl-6-tert-butylphenyl) ditridecyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2-tert-butyl-4-methylphenyl) ) Phosphite, tris (2,4-di-t-amylphenyl) phosphite, tris (2-tert-butylphenyl) phosphite, tris [2- (1,1-dimethylpropyl)
- bis (alkylaryl) pentaerythritol diphosphite is preferred from the viewpoint of heat stability of the phosphorus stabilizer (C), and bis (2,4-di-t-butyl-4-methylphenyl) pentaerythritol.
- Diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite is more preferred.
- the blending amount of the (C) phosphorus stabilizer can be appropriately adjusted according to the type and blending amount of the novolak type epoxy resin represented by (B) the general formula (1).
- Thermoplastic 0.01 to 1 part by weight is preferable with respect to 100 parts by weight of the polyester resin.
- Color tone can be improved by making the compounding quantity of a phosphorus stabilizer into 0.01 weight part or more.
- long-term hydrolysis resistance and mechanical properties can be further improved by setting the blending amount of the (C) phosphorus stabilizer to 1 part by weight or less.
- the blending amount is more preferably 0.5 parts by weight or less.
- the thermoplastic polyester resin composition of the present invention preferably further comprises (D) a monofunctional epoxy compound.
- the monofunctional epoxy compound (D) generally has less steric hindrance around the epoxy group than the polyfunctional epoxy group in which the ester group generated by the reaction of a part of the epoxy groups in the molecule is sterically hindered. Since the reactivity with the carboxyl terminal group of the thermoplastic polyester resin (A) is superior to the novolak epoxy resin represented by the general formula (1), (B) the novolac type represented by the general formula (1) Thickening due to crosslinking of the epoxy resin can be suppressed, and the residence stability of the thermoplastic polyester resin composition can be further improved.
- (D) monofunctional epoxy compound with little steric hindrance is (B) the carboxyl of the thermoplastic polyester resin in which the novolak type epoxy resin represented by the general formula (1) cannot react due to steric hindrance. Since it can also react with a terminal group, the increase in the carboxyl terminal group concentration can be further suppressed, and the long-term hydrolysis resistance can be further improved.
- the monofunctional epoxy compound is not particularly limited as long as it is a compound having only one epoxy group, but monofunctional glycidyl ether compounds, monofunctional glycidyl ester compounds, and the like are preferable.
- Examples of the glycidyl ether compound having only one epoxy group include monovalent alcohols having only one hydroxyl group and glycidyl ethers of phenols.
- Examples of monovalent alcohol glycidyl ethers include butyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, ethylene oxide lauryl alcohol glycidyl ether, and ethylene oxide phenol glycidyl ether.
- Examples of glycidyl ethers of monovalent phenols include phenyl glycidyl ether and o-phenylphenyl glycidyl ether. Two or more of these may be used.
- Examples of the glycidyl ester compound having only one epoxy group include saturated aliphatic monocarboxylic acid glycidyl ester, unsaturated fatty monocarboxylic acid glycidyl ester, and aromatic monocarboxylic acid glycidyl ester.
- Examples of the saturated aliphatic monocarboxylic acid glycidyl ester include cyclohexanecarboxylic acid glycidyl ester, stearic acid glycidyl ester, lauric acid glycidyl ester, palmitic acid glycidyl ester, versatic acid glycidyl ester, and the like.
- Examples of the unsaturated aliphatic monocarboxylic acid glycidyl ester include oleic acid glycidyl ester, linoleic acid glycidyl ester, and linolenic acid glycidyl ester.
- Examples of the aromatic monocarboxylic acid glycidyl ester include 4-t-butylbenzoic acid glycidyl ester, p-toluic acid glycidyl ester, and the like. Two or more of these may be used.
- thermoplastic polyester resin (A) a glycidyl ester compound of a saturated aliphatic monocarboxylic acid and / or a glycidyl ester of an aromatic monocarboxylic acid is preferable.
- (D) Although the compounding quantity of a monofunctional epoxy compound can be suitably adjusted according to the kind and compounding quantity of (B) said novolak type epoxy resin represented by the said General formula (1), (A) Thermoplastic 0.01 to 1 part by weight is preferable with respect to 100 parts by weight of the polyester resin. (D) By making the compounding quantity of a monofunctional epoxy compound 0.01 weight part or more, the residence stability of a thermoplastic polyester resin composition can be improved more. The blending amount is more preferably 0.1 parts by weight or more. On the other hand, (D) By making the compounding quantity of a monofunctional epoxy compound into 1 weight part or less, mechanical property can be improved more and bleed-out can be suppressed. The blending amount is more preferably 0.6 parts by weight or less.
- thermoplastic polyester resin composition of the present invention It is preferable to further mix (E) a reaction catalyst with the thermoplastic polyester resin composition of the present invention.
- the reaction catalyst promotes the reaction between (A) the carboxyl end group of the thermoplastic polyester resin and (B) the epoxy group of the novolac type epoxy resin represented by the general formula (1). Can greatly improve the performance.
- the (E) reaction catalyst is not particularly limited as long as it promotes the reaction of (A) the carboxyl end group of the thermoplastic polyester resin and (B) the epoxy group of the novolak type epoxy resin represented by the general formula (1). It will never be done.
- tertiary amines, amidine compounds, organometallic compounds, organic phosphines, imidazoles, boron compounds and the like can be used. Two or more of these may be blended.
- tertiary amine examples include benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (diaminomethyl) phenol, 2,4,6-tris (diaminomethyl) phenol, and the like. It is done.
- the tertiary amine can be used in the form of a salt such as a salt with tri-2-ethylhexyl acid.
- amidine compounds include 1,8-diazabicyclo (5,4,0) undecene-7, 1,5-diazabicyclo (4,3,0) nonene-5,6-dibutylamino-1,8diazabicyclo (5). , 4,0) undecene-7,7-methyl-1,5,7-triazabicyclo (4,4,0) decene-5.
- the amidine compound can also be used in the form of a salt with an inorganic acid or an organic acid, such as 1,8-diazabicyclo (5,4,0) undecene-7.tetraphenylborate.
- organic metal compound examples include sodium stearate, magnesium stearate, calcium stearate, potassium stearate, lithium stearate, and other stearic acid metal salts, acetylacetonate chromium, acetylacetonate zinc, acetylacetonate nickel, and triethanol.
- examples include amine titanate and tin octylate.
- organic phosphine examples include triparatolylphosphine, tris-4-methoxyphenylphosphine, tetrabutylphosphonium bromide, butyltriphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, triphenylphosphine, triphenylphosphinetriphenylborane, And triphenylphosphine 1,4-benzoquinone adduct.
- imidazole examples include 2-methylimidazole, 2-aminoimidazole, 2-methyl-1-vinylimidazole, 2-ethyl-4-methylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-undecylimidazole.
- 1-allylimidazole 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-benzyl-2-methylimidazole, 1- Cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazolium isocyanurate 2-phenylimidazolium isocyanurate, 2,4-diamino-6- [2-methylimidazolyl- (1)] ethyl S-triazine, 1,3-dibenzyl-2-methylimidazolium chloride, 1,3-diazole Iminazole, 1-cyanoethyl-2-phenyl-4,5-di (cyanoe
- boron compounds include boron trifluoride-n-hexylamine, boron trifluoride-monoethylamine, boron trifluoride-benzylamine, boron trifluoride-diethylamine, boron trifluoride-piperidine, trifluoride.
- the compounding amount of the reaction catalyst is preferably 0.001 to 5 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin. If the compounding quantity of (E) component is 0.001 weight part or more, long-term hydrolysis resistance can be improved more.
- the blending amount is more preferably 0.01 parts by weight or more, and further preferably 0.02 parts by weight or more. On the other hand, if the amount of component (E) is 5 parts by weight or less, long-term hydrolysis resistance can be further improved while maintaining the mechanical properties.
- the amount is more preferably 3 parts by weight or less, and still more preferably 1 part by weight or less.
- the more preferable range of the compounding amount of (E) the reaction catalyst can be set according to the epoxy equivalent of the (B) novolac type epoxy resin represented by the above general formula (1).
- (B) in the thermoplastic polyester resin composition with respect to the compounding concentration (eq / g) of the epoxy group derived from the novolac type epoxy resin represented by the general formula (1) ( E)
- the ratio of the concentration (mol / g) of the reaction catalyst is preferably 0.01 to 0.1.
- the blending concentration / epoxy group concentration of the reaction catalyst is 0.01 or more, the long-term hydrolysis resistance can be further improved.
- the blending concentration / epoxy group concentration of the reaction catalyst is 0.1 or less, long-term hydrolysis resistance, residence stability, and mechanical properties can be balanced at a higher level. More preferably, it is 0.06 or less.
- the blending concentration of the (E) reaction catalyst in the thermoplastic polyester resin composition is a value calculated from the molecular weight of the reaction catalyst and the blending ratio of the (E) component in the entire thermoplastic polyester resin composition.
- thermoplastic polyester resin composition of the present invention is blended with one or more kinds of known additives such as an ultraviolet absorber, a light stabilizer, a plasticizer and an antistatic agent within a range not impairing the object of the present invention. Also good.
- the thermoplastic polyester resin composition of the present invention may contain a thermoplastic resin other than the component (A), and can improve moldability, dimensional accuracy, molding shrinkage, toughness, and the like.
- thermoplastic resins include low-density polyethylene resins, high-density polyethylene resins, polypropylene resins, polyamide resins, polyacetal resins, polyurethane resins, aromatic or aliphatic polyketone resins, polyphenylene sulfide resins, and polyether ether ketone resins.
- Polyimide resin thermoplastic starch resin, polyurethane resin, methyl methacrylate styrene resin (MS resin), aromatic polycarbonate resin, polyarylate resin, polysulfone resin, polyethersulfone resin, phenoxy resin, polyphenylene ether resin, poly-4-methyl
- aromatic polycarbonate resin polyarylate resin, polysulfone resin, polyethersulfone resin, phenoxy resin, polyphenylene ether resin, poly-4-methyl
- pentene-1 polyetherimide resin, cellulose acetate resin, and polyvinyl alcohol resin. Two or more of these may be blended.
- an aromatic polycarbonate resin is preferable from the viewpoint of improving dimensional accuracy and reducing molding shrinkage.
- aromatic polycarbonate resin examples include aromatic homo or copolycarbonates obtained by reacting an aromatic dihydric phenol compound with phosgene or a carbonic acid diester.
- aromatic dihydric phenol compounds examples include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, and bis (4-hydroxyphenyl).
- the weight average molecular weight of the aromatic polycarbonate resin is preferably in the range of 10,000 to 1100000. When the weight average molecular weight is 10,000 or more, the mechanical properties are further improved. The weight average molecular weight is more preferably 60000 or more. On the other hand, if the weight average molecular weight is 1100000 or less, the fluidity during molding is improved.
- the weight average molecular weight here is obtained by measuring in terms of polystyrene by gel permeation chromatography using tetrahydrofuran as a solvent.
- the aromatic polycarbonate resin preferably has a melt flow rate (MFR) measured at a temperature of 300 ° C. and a load condition of 11.8 N in the range of 1 to 100 g / 10 minutes, from the viewpoint of mechanical properties.
- MFR melt flow rate
- a more preferred embodiment is in the range of 1 to 50 g / 10 min.
- the blending amount of the aromatic polycarbonate resin is preferably 1 to 100 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin.
- the blending amount is more preferably 10 parts by weight or more.
- the heat resistance of the molded product can be further improved.
- the blending amount is more preferably 60 parts by weight or less.
- an acidic phosphate compound may be blended together with the aromatic polycarbonate resin.
- the acidic phosphoric ester compound is useful for preventing transesterification of (A) the thermoplastic polyester resin and the aromatic polycarbonate resin, and thus can further improve the heat resistance.
- the above acidic phosphoric acid ester compound is a general term for partial ester compounds of alcohols and phosphoric acid.
- the low molecular weight is a colorless liquid
- the high molecular weight is a white waxy or flaky solid
- the hydrogen of phosphoric acid is alkylated.
- acidic phosphate ester compound examples include long-chain alkyl acid phosphate compounds such as a mixture of mono and distearyl acid phosphates.
- a compound is, for example, a flaky solid having a melting point which is commercially available from ADEKA Corporation under the name “Adeka Stub” (registered trademark) AX-71. Two or more of these may be blended.
- the compounding amount of the acidic phosphoric ester compound is preferably 0.01 parts by weight or more with respect to (A) 100 parts by weight of the total of the thermoplastic polyester resin and the aromatic polycarbonate resin, and further improves the heat resistance of the molded product. Can do.
- the blending amount is more preferably 0.05 parts by weight or more.
- the amount is preferably 2 parts by weight or less, and higher mechanical properties can be maintained.
- the blending amount is more preferably 1 part by weight or less.
- the vinyl resin can be obtained, for example, by polymerizing one or more monomers selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds, alkyl (meth) acrylates and maleimide monomers. Examples thereof include resins obtained by graft polymerization or copolymerization of these monomers with resins or rubber components such as polybutadiene rubber.
- the total amount of aromatic vinyl compound, vinyl cyanide compound, (meth) acrylic acid alkyl ester and maleimide monomer in all monomers is preferably 50% by weight or more.
- Examples of the aromatic vinyl compound include styrene, ⁇ -methylstyrene, vinyl toluene, and divinyl benzene.
- Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile.
- Examples of the maleimide monomer include N-substituted maleimides such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide and derivatives thereof.
- vinyl resins include methyl methacrylate / acrylonitrile, polystyrene resin, acrylonitrile / styrene resin (AS resin), styrene / butadiene resin, styrene / N-phenylmaleimide resin, styrene / acrylonitrile / N-phenylmaleimide resin, etc.
- AS resin acrylonitrile / styrene resin
- ABS resin acrylonitrile / butadiene / styrene resin
- MABS resin acrylonitrile / butadiene / methyl methacrylate / styrene resin
- high impact polystyrene resin etc.
- Examples thereof include styrene resins, styrene / butadiene / styrene resins, styrene / isoprene / styrene resins, block copolymers such as styrene / ethylene / butadiene / styrene resins, and the like. Two or more of these may be blended. Among them, polystyrene resin and acrylonitrile / styrene resin are preferable, and acrylonitrile / styrene resin is more preferably used.
- an acrylonitrile / styrene resin containing 15% by weight or more and less than 35% by weight of acrylonitrile is particularly preferably used.
- the vinyl resin may be graft polymerized or copolymerized with unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated acid anhydrides, or epoxy group-containing vinyl monomers.
- unsaturated monocarboxylic acids unsaturated monocarboxylic acids
- unsaturated dicarboxylic acids unsaturated acid anhydrides
- epoxy group-containing vinyl monomers vinyl resins obtained by graft polymerization or copolymerization of unsaturated acid anhydrides or epoxy group-containing vinyl monomers are preferable.
- the unsaturated acid anhydrides are compounds that share both radically polymerizable vinyl groups and acid anhydrides in one molecule, and preferred examples include maleic anhydride.
- the epoxy group-containing vinyl monomer is a compound that shares both a vinyl group capable of radical polymerization and two or more epoxy groups in one molecule.
- Specific examples thereof include glycidyl acrylate, glycidyl methacrylate, Examples include glycidyl esters of unsaturated organic acids such as glycidyl ethacrylate and glycidyl itaconate, and glycidyl ethers such as allyl glycidyl ether and 2-methylglycidyl methacrylate.
- glycidyl acrylate and glycidyl methacrylate are used. It can be preferably used. Two or more of these can be used in combination.
- the amount used for graft polymerization or copolymerization of unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated acid anhydrides or epoxy group-containing vinyl monomers is 0.05% by weight or more based on the vinyl resin. It is preferable that From the viewpoint of suppressing gelation and improving fluidity, the preferred amount of use is 20% by weight or less, more preferably 10% by weight or less, and further preferably 5% by weight or less.
- the vinyl resin may be epoxy-modified with an epoxidizing agent such as peroxides, performic acid, peracetic acid, and perbenzoic acid.
- an epoxidizing agent such as peroxides, performic acid, peracetic acid, and perbenzoic acid.
- the number of epoxy groups in one molecule is 2 or more.
- a diene monomer is randomly copolymerized or block copolymerized with the vinyl resin.
- diene monomers butadiene, isoprene, and the like are preferably used. Examples of suitable methods for producing these epoxy-modified vinyl resins are disclosed in JP-A-6-256417 and JP-A-6-220124.
- a core shell type rubber having a so-called core shell type structure constituted by an inner layer (core layer) made of rubber and an outer layer (shell layer) made of vinyl resin covering the same is also preferably used.
- the rubber used for the core layer may be composed of a polymer component having rubber elasticity.
- the polymer component having rubber elasticity include rubber constituted by polymerizing an acrylic component, a silicone component, a styrene component, a nitrile component, a conjugated diene component, a urethane component, an ethylene propylene component, and the like.
- Preferred rubbers include, for example, acrylic components such as ethyl acrylate units and butyl acrylate units; silicone components such as dimethylsiloxane units and phenylmethylsiloxane units; styrene components such as styrene units and ⁇ -methylstyrene units; acrylonitrile units and A rubber composed of a polymer obtained by polymerizing a nitrile component such as a methacrylonitrile unit; and a conjugated diene component such as a butanediene unit or an isoprene unit. A rubber composed of a combination of two or more of these components and copolymerized is also preferably used.
- the vinyl resin used for the outer layer (shell layer) is a vinyl resin obtained by graft polymerization or copolymerization of unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated acid anhydrides, or epoxy group-containing vinyl monomers. It may be a resin or a vinyl resin obtained by epoxy-modifying a vinyl resin with an epoxidizing agent such as peroxides, performic acid, peracetic acid or perbenzoic acid.
- the core-shell type rubber include those in which the core layer is a dimethylsiloxane / butyl acrylate copolymer and the outermost layer is a methyl methacrylate polymer or an acrylonitrile / styrene copolymer, and the core layer is a butanediene / styrene copolymer.
- the outermost layer is a methyl methacrylate polymer or acrylonitrile / styrene copolymer
- the core layer is a butyl acrylate polymer and the outermost layer is a methyl methacrylate polymer or an acrylonitrile / styrene copolymer.
- it is a more preferable embodiment that either one or both of the rubber layer and the outermost layer is a polymer containing a glycidyl methacrylate unit.
- the weight ratio of the core to the shell is preferably 10% by weight or more and 90% by weight or less, more preferably 30% by weight or more, 80% by weight of the core layer with respect to the entire core-shell type rubber. % By weight or less.
- the core-shell type rubber As the core-shell type rubber, a commercially available product that satisfies the above-described conditions may be used, or it may be prepared and used by an arbitrary method.
- Commercially available products include, for example, “Metablene” (registered trademark) manufactured by Mitsubishi Rayon Co., Ltd., “Kane Ace” (registered trademark) manufactured by Kaneka Corporation, “Paralloid” (registered trademark) manufactured by Dow Chemical Co., Ltd., and Examples include “Parapet” (registered trademark) SA manufactured by Kuraray Co., Ltd. Two or more of these may be used.
- a vinyl resin containing a vinyl resin as a branched chain of the graft copolymer may be used.
- the resin that becomes the main chain include polyolefin resins, acrylic resins, and polycarbonate resins. Either the branched chain or the main chain may be modified with glycidyl methacrylate or acid anhydride.
- Specific examples include poly (ethylene / glycidyl methacrylate) -g-polymethyl methacrylate (E / GMA-g -PMMA), poly (ethylene / glycidyl methacrylate) -g-polystyrene (E / GMA-g-PS), poly (ethylene / glycidyl methacrylate) -g-acrylonitrile / styrene (E / GMA-g-AS), poly ( Ethylene-g-acrylonitrile / styrene (Eg-AS), polycarbonate-g-acrylonitrile / styrene (PC-g-AS), etc. (where “-g-” represents graft polymerization, "-/-” Represents copolymerization).
- Examples of a commercially available vinyl resin containing a vinyl resin as a branched chain of a graft copolymer include “Modiper” (registered trademark) manufactured by NOF Corporation. These may be used in combination with other vinyl resins.
- the blending amount of the vinyl resin is preferably 0.1 to 40 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin, from the viewpoint of further improving toughness and mechanical properties. If the compounding amount of the vinyl resin is 0.1 parts by weight or more, the toughness is further improved. As for the compounding quantity of vinyl-type resin, 0.5 weight part or more is more preferable, More preferably, it is 1 weight part or more. On the other hand, when the compounding amount of the vinyl resin is 40 parts by weight or less, the mechanical properties are further improved. The compounding amount of the vinyl resin is more preferably 35 parts by weight or less, and more preferably 30 parts by weight or less.
- the thermoplastic polyester resin composition of the present invention may further contain a resin for improving impact strength other than the above-mentioned (A) thermoplastic polyester resin, thermoplastic resins other than (A), and vinyl resins.
- the resin for improving the impact strength include ethylene-propylene copolymer, ethylene-propylene-nonconjugated diene copolymer, ethylene-butene-1 copolymer, natural rubber, thiocol rubber, polysulfide rubber, and polyether.
- examples thereof include rubber, epichlorohydrin rubber, and modified olefin resin obtained by acid-modifying ethylene with an acid anhydride such as maleic anhydride or epoxy-modifying with glycidyl methacrylate and an epoxidizing agent.
- the number of epoxy groups in one molecule when epoxy-modified is 2 or more. These may have various degrees of crosslinking, and may have various microstructures such as a cis structure and a trans structure.
- modified olefin resins obtained by acid-modifying ethylene with an acid anhydride such as maleic anhydride or epoxy-modifying with glycidyl methacrylate and an epoxidizing agent include, for example, ethylene / glycidyl methacrylate, ethylene / butene-1 / maleic anhydride, Examples thereof include ethylene / propylene / maleic anhydride, ethylene / maleic anhydride, and epoxidized olefin resin obtained by epoxidizing ethylene with a peroxide.
- Examples of these commercially available products include “Bond First” (registered trademark) E (ethylene / glycidyl methacrylate) manufactured by Sumitomo Chemical Co., Ltd., “Toughmer” (registered trademark) MH-5010 and MH- manufactured by Mitsui Chemicals, Inc. 5020 (ethylene / butene-1 / maleic anhydride) and the like.
- ethylene / butene-1 / maleic anhydride is preferably used because it greatly improves impact strength.
- the blending amount of the resin for improving the impact strength is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin.
- the impact strength is further improved.
- the blending amount is more preferably 0.5 parts by weight or more, and still more preferably 1 part by weight or more.
- the amount is 10 parts by weight or less, the mechanical properties are further improved.
- the amount is preferably 8 parts by weight or less, more preferably 6 parts by weight or less.
- a polyhydric alcohol compound containing an alkylene oxide unit having three or more functional groups can be further blended.
- the polyhydric alcohol compound refers to a compound having two or more hydroxyl groups.
- the polyhydric alcohol compound may be a low molecular compound, a polymer, or any polyhydric alcohol compound containing one or more alkylene oxide units having three or more functional groups. However, it is preferably used.
- the functional group here means hydroxyl group, aldehyde group, carboxylic acid group, sulfo group, amino group, glycidyl group, isocyanate group, carbodiimide group, oxazoline group, oxazine group, ester group, amide group, silanol group and silyl ether group.
- a functional group selected from Among these it is more preferable to have three or more functional groups that are the same or different. Particularly, in terms of fluidity, mechanical properties, durability, heat resistance, and productivity, the same three or more functional groups. It is a more preferable aspect that it has.
- alkylene oxide unit contained in the polyhydric alcohol compound include aliphatic alkylene oxide units having 1 to 4 carbon atoms. Specific examples include methylene oxide units, ethylene oxide units, trimethylene oxide units, propylene oxide units, tetramethylene oxide units, 1,2-butylene oxide units, 2,3-butylene oxide units, isobutylene oxide units, and the like. it can.
- the number of alkylene oxide units is preferably 0.1 or more, more preferably 0.5 or more, and even more preferably 1 or more in terms of superior fluidity. is there.
- the alkylene oxide unit per functional group is preferably 20 or less, more preferably 10 or less, and even more preferably 5 or less in terms of better mechanical properties.
- the polyhydric alcohol compound may react with the thermoplastic polyester resin (A) and may be introduced into the main chain and side chain of the component (A). The structure may be maintained.
- the blending amount of the polyhydric alcohol compound containing an alkylene oxide unit having three or more functional groups is preferably 0.01 to 3 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin. If the blending amount of the polyhydric alcohol compound is 0.01 parts by weight or more, the fluidity can be improved. The blending amount is more preferably 0.05 parts by weight or more, and still more preferably 0.1 parts by weight or more. On the other hand, if the blending amount of the polyhydric alcohol compound is 3 parts by weight or less, the mechanical properties can be further improved. The blending amount is more preferably 2.0 parts by weight or less, and further preferably 1.5 parts by weight or less.
- thermoplastic polyester resin composition of the present invention includes a phosphorus flame retardant, a halogen flame retardant, a salt of a triazine compound and cyanuric acid or isocyanuric acid, and a silicone flame retardant, as long as the effects of the present invention are not impaired. Further, an inorganic flame retardant and the like can be further blended.
- the phosphorus-based flame retardant is a flame retardant containing a phosphorus component, and is an aromatic phosphate compound, a phosphazene compound, a phosphaphenanthrene compound, a phosphinic acid metal salt, ammonium polyphosphate, melamine polyphosphate, phosphate amide and red Phosphorus etc. are mentioned.
- aromatic phosphate ester compounds, phosphazene compounds, phosphaphenanthrene compounds, and phosphinic acid metal salts are preferably used. Two or more of these may be blended.
- aromatic phosphate compound examples include resorcinol diphenyl phosphate, hydroquinone diphenyl phosphate, bisphenol A diphenyl phosphate, and biphenyl diphenyl phosphate.
- Commercially available products include PX-202, CR-741, PX-200, PX-201 manufactured by Daihachi Chemical Industry Co., Ltd., FP-500, FP-600, FP-700 and PFR manufactured by Adeka Co., Ltd. And so on.
- the phosphazene compound examples include a phosphonitrile linear polymer and / or a cyclic polymer, and a compound mainly composed of a linear phenoxyphosphazene is preferably used.
- the phosphazene compound can be synthesized by a known method described in the author Sugawara “Synthesis and application of phosphazene compounds”, for example, phosphorus pentachloride or phosphorus trichloride as a phosphorus source, ammonium chloride or ammonia as a nitrogen source. It can be synthesized by reacting the gas by a known method (the cyclic product may be purified) and substituting the obtained substance with alcohol, phenol and amines.
- “RABITL” registered trademark
- FP-110 manufactured by Fushimi Pharmaceutical Co., Ltd.
- the phosphaphenanthrene compound is a phosphorus-based flame retardant having at least one phosphaphenanthrene skeleton in the molecule, and commercially available products include HCA, HCA-HQ, BCA, SANKO-220 and MKO manufactured by Sanko Co., Ltd. -Ester and the like.
- M-Ester is preferably used because it can be expected to react with a hydroxyl group at the terminal and the terminal of the thermoplastic polyester resin (A) at the time of melt-kneading, and is effective in suppressing bleed-out under high temperature and high humidity.
- the phosphinic acid metal salt is a phosphinate and / or diphosphinate and / or a polymer thereof, and is a compound useful as a flame retardant for (A) a thermoplastic polyester resin.
- salts such as calcium, aluminum, and zinc, are mentioned.
- Commercially available phosphinic acid metal salts include “Exolit” (registered trademark) OP1230 and OP1240 manufactured by Clariant Japan.
- Phosphoric ester amide is an aromatic amide flame retardant containing a phosphorus atom and a nitrogen atom. Since it is a powdery substance at room temperature having a high melting point, it is excellent in handling at the time of blending, and the heat distortion temperature of the molded product can be further improved.
- a commercial product of phosphoric ester amide SP-703 manufactured by Shikoku Kasei Co., Ltd. is preferably used.
- ammonium polyphosphate examples include ammonium polyphosphate, melamine-modified ammonium polyphosphate, and ammonium carbamyl polyphosphate.
- melamine polyphosphate examples include melamine phosphate, melamine pyrophosphate, and melamine polyphosphate such as melamine, melam, and phosphate with melem.
- MPP-A manufactured by Sanwa Chemical Co., Ltd., PMP-100 and PMP-200 manufactured by Nissan Chemical Co., Ltd. are preferably used.
- red phosphorus not only untreated red phosphorus but also red phosphorus treated with a compound film such as a thermosetting resin film, a metal hydroxide film, or a metal plating film can be preferably used.
- thermosetting resin used for the thermosetting resin film include phenol-formalin resin, urea-formalin resin, melamine-formalin resin, alkyd resin, and the like.
- metal hydroxide used for the metal hydroxide film include aluminum hydroxide, magnesium hydroxide, zinc hydroxide, and titanium hydroxide.
- the metal of the metal plating film is not particularly limited as long as it is a resin capable of coating red phosphorus, and examples thereof include Fe, Ni, Co, Cu, Zn, Mn, Ti, Zr, Al, and alloys thereof. Furthermore, these coatings may be laminated in combination of two or more or in combination of two or more.
- the blending amount of the phosphorus-based flame retardant is preferably 1 to 40 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin. If the compounding quantity of a phosphorus flame retardant is 1 weight part or more, the flame retardance of a resin composition and a molded article can be improved. The amount is more preferably 3 parts by weight or more, and still more preferably 10 parts by weight or more. On the other hand, when the blending amount of the phosphorus-based flame retardant is 40 parts by weight or less, bleed-out in which the phosphorus-based flame retardant is deposited on the surface of the molded product can be suppressed. The blending amount is more preferably 35 parts by weight or less.
- halogen flame retardants include decabromodiphenyl oxide, octabromodiphenyl oxide, tetrabromodiphenyl oxide, tetrabromophthalic anhydride, hexabromocyclododecane, bis (2,4,6-tribromophenoxy) ethane, ethylene Bistetrabromophthalimide, hexabromobenzene, 1,1-sulfonyl [3,5-dibromo-4- (2,3-dibromopropoxy)] benzene, polydibromophenylene oxide, tetrabromobisphenol-S, tris (2,3 -Dibromopropyl-1) isocyanurate, tribromophenol, tribromophenyl allyl ether, tribromoneopentyl alcohol, brominated polystyrene, brominated polyethylene, tetrabromobisphenol- Tet
- the blending amount of the halogen-based flame retardant is preferably 1 to 50 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin. If the compounding quantity of a halogen-type flame retardant is 1 weight part, the flame retardance of a resin composition and a molded article can be improved.
- the blending amount is more preferably 2 parts by weight or more, and further preferably 3 parts by weight or more.
- the blending amount of the halogen-based flame retardant is 50 parts by weight or less, bleed-out in which the halogen-based flame retardant is deposited on the surface of the molded product can be suppressed.
- the blending amount is more preferably 45 parts by weight or less, and still more preferably 40 parts by weight or less.
- a salt of a triazine compound and cyanuric acid or isocyanuric acid is a nitrogen-containing heterocyclic compound having a triazine skeleton, and melamine cyanurate and melamine isocyanurate are preferably used.
- blending this compound the flame retardance of a resin composition and a molded article can be improved more according to the cooling effect. Two or more of these may be blended.
- melamine cyanurate or melamine isocyanurate an adduct of cyanuric acid or isocyanuric acid and a triazine compound is preferable, and usually has a composition of 1: 1 (molar ratio), sometimes 1: 2 (molar ratio), etc. There may be mentioned adducts.
- Melamine cyanurate or melamine isocyanurate can be produced by any method. For example, a mixture of melamine and cyanuric acid or isocyanuric acid is made into a water slurry, mixed well to form both salts in the form of fine particles, and then the slurry is filtered and dried. .
- the salt does not need to be completely pure, and some unreacted melamine, cyanuric acid or isocyanuric acid may remain. Further, it may be treated with a dispersant such as tris ( ⁇ -hydroxyethyl) isocyanurate or a known surface treatment agent such as a metal oxide such as polyvinyl alcohol and silica, and the dispersibility can be improved.
- a dispersant such as tris ( ⁇ -hydroxyethyl) isocyanurate or a known surface treatment agent such as a metal oxide such as polyvinyl alcohol and silica
- the average particle diameter before and after blending with the resin of melamine cyanurate or melamine isocyanurate is preferably 0.1 to 100 ⁇ m from the viewpoint of flame retardancy, mechanical strength and surface property of the molded product.
- the average particle diameter is more preferably 0.2 ⁇ m or more, and further preferably 0.3 ⁇ m or more.
- the average particle diameter is more preferably 50 ⁇ m or less, and further preferably 10 ⁇ m or less.
- An average particle diameter here is an average particle diameter measured by 50% of cumulative distribution particle diameter by a laser micron sizer method.
- MC-4000, MC-4500 and MC-6000 manufactured by Nissan Chemical Co., Ltd. are preferably used as commercial products of salts of triazine compounds with cyanuric acid or isocyanuric acid.
- the blending amount of the salt of the triazine compound and cyanuric acid or isocyanuric acid is preferably 1 to 50 parts by weight with respect to 100 parts by weight of the thermoplastic polyester resin (A) from the viewpoint of flame retardancy and tensile properties.
- the blending amount of the salt of the triazine compound and cyanuric acid or isocyanuric acid is 1 part by weight or more, the flame retardancy of the resin composition and the molded product can be improved.
- the amount is more preferably 3 parts by weight or more, and still more preferably 10 parts by weight or more.
- the blending amount of the salt of the triazine compound and cyanuric acid or isocyanuric acid is 50 parts by weight or less, the tensile properties of the molded product can be further improved.
- the blending amount is more preferably 45 parts by weight or less.
- silicone flame retardant examples include silicone resin and silicone oil.
- silicone resin examples include a resin having a three-dimensional network structure formed by combining SiO 2 , RSiO 3/2 , and R 2 SiO, R 3 SiO 1/2 structural units.
- R represents an alkyl group aromatic hydrocarbon group which may be substituted.
- alkyl group examples include a methyl group, an ethyl group, and a propyl group
- examples of the aromatic hydrocarbon group include a phenyl group and a benzyl group.
- a vinyl group etc. are mentioned as a substituent.
- polydimethylsiloxane and at least one methyl group at the side chain or terminal of polydimethylsiloxane are hydrogen element, alkyl group, cyclohexyl group, phenyl group, benzyl group, amino group, epoxy group, polyether group , Modified polysiloxane modified with at least one group selected from the group consisting of carboxyl group, mercapto group, chloroalkyl group, alkyl higher alcohol ester group, alcohol group, aralkyl group, vinyl group and trifluoromethyl group. . Two or more of these may be blended.
- Inorganic flame retardants include magnesium hydroxide hydrate, aluminum hydroxide hydrate, antimony trioxide, antimony pentoxide, sodium antimonate, zinc hydroxystannate, zinc stannate, metastannic acid, tin oxide, tin oxide Salt, zinc sulfate, zinc oxide, zinc borate, zinc borate hydrate, zinc hydroxide ferrous oxide, ferric oxide, sulfur sulfide, stannous oxide, stannic oxide, ammonium borate, octamolybdic acid Examples include ammonium, metal salts of tungstic acid, complex oxide acids of tungsten and metalloid, ammonium sulfamate, zirconium compounds, graphite, and swellable graphite.
- the inorganic flame retardant may be surface-treated with a fatty acid or a silane coupling agent.
- a fatty acid or a silane coupling agent zinc borate hydrate and swellable graphite are preferable in terms of flame retardancy.
- an inorganic flame retardant excellent in flame retardancy and retention stability a mixture of magnesium oxide and aluminum oxide, zinc stannate, metastannic acid, tin oxide, zinc sulfate, zinc oxide, zinc borate, zinc ferrous oxide, Ferric oxide and sulfur sulfide are particularly preferably used.
- the blending amount of the inorganic flame retardant is 0.05 parts by weight or more with respect to 100 parts by weight of the thermoplastic polyester resin (A) in that the endothermic effect of combustion heat and the effect of preventing combustion due to expansion are exhibited. Is more preferably 0.1 parts by weight or more, and still more preferably 0.15 parts by weight or more.
- the blending amount of the inorganic flame retardant is preferably 4 parts by weight or less, more preferably 3 parts by weight with respect to 100 parts by weight of the thermoplastic polyester resin (A) from the viewpoint of superior mechanical properties. Or less, more preferably 2 parts by weight or less.
- Fluorine resin can be further blended in the thermoplastic polyester resin composition of the present invention.
- blending a fluorine resin the melting fall at the time of combustion can be suppressed and a flame retardance can be improved.
- the fluorine-based resin is a resin containing fluorine in a substance molecule.
- polytetrafluoroethylene (tetrafluoroethylene / perfluoroalkyl vinyl ether) copolymer, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethylene / ethylene) copolymer, polyvinylidene fluoride Ride is preferable, and polytetrafluoroethylene and (tetrafluoroethylene / ethylene) copolymer are particularly preferable.
- the blending amount of the fluororesin is preferably 0.05 to 3 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin. If the amount is 0.05 parts by weight or more, the effect of preventing melting and dropping during combustion is improved. The blending amount is more preferably 0.1 parts by weight or more, and still more preferably 0.15 parts by weight or more. On the other hand, if the amount is 2 parts by weight or less, the mechanical properties are further improved. The blending amount is more preferably 2 parts by weight or less, and still more preferably 1.5 parts by weight or less.
- a mold release agent can be further blended in the thermoplastic polyester resin composition of the present invention.
- blending a mold release agent the mold release property at the time of injection molding can be improved.
- the release agent include fatty acid amides such as ethylene bisstearyl amide, polycondensates composed of ethylenediamine and stearic acid and sebacic acid, or fatty acid amides composed of polycondensate of phenylenediamine, stearic acid and sebacic acid, and polyalkylene wax.
- known release agents for plastics such as acid anhydride-modified polyalkylene waxes and mixtures of the above-mentioned lubricants with fluorine resins and fluorine compounds can be used.
- the compounding amount of the release agent is preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin. If the blending amount is 0.01 parts by weight or more, a sufficient releasability effect can be obtained. The blending amount is more preferably 0.02 parts by weight or more, and still more preferably 0.03 parts by weight or more. On the other hand, if the amount is 1 part by weight or less, the mechanical properties are further improved. The blending amount is more preferably 0.8 parts by weight or less, and still more preferably 0.6 parts by weight or less.
- thermoplastic polyester resin composition of the present invention a fiber reinforcing material can be further blended as long as the effects of the present invention are not impaired.
- the mechanical strength and heat resistance can be further improved.
- fiber reinforcement examples include glass fiber, aramid fiber, and carbon fiber.
- glass fiber chopped strand type or roving type glass fiber, which is treated with a silane coupling agent and / or a sizing agent, is preferably used.
- silane coupling agent an aminosilane compound or an epoxysilane compound is preferably used.
- sizing agent epoxy compounds such as urethane, vinyl acetate, bisphenol A diglycidyl ether, and novolac epoxy compounds are preferably used.
- the fiber diameter of the fiber reinforcement is preferably 1 to 30 ⁇ m, more preferably 5 to 15 ⁇ m.
- the fiber cross section of the fiber reinforcement is usually circular, but fiber reinforcements having a non-circular cross section such as elliptical glass fiber, flat glass fiber, and eyebrow-shaped glass fiber of any aspect ratio can be used. .
- fiber reinforcements having a non-circular cross section such as elliptical glass fiber, flat glass fiber, and eyebrow-shaped glass fiber of any aspect ratio can be used.
- a fiber reinforcing material having a non-circular cross section there is a characteristic that a fluidity improvement at the time of injection molding and a molded product with less warpage can be obtained.
- the blending amount of the fiber reinforcement is preferably 1 to 100 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin.
- the blending amount is more preferably 2 parts by weight or more, and further preferably 3 parts by weight or more.
- the mechanical strength and heat resistance can be further improved by blending 100 parts by weight or less of the fiber reinforcement.
- the blending amount is more preferably 95 parts by weight or less, and still more preferably 90 parts by weight or less.
- an inorganic filler other than the fiber reinforcement can be further blended.
- an inorganic filler other than the fiber reinforcing material By blending an inorganic filler other than the fiber reinforcing material, it is possible to improve some of the crystallization characteristics, arc resistance, anisotropy, mechanical strength, flame retardancy, or heat distortion temperature of the molded product.
- Inorganic fillers other than the fiber reinforcing material are particularly effective in anisotropy, so that a molded product with less warpage can be obtained.
- inorganic fillers other than fiber reinforcement include needle-like, granular, powdery and layered inorganic fillers. Specific examples include glass beads, milled fiber, glass flake, potassium titanate whisker, calcium sulfate whisker, wollastonite, silica, kaolin, talc, calcium carbonate, zinc oxide, magnesium oxide, aluminum oxide, magnesium oxide and aluminum oxide. Examples thereof include a mixture, finely divided silicic acid, aluminum silicate, silicon oxide, smectite clay mineral (montmorillonite, hectorite), vermiculite, mica, fluorine teniolite, zirconium phosphate, titanium phosphate, and dolomite. Two or more of these may be blended.
- the inorganic filler other than the fiber reinforcing material may be subjected to a surface treatment such as a coupling agent treatment, an epoxy compound, or an ionization treatment.
- the average particle size of the granular, powdery and layered inorganic fillers is preferably 0.1 to 20 ⁇ m, particularly preferably 0.2 to 10 ⁇ m from the viewpoint of impact strength.
- the blending amount of the inorganic filler other than the fiber reinforcing material is combined with the blending amount of the fiber reinforcing material from the viewpoint of fluidity at the time of molding and durability of the molding machine and the mold (A) thermoplastic polyester resin 100. 100 parts by weight or less is preferable with respect to parts by weight.
- the blending amount of the inorganic filler other than the fiber reinforcing material is preferably 1 to 50 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin. If the blending amount of the inorganic filler other than the fiber reinforcement is 1 part by weight or more, the anisotropy can be reduced and the retention stability can be further improved. 2 parts by weight or more is more preferable, and 3 parts by weight or more is more preferable. On the other hand, if the blending amount of the inorganic filler other than the fiber reinforcement is 50 parts by weight or less, the mechanical strength can be improved.
- An antioxidant may be further blended in the thermoplastic polyester resin composition of the present invention.
- an antioxidant By blending an antioxidant, it is possible to give extremely good heat aging resistance even when exposed to a high temperature for a long time.
- examples of the antioxidant include hindered phenol antioxidants and thioether antioxidants. Two or more of these may be blended.
- the blending amount of the antioxidant is preferably 0.01 parts by weight or more, more preferably 0.02 parts by weight or more with respect to 100 parts by weight of the thermoplastic polyester resin (A) from the viewpoint of improving heat aging resistance. More preferably, it is 0.03 parts by weight or more.
- the blending amount of the antioxidant is preferably 2 parts by weight or less, more preferably 1.5 parts by weight or less, and still more preferably 1 part by weight or less from the viewpoint of superior mechanical properties.
- thermoplastic polyester resin composition of the present invention can be adjusted to various colors by combining one or more kinds of carbon black, titanium oxide and various color pigments and dyes, It is also possible to improve the conductivity.
- the blending amount of the pigment or dye is preferably 0.01 to 3 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin. If the blending amount is 0.01 parts by weight, toning, weather resistance (light) resistance and conductive effect can be obtained.
- the blending amount is more preferably 0.02 parts by weight or more, and still more preferably 0.03 parts by weight or more. On the other hand, if the amount is 3 parts by weight or less, the mechanical properties are further improved.
- the blending amount is more preferably 2 parts by weight or less, and still more preferably 1 part by weight or less.
- carbon black examples include channel black, furnace black, acetylene black, anthracene black, oil smoke, pine smoke, and graphite. Carbon black has an average particle diameter of at 500nm or less, and dibutyl phthalate oil absorption amount is 50 ⁇ 400cm 3 / 100g is preferably used. Carbon black may be treated with aluminum oxide, silicon oxide, zinc oxide, zirconium oxide, polyol, silane coupling agent, and the like.
- titanium oxide having a crystal form such as a rutile form or anatase form and having an average particle diameter of 5 ⁇ m or less is preferably used. Titanium oxide may be treated with aluminum oxide, silicon oxide, zinc oxide, zirconium oxide, polyol, silane cup, ring agent, or the like.
- carbon black, titanium oxide, and pigments and dyes of various colors may be blended with various thermoplastic resins or melt blended for improving dispersibility with the thermoplastic polyester resin composition and handling at the time of production. It may be used as a blended mixed material.
- thermoplastic polyester resin composition of the present invention can be obtained, for example, by melt-kneading the component (A), the component (B) and other components as necessary.
- melt kneading method examples include (A) a thermoplastic polyester resin, (B) a novolac type epoxy resin represented by the general formula (1), if necessary (C) a phosphorus stabilizer, (D) Pre-mix monofunctional epoxy compound, (E) reaction catalyst and various additives, supply to an extruder, etc., and melt and knead well, or use a quantitative feeder such as a weight feeder, etc. Examples thereof include a method of supplying to an extruder or the like and sufficiently melting and kneading.
- premixing examples include a dry blending method and a mixing method using a mechanical mixing device such as a tumbler, ribbon mixer, and Henschel mixer.
- inorganic fillers other than fiber reinforcements and fiber reinforcements may be added from a side feeder installed between a feed-in part and a vent part of a multi-screw extruder such as a twin screw extruder.
- a method of adding using a plunger pump by installing a liquid addition nozzle in the middle of the original storage part and vent part of a multi-screw extruder such as a twin screw extruder A method of supplying a metering pump from a section or the like may be used.
- thermoplastic polyester resin composition of the present invention is preferably molded after being pelletized.
- a pelletizing method for example, a single-screw extruder, a twin-screw extruder, a three-screw extruder, a conical extruder, a kneader-type kneader or the like equipped with a “unimelt” or “dalmage” type screw is used.
- the method of discharging a plastic polyester resin composition in strand shape and cutting using a strand cutter is mentioned.
- thermoplastic polyester resin composition of the present invention By melt molding the thermoplastic polyester resin composition of the present invention, it is possible to obtain molded products of films, fibers and other various shapes.
- melt molding method include injection molding, extrusion molding and blow molding, and injection molding is particularly preferably used.
- injection molding methods gas assist molding, two-color molding, sandwich molding, in-mold molding, insert molding, and injection press molding are known in addition to the usual injection molding methods. it can.
- the molded article of the present invention can be suitably used as a mechanical mechanism part, electrical part, electronic part, and automobile part, taking advantage of its long-term hydrolysis resistance, mechanical properties such as tensile strength and elongation, and heat resistance. it can.
- the molded product obtained from the thermoplastic polyester resin composition of the present invention is particularly useful for outer layer parts because of its excellent long-term hydrolysis resistance.
- mechanical mechanism parts, electrical parts, electronic parts, and automobile parts include breakers, electromagnetic switches, focus cases, flyback transformers, molded products for copiers and printer fixing machines, general household appliances, and OA.
- thermoplastic polyester resin composition of the present invention will be specifically described by way of examples.
- the raw materials used in the examples and comparative examples are shown below.
- “%” and “part” all represent “% by weight” and “part by weight”, and “/” in the following resin name means copolymerization.
- Thermoplastic polyester resin ⁇ A-1> Polybutylene terephthalate resin: Polybutylene terephthalate resin having a carboxyl end group concentration of 30 eq / t manufactured by Toray Industries, Inc. was used. ⁇ A-2> Polyethylene terephthalate resin: Polyethylene terephthalate resin having a carboxyl end group concentration of 40 eq / t manufactured by Toray Industries, Inc. was used.
- n a value of 2 to 4.
- n a value of 2 to 4.
- n represents a value of 1 to 3.
- n a value of 3 to 5.
- n a value of 3 to 5.
- n represents a value of 1 to 5.
- (C) Phosphorus stabilizer ⁇ C-1> Bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite: “ADEKA STAB” (registered trademark) PEP36 manufactured by ADEKA Corporation is used It was. ⁇ C-2> Tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenediphosphonite: “Hostanox” (registered trademark) P-EPQ manufactured by Clariant Japan Co., Ltd. was used. .
- (E) Reaction catalyst ⁇ E-1> Amidine compound: 1,8-diazabicyclo (5,4,0) undecene-7, “DBU” (registered trademark) manufactured by San Apro Co., Ltd., molecular weight 152 was used.
- triphenylphosphine (reagent), molecular weight 262.29 ⁇ E-4>
- Organometallic compound lithium stearate, Tokyo Chemical Industry Lithium stearate (reagent) manufactured by Co., Ltd., molecular weight 290.42 was used.
- (F) Other additives ⁇ F-1> Vinyl-based resin: Silicone / acrylic composite core-shell type rubber, “METABRENE” (registered trademark) S-2001 manufactured by Mitsubishi Rayon Co., Ltd. was used.
- ⁇ F-4> Mold release agent Montanic acid ester wax, Rico wax E manufactured by Clariant Japan Co., Ltd. was used.
- Polyhydric alcohol Polyoxypropylene trimethylolpropane (molecular weight 308, 1 alkylene oxide (propylene oxide) unit per functional group, TMP-F32 manufactured by Nippon Emulsifier Co., Ltd.) was used.
- a solution obtained by dissolving a thermoplastic polyester resin in an o-cresol / chloroform (2/1 vol) mixed solution was used with 1% bromophenol blue as an indicator.
- the solution was titrated with 0.05 mol / L ethanolic potassium hydroxide, and the carboxyl end group concentration was calculated according to the following formula. The end point of the titration was blue (color tone D55-80 (2007 Dpockettype Japan Paint Industry Association).
- Carboxyl end group concentration [eq / g] (0.05 mol / L ethanolic potassium hydroxide [ml] required for titration of a mixed solution of o-cresol / chloroform (2/1 vol) in which component (A) was dissolved) 0.05 mol / L ethanolic potassium hydroxide [ml] required for titration of o-cresol / chloroform (2/1 vol) mixed solution) ⁇ 0.05 mol / L ethanolic potassium hydroxide concentration [mol / ml] ⁇ 1 / Amount of component (A) used for titration [g].
- the concentration of the carboxyl end group derived from the component (A) in the thermoplastic polyester resin composition is calculated according to the following formula. Calculated.
- Component (A) carboxyl end group compound concentration [eq / g] in the thermoplastic polyester resin composition ((A) component carboxyl end group concentration [eq / g] ⁇ (A) component amount [weight] Parts]) / total amount of thermoplastic polyester resin composition [parts by weight].
- Epoxy group concentration [eq / g] (0.1 mol / L perchlorine required for titration of a solution in which acetic acid and triethylammonium bromide / acetic acid solution were added after dissolving in chloroform in which component (B) was dissolved)
- the epoxy group concentration derived from (B) in the thermoplastic polyester resin composition was calculated by the following formula.
- Component (B) component-derived epoxy group blending concentration [eq / g] in the thermoplastic polyester resin composition ((B) component epoxy group concentration [eq / g] ⁇ (B) component blending amount [parts by weight]) ) / Total amount of thermoplastic polyester resin composition [parts by weight].
- (B ′) was calculated by replacing (B ′) with (B) when using a novolac epoxy resin other than the general formula (1).
- reaction catalyst concentration in the thermoplastic polyester resin composition was calculated from the molecular weight and blending amount of the reaction catalyst and the total amount of the thermoplastic polyester resin composition by the following formula.
- thermoplastic polyester resin composition was molded using an IS55EPN injection molding machine manufactured by Toshiba Machine.
- the molding temperature is 250 ° C. and the mold temperature is 80 ° C.
- the molding temperature is 270 ° C.
- gold The mold temperature was 80 ° C.
- the maximum tensile point strength (tensile strength) and the maximum tensile point elongation (tensile elongation) were measured according to ASTM D638 (2005). The value was the average of the measured values of the three test pieces. A material having a large value of tensile strength and tensile elongation was judged to have excellent mechanical properties.
- Heat resistance heat distortion temperature
- IS55EPN injection molding machine manufactured by Toshiba Machine
- the thermal deformation temperature was measured under a measurement load of 1.82 MPa in accordance with ASTM D648 (2005). The value was the average of three measured values.
- a material having a heat distortion temperature of less than 50 ° C. was judged to be inferior in heat resistance, and a material having a larger heat deformation temperature was judged to be excellent in heat resistance.
- thermoplastic polyester resin composition containing glass fiber or (E) reaction catalyst was further subjected to wet heat treatment for 96 hours (4 days) (total 192 hours (8 days)).
- total 192 hours (8 days) Regarding the molded product after the wet heat treatment, the above 4.
- the tensile maximum point strength was measured under the same conditions as the tensile test of the item, and the average value of the measured values of the three test pieces was obtained. From the tensile maximum point strength of the test piece after the wet heat treatment and the tensile maximum point strength of the test piece not subjected to the wet heat treatment, the tensile strength retention rate was determined by the following formula.
- Tensile strength retention rate (%) (maximum tensile point strength after wet heat treatment ⁇ tensile maximum point strength without wet heat treatment) ⁇ 100 A material having a tensile strength retention rate of less than 50% was judged to be inferior in hydrolysis resistance, and a material having a larger tensile strength retention rate was judged to be excellent in hydrolysis resistance.
- melt viscosity index (residence stability)
- melt viscosity index (melt flow index) of the thermoplastic polyester resin composition was measured according to ASTM D1238 (1999) under the conditions of a temperature of 250 ° C. and a load of 2160 g using C501DOS manufactured by Toyo Seiki Co., Ltd.
- the melt viscosity index was measured under the same conditions, and the difference (change rate (%)) of the melt viscosity index before and after the stay relative to the melt viscosity index before the stay )
- change rate of the melt viscosity index exceeded 50%, it was judged that the residence stability was poor, and it was judged that the smaller the difference, the better the residence stability.
- (A) Carboxyl terminal group concentration with respect to thermoplastic polyester resin in thermoplastic polyester resin composition is 2 g of thermoplastic polyester resin composition.
- a solution of 50-mL mixed solution of o-cresol / chloroform (2/1 vol) was titrated with 0.05 mol / L ethanolic potassium hydroxide using 1% bromophenol blue as an indicator, and the entire thermoplastic polyester resin composition The carboxyl group concentration was calculated by dividing the concentration by the blending ratio of the thermoplastic polyester resin (A).
- Epoxy group concentration in the thermoplastic polyester resin composition was determined by dissolving 2 g of the thermoplastic polyester resin composition in 30 mL of o-cresol / chloroform (2/1 vol), 20 mL of acetic acid and 10 mL of a triethylammonium bromide / acetic acid 20 wt% solution were added, and potentiometric titration was performed with 0.1 mol / L perchloric acid acetic acid.
- the obtained pellets were dried by a hot air dryer at a temperature of 110 ° C. for 6 hours and then evaluated by the above method.
- the results are shown in Tables 1 to 16.
- concentration with respect to (A) thermoplastic polyester resin in a thermoplastic polyester resin composition was described in the table
- hydrolysis resistance is within a specific range of the blending amount of the component (B). A material having an excellent balance of heat resistance, bleed-out suppression, and retention stability was obtained.
- Example 2 From a comparison between Example 2 and Examples 31 and 35 to 40, when 0.01 to 1 part by weight of the (C) phosphorus stabilizer was blended, a material with excellent color tone was obtained.
- Example 31 From a comparison between Example 31 and Examples 43 and 46 to 49, when 0.01 to 1 part by weight of (D) monofunctional epoxy compound was blended, the retention stability and long-term hydrolysis resistance were further improved.
- Example 2 From a comparison between Example 2 and Examples 11 to 13, 19 to 21, and 26 to 29, and a comparison between Example 43 and Examples 54 to 56, 64 to 66, and 71 to 74, (E) the reaction catalyst was 0.001. When ⁇ 5 parts by weight were blended, a material excellent in balance between mechanical properties and long-term hydrolysis resistance was obtained. Further, from the comparison of Examples 19 to 25 and the comparison of Examples 64 to 70, the blending concentration of (E) reaction catalyst in the composition relative to the epoxy group concentration derived from (B) novolak type epoxy resin in the composition When the ratio was in the range of 0.01 to 0.1, the balance between mechanical properties and long-term hydrolysis resistance was particularly excellent.
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Abstract
Description
本発明の熱可塑性ポリエステル樹脂組成物は、(A)熱可塑性ポリエステル樹脂100重量部に対し、(B)前記一般式(1)で表されるノボラック型エポキシ樹脂0.1~10重量部を配合してなる。(A)熱可塑性ポリエステル樹脂は、射出成形性や機械物性に優れるものの、加水分解によりエステル結合が分解しやすい。エステル結合が分解すると、カルボキシル末端基濃度が増加する。カルボキシル末端基濃度の増加に伴い(A)熱可塑性ポリエステル樹脂の分子量低下が促進され、機械物性が低下する。本発明においては、(A)熱可塑性ポリエステル樹脂に(B)前記一般式(1)で表されるノボラック型エポキシ樹脂を配合することにより、加水分解により生じる(A)熱可塑性ポリエステル樹脂のカルボキシル末端基と(B)前記一般式(1)で表されるノボラック型エポキシ樹脂とが反応してカルボキシル末端基濃度の増加を抑制し、(A)熱可塑性ポリエステル樹脂の有する高い機械物性を維持することができる。
<A-1>ポリブチレンテレフタレート樹脂:東レ(株)製、カルボキシル末端基濃度30eq/tのポリブチレンテレフタレート樹脂を用いた。
<A-2>ポリエチレンテレフタレート樹脂:東レ(株)製、カルボキシル末端基濃度40eq/tのポリエチレンテレフタレート樹脂を用いた。
<B-1>下記一般式(6)で表されるエポキシ当量290g/eqのノボラック型エポキシ樹脂:日本化薬(株)製“NC-3000H”を用いた。
<B-2>下記一般式(7)で表されるエポキシ当量253g/eqのノボラック型エポキシ樹脂:日本化薬(株)製“XD-1000”を用いた。
<B’-1>下記一般式(8)で表されるエポキシ当量211g/eqのノボラック型エポキシ樹脂:日本化薬(株)製“EOCN-102S”を用いた。
<B’-2>下記一般式(9)で表されるエポキシ当量237g/eqのノボラック型エポキシ樹脂:日本化薬(株)製“NC-2000L”を用いた。
<C-1>ビス(2,6-ジ-t-ブチル-4-メチルフェニル)ペンタエリスリトールジホスファイト:(株)ADEKA製“アデカスタブ”(登録商標)PEP36を用いた。
<C-2>テトラキス(2,4-ジ-t-ブチルフェニル)-4,4’-ビフェニレンジホスフォナイト:クラリアントジャパン(株)製“ホスタノックス”(登録商標)P-EPQを用いた。
<D-1>バーサティック酸グリシジルエステル:モメンティブスペシャルケミカルズ(株)製“カージュラE10P”を用いた。
<D-2>4-t-ブチル安息香酸グリシジルエステル:東京化成工業(株)製(試薬)を用いた。
<E-1>アミジン化合物:1,8-ジアザビシクロ(5,4,0)ウンデセン-7、サンアプロ(株)製“DBU”(登録商標)、分子量152を用いた。
<E-2>イミダゾール:2-エチル-4-メチルイミダゾール、四国化成(株)製2E4MZ、分子量110.16を用いた。
<E-3>有機ホスフィン:トリフェニルホスフィン、和光純薬工業(株)製トリフェニルホスフィン(試薬)、分子量262.29を用いた
<E-4>有機金属化合物:ステアリン酸リチウム、東京化成工業(株)製ステアリン酸リチウム(試薬)、分子量290.42を用いた。
<F-1>ビニル系樹脂:シリコーン・アクリル複合コアシェル型ゴム、三菱レイヨン(株)製“メタブレン”(登録商標)S-2001を用いた。
<F-2>エチレン共重合体:エチレン/ブテン-1/無水マレイン酸共重合体、三井石油化学工業(株)製MH-5020を用いた。
<F-3>ヒンダードフェノール系酸化防止剤:テトラキス[メチレン-3-(3’,5’-ジ-t-ブチル-4’-ヒドロキシフェニル)プロピオネート]メタン、BASFジャパン(株)製“IRGANOX”(登録商標)1010を用いた。
<F-4>離型剤:モンタン酸のエステルワックス、クラリアントジャパン(株)製リコワックスEを用いた。
<F-5>ガラス繊維:繊維径約10μmのチョップドストランド状のガラス繊維、日東紡績(株)製の3J948を用いた。
<F-6>臭素系難燃剤:テトラブロムビスフェノール-A-カーボネートオリゴマー、(帝人化成(株)製“ファイヤガード”(登録商標)FG8500)を用いた。
<F-7>多価アルコール:ポリオキシプロピレントリメチロールプロパン(分子量308、1官能基当たりのアルキレンオキシド(プロピレンオキシド)単位数1、日本乳化剤(株)製TMP-F32)を用いた。
実施例、比較例においては、次に記載する測定方法によって、その特性を評価した。
(A)熱可塑性ポリエステル樹脂をo-クレゾール/クロロホルム(2/1vol)混合溶液に溶解させた溶液を、1%ブロモフェノールブルーを指示薬として、0.05mol/Lエタノール性水酸化カリウムで滴定し、下記式によりカルボキシル末端基濃度を算出した。なお、滴定の終点は、青色(色調D55-80(2007年Dpockettype日本塗料工業会)とした。
カルボキシル末端基濃度[eq/g]=((A)成分を溶解させたo-クレゾール/クロロホルム(2/1vol)混合溶液の滴定に要した0.05mol/Lエタノール性水酸化カリウム[ml]-o-クレゾール/クロロホルム(2/1vol)混合溶液の滴定に要した0.05mol/Lエタノール性水酸化カリウム[ml])×0.05mol/Lエタノール性水酸化カリウムの濃度[mol/ml]×1/滴定に用いた(A)成分の採取量[g]。
熱可塑性ポリエステル樹脂組成物中における(A)成分由来のカルボキシル末端基配合濃度[eq/g]=((A)成分のカルボキシル末端基濃度[eq/g]×(A)成分の配合量[重量部])/熱可塑性ポリエステル樹脂組成物の全体量[重量部]。
JISK7236:2001に従い、(B)前記一般式(1)で表されるノボラック型エポキシ樹脂をクロロホルムに溶解させた溶液に、酢酸および臭化トリエチルアンモニウム/酢酸溶液を加え、0.1mol/L過塩素酸酢酸によって電位差滴定し、下記式によりエポキシ基濃度を算出した。
エポキシ基濃度[eq/g]=((B)成分を溶解させたクロロホルムに溶解させた後、酢酸および臭化トリエチルアンモニウム/酢酸溶液を加えた溶液の滴定に要した0.1mol/L過塩素酸酢酸[ml]-クロロホルムに酢酸および臭化トリエチルアンモニウム/酢酸溶液を加えた溶液の滴定に要した0.1mol/L過塩素酸酢酸[ml])×0.1mol/L過塩素酸酢酸の濃度[mol/ml]×1/滴定に用いた(B)成分の採取量[g])。
熱可塑性ポリエステル樹脂組成物中における(B)成分由来のエポキシ基配合濃度[eq/g]=((B)成分のエポキシ基濃度[eq/g]×(B)成分の配合量[重量部])/熱可塑性ポリエステル樹脂組成物の全体量[重量部]。
なお、参考のため、(B’)一般式(1)以外のノボラック型エポキシ樹脂を用いた場合は、(B’)を(B)と読み替えて算出した。
反応触媒の分子量と配合量、熱可塑性ポリエステル樹脂組成物全体量から、下記式により熱可塑性ポリエステル樹脂組成物中における反応触媒濃度を算出した。
熱可塑性樹脂組成物中における反応触媒の配合濃度[mol/g]=(1/(E)成分の分子量)×(E)成分の配合量[重量部]/熱可塑性ポリエステル樹脂組成物の全体量[重量部])。
東芝機械製IS55EPN射出成形機を用いて、熱可塑性ポリエステル樹脂組成物の成形を行った。(A)成分としてポリブチレンテレフタレート樹脂を使用した場合、成形温度250℃、金型温度80℃の温度条件で、また、(A)成分としてポリエチレンテレフタレート樹脂を使用した場合、成形温度270℃、金型温度80℃の温度条件で行った。射出時間と保圧時間は合わせて10秒、冷却時間10秒の成形サイクル条件で射出成形を行い、試験片厚み1/8インチ(約3.2mm)厚みのASTM1号ダンベルの引張物性評価用試験片を得た。得られた引張物性評価用試験片を用い、ASTMD638(2005年)に従い、引張最大点強度(引張強度)および引張最大点伸び(引張伸度)を測定した。値は3本の試験片の測定値の平均値とした。引張強度および引張伸度の値が大きい材料を機械物性に優れていると判断した。
東芝機械製IS55EPN射出成形機を用いて、上記4.項の引張物性と同一の射出成形条件で、1/8インチ(約3.2mm)厚みの熱変形温度評価用試験片を得た。得られた熱変形温度評価用試験片を用い、ASTMD648(2005年)に従い、測定荷重1.82MPaの条件で熱変形温度を測定した。値は3本の測定値の平均値とした。熱変形温度が50℃未満の材料は耐熱性に劣ると判断し、熱変形温度の数字が大きい材料ほど耐熱性に優れると判断した。
東芝機械製IS55EPN射出成形機を用いて、上記4.項の引張物性と同一射出成形条件で、試験片厚み1/8インチ(約3.2mm)厚みのASTM1号ダンベルの引張物性評価用試験片を得た。得られたASTM1号ダンベルを121℃×100%RHの温度と湿度に設定されたエスペック(株)社製高度加速寿命試験装置EHS-411に投入し、96時間(4日間)、湿熱処理を行った。ガラス繊維または(E)反応触媒を配合した熱可塑性ポリエステル樹脂組成物は、さらに96時間(4日)(合計192時間(8日間))、湿熱処理を行った。湿熱処理後の成形品について、上記4.項の引張試験と同一の条件で引張最大点強度を測定し、3本の試験片の測定値の平均値を求めた。湿熱処理後の試験片の引張最大点強度と湿熱処理未処理の試験片の引張最大点強度から、下記式により引張強度保持率を求めた。
引張強度保持率(%)=(湿熱処理後の引張最大点強度÷湿熱処理未処理の引張最大点強度)×100
引張強度保持率が50%未満の材料は耐加水分解性に劣ると判断し、引張強度保持率の数字が大きい材料ほど耐加水分解性に優れていると判断した。
東洋精機(株)製C501DOSを用いて、温度250℃、荷重2160gの条件で、ASTM D1238(1999年)に準じて熱可塑性ポリエステル樹脂組成物の溶融粘度指数(メルトフローインデックス)を測定した。
東芝機械製IS55EPN射出成形機を用いて、上記4.項の引張物性と同一射出成形条件で、試験片厚み1/8インチ(約3.2mm)厚みのASTM1号ダンベルの色調評価用試験片を得た。得られたASTM1号ダンベルの色調を、日本電色工業製スペクトルカラーメーターSE2000を用いて測定し、黄色度(YI値)を算出した。黄色度(YI値)が30を超える場合は色調が劣ると判断し黄色度(YI値)が小さい材料ほど色調が優れていると判断した。
熱可塑性ポリエステル樹脂組成物中における(A)熱可塑性ポリエステル樹脂に対するカルボキシル末端基濃度は、熱可塑性ポリエステル樹脂組成物2gをo-クレゾール/クロロホルム(2/1vol)混合溶液50mLに溶解させた溶液を、1%ブロモフェノールブルーを指示薬として、0.05mol/Lエタノール性水酸化カリウムで滴定し、熱可塑性ポリエステル樹脂組成物全体に対するカルボキシル基濃度を算出した後に、該濃度を(A)熱可塑性ポリエステル樹脂の配合比で割り返すことにより求めた。
熱可塑性ポリエステル組成物中のエポキシ基濃度は、熱可塑性ポリエステル樹脂組成物2gをo-クレゾール/クロロホルム(2/1vol)30mL混合溶液に溶解させた後、酢酸20mLおよび臭化トリエチルアンモニウム/酢酸20wt%溶液10mLを加え、0.1mol/L過塩素酸酢酸によって電位差滴定することにより算出した。
東芝機械製IS55EPN射出成形機を用いて、上記4.項の引張物性と同一射出成形条件で、試験片厚み1/8インチ(約3.2mm)厚みのASTM1号ダンベルのブリードアウト評価用試験片を得た。得られたASTM1号ダンベルを121℃×100%RHの温度と湿度に設定されたエスペック(株)社製高度加速寿命試験装置EHS-411に96時間(4日間)投入し湿熱処理を行った。湿熱処理後の成形品外観を目視観察し、次の基準によりブリードアウトの判定を行った。
良:成形品に液状もしくは白粉状のブリードアウトが観察されない。
不良:成形品の一部もしくは随所に液状または白粉状のブリードアウトが観察される。
スクリュー径30mm、L/D35の同方向回転ベント付き2軸押出機(日本製鋼所製、TEX-30α)を用いて、(A)熱可塑性ポリエステル樹脂、(B)または(B’)ノボラックエポキシ樹脂、(C)リン系安定剤、(D)単官能エポキシ化合物、(E)反応触媒、および必要に応じてガラス繊維を除くその他の材料を表1~表16に示した含有組成で混合し、2軸押出機の元込め部から添加した。(F-5)ガラス繊維は、表2、8、15に示した含有組成に従い、サイドフィーダーを用い、元込め部とベント部の間から添加した。混練温度260℃、スクリュー回転150rpmの押出条件で溶融混合を行い、得られた樹脂組成物をストランド状に吐出し、冷却バスを通し、ストランドカッターによりペレット化した。
Claims (11)
- (A)熱可塑性ポリエステル樹脂100重量部に対し、(B)下記一般式(1)で表されるノボラック型エポキシ樹脂0.1~10重量部を配合してなる熱可塑性ポリエステル樹脂組成物;
- 熱可塑性ポリエステル樹脂組成物中における(A)熱可塑性ポリエステル樹脂由来のカルボキシル末端基配合濃度(eq/g)に対する、(B)前記一般式(1)で表されるノボラック型エポキシ樹脂由来のエポキシ基配合濃度(eq/g)の比(エポキシ基配合濃度/カルボキシル末端基配合濃度)が1~8である請求項1に記載の熱可塑性ポリエステル樹脂組成物。
- 熱可塑性ポリエステル樹脂組成物中における、(A)熱可塑性ポリエステル樹脂に対するカルボキシル末端基濃度が20eq/t以下である請求項1または2記載の熱可塑性ポリエステル樹脂組成物。
- 熱可塑性ポリエステル樹脂組成物中におけるエポキシ基濃度が5eq/t以上である請求項1~3のいずれかに記載の熱可塑性ポリエステル樹脂組成物。
- (A)熱可塑性ポリエステル樹脂100重量部に対し、さらに(C)リン系安定剤0.01~1重量部を配合してなる請求項1~4のいずれかに記載の熱可塑性ポリエステル樹脂組成物。
- (A)熱可塑性ポリエステル樹脂100重量部に対し、さらに(D)単官能エポキシ化合物0.01~1重量部を配合してなる請求項1~5のいずれかに記載の熱可塑性ポリエステル樹脂組成物。
- (A)熱可塑性ポリエステル樹脂100重量部に対し、さらに(E)反応触媒0.001~5重量部を配合してなる請求項1~6のいずれかに記載の熱可塑性ポリエステル樹脂組成物。
- 熱可塑性ポリエステル樹脂組成物中における(B)前記一般式(1)で表されるノボラック型エポキシ樹脂由来のエポキシ基配合濃度(eq/g)に対する、(E)反応触媒の配合濃度(mol/g)の比(反応触媒の配合濃度/エポキシ基の配合濃度)が0.01~0.1である請求項7に記載の熱可塑性ポリエステル樹脂組成物。
- (E)反応触媒が窒素またはリンを含有する化合物を含有する請求項7または8に記載の熱可塑性ポリエステル樹脂組成物。
- (E)反応触媒がアミジン化合物を含有する請求項7~9のいずれかに記載の熱可塑性ポリエステル樹脂組成物。
- 請求項1~10のいずれかに記載の熱可塑性ポリエステル樹脂組成物を溶融成形してなる成形品。
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US11319437B2 (en) * | 2017-04-06 | 2022-05-03 | Toray Industries, Inc. | Thermoplastic polyester resin composition and molded article |
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WO2019044813A1 (ja) * | 2017-08-30 | 2019-03-07 | ウィンテックポリマー株式会社 | ポリブチレンテレフタレート樹脂組成物、成形品及び複合体 |
JP2019043991A (ja) * | 2017-08-30 | 2019-03-22 | ウィンテックポリマー株式会社 | ポリブチレンテレフタレート樹脂組成物、成形品及び複合体 |
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JP7338470B2 (ja) | 2018-08-09 | 2023-09-05 | 東レ株式会社 | 熱可塑性ポリエステル樹脂組成物およびその成形品 |
WO2021153414A1 (ja) | 2020-01-31 | 2021-08-05 | 東レ株式会社 | 熱可塑性ポリエステル樹脂組成物および成形品 |
WO2022191314A1 (ja) | 2021-03-12 | 2022-09-15 | 東レ株式会社 | 3-ヒドロキシアジピン酸-3,6-ラクトン組成物 |
Also Published As
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JPWO2015072216A1 (ja) | 2017-03-16 |
JP6428264B2 (ja) | 2018-11-28 |
US11319436B2 (en) | 2022-05-03 |
KR102157130B1 (ko) | 2020-09-17 |
EP3072928A4 (en) | 2017-08-02 |
US20200172726A1 (en) | 2020-06-04 |
CN105793354B (zh) | 2018-05-29 |
KR20160088292A (ko) | 2016-07-25 |
US20160289445A1 (en) | 2016-10-06 |
EP3072928A1 (en) | 2016-09-28 |
EP3072928B1 (en) | 2019-03-20 |
CN105793354A (zh) | 2016-07-20 |
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