JP6438271B2 - Thermoplastic polyester resin composition - Google Patents

Description

  The present invention relates to a thermoplastic polyester resin composition, and more particularly, to a thermoplastic polyester resin composition having excellent impact resistance and exhibiting excellent resistance in an alkaline environment (hereinafter abbreviated as “alkali resistance”). .

  Thermoplastic polyester resins represented by polybutylene terephthalate resin and polyethylene terephthalate resin are excellent in ease of processing, mechanical properties, heat resistance and other physical and chemical properties. Widely used in fields such as automotive parts, building material parts, and other precision equipment parts. However, thermoplastic polyester resins such as polybutylene terephthalate resin and polyethylene terephthalate resin have a problem of environmental stress cracking in an alkaline environment.

  Conventionally, in the automotive field, connectors, distributor parts, ignition coil parts, engine parts, various control units, various sensors, electrical and electronic equipment parts are connectors, switch parts, relay parts, coil parts, building material parts, etc. Typical materials used in a wide range of fields such as sanitary parts and concrete embedding bolts mainly include polyester resins such as polybutylene terephthalate resin and polyethylene terephthalate resin. Particularly for automotive parts for automobiles, moisture and heat resistance (hydrolysis resistance) has been required. In response to this requirement, hydrolysis resistance is improved by using polybutylene terephthalate resin with a small amount of carboxyl end groups, or by reacting carboxyl end groups with specific compounds to cap the carboxyl end groups. Can be made.

  However, the polyester resin or resin composition having improved hydrolysis resistance as described above is insufficient in long-term durability against an alkaline solution, and the usage environment and usage are limited. For example, depending on the application of the resin molded product, it may be used in contact with chemicals such as a snow melting agent, a toilet cleaner, a bathroom cleaner, a bleaching agent, and cement. In particular, in a glass fiber reinforced product, strength reduction due to alkali is remarkable, and deterioration in an alkaline environment is regarded as a problem. In parts made of polybutylene terephthalate resin, there is a risk that cracks may occur or eventually break down due to the action of an alkaline substance, especially in thin-walled parts or parts where distortion remains.

  Therefore, polybutylene terephthalate resin compositions with improved alkali resistance have been studied. Patent Document 1 includes (A) a thermoplastic polyester resin, (B) an impact resistance imparting agent of 1 to 25% by mass, (C) a silicone compound and / or a fluorine compound of 0.1 to 15% by mass, (D A thermoplastic polyester resin composition containing 1 to 50% by mass of an inorganic filler and 0.1 to 10% by mass of a multifunctional compound such as (E) an epoxy compound, an isocyanate compound, and a carboxylic dianhydride has an alkali resistance. It is disclosed that it is excellent. However, with such a resin composition, cracks and cracks in the weld portion in an alkaline environment are improved to some extent, but moldability and appearance characteristics associated with the seepage of silicone compounds and fluorine compounds, as well as alkali resistance There is a fear of falling.

  Patent Document 2 discloses polybutylene terephthalate composed of a polybutylene terephthalate resin (A) containing at least a polybutylene terephthalate copolymer, a polyolefin-modified polysiloxane (B), and a filler (C). It is disclosed that the resin-based resin composition is excellent in alkali resistance. What is disclosed in the examples has a problem that the copolymer is 50% or more and the melting point of the polyolefin-modified polysiloxane is 85 ° C., so that heat resistance and moldability are slightly inferior.

  Further, Patent Documents 3 and 4 include thermoplastic polyester resin (component A) 95 to 10% by mass, polyamide resin (component B) 4 to 50% by mass, and α-olefin and α, β-unsaturated glycidyl ester. It is characterized in that 0 to 150 parts by mass of reinforcing filler (D component) is blended with 100 parts by mass of a resin composition consisting of 1 to 40% by mass of an olefin copolymer (C component) consisting of It has been shown that polyester resin compositions that have improved alkali resistance.

  With the recent trend of reducing the weight and performance of products, resin parts are also being made thinner and smaller. Even if these resin parts are reduced in thickness and size, it is necessary to exhibit sufficient characteristics over a long period of time. For this reason, the present condition is that the polyester resin composition excellent in alkali resistance in which a crack does not generate | occur | produce even in the thin-walled part or the site | part in which distortion remains is being sought.

International Publication WO00 / 078867 JP 2006-291100 A JP 2002-128999 A JP 2006-206921 A

According to the study by the present inventors, it has been found that the thermoplastic polyester resin compositions described in Patent Documents 3 and 4 have insufficient alkali resistance. In particular, in recent years, specifications for alkali resistance have been required to have a very high level. For example, in the alkali resistance test, the details will be described later. However, when the insert molded product is immersed in a 10% by weight NaOH aqueous solution, the time until crack generation is 300 hours or more must be cleared. Is also being sought.
The object of the present invention is to solve the above-mentioned problems of the prior art and to provide an excellent thermoplastic polyester resin composition having improved alkali resistance as described above.

As a result of intensive studies to solve the above problems, the present inventors have used a copolymer of an α-olefin, an unsaturated glycidyl compound and butyl acrylate, and treated with a novolac type epoxy compound as a reinforcing filler. The present invention has been completed by finding that the above-mentioned problems can be solved by using the reinforcing filler, and that the synergistic effect of improving the alkali resistance is further enhanced by the combined use of the polyamide resin and the epoxy compound.
According to the present invention, the following thermoplastic polyester resin composition is provided.

[1] (B) 10-80 parts by mass of (B) polyamide resin, (C) copolymer of α-olefin, unsaturated glycidyl compound and butyl acrylate with respect to 100 parts by mass of (A) thermoplastic polyester resin Parts, (D) 1 to 15 parts by mass of an epoxy compound, (E) 30 to 100 parts by mass of a reinforcing filler treated with a novolac type epoxy compound, and (F) 0.1 to 3 parts by mass of a release agent. A thermoplastic polyester resin composition characterized by the above.
[2] (C) The content of each constituent unit of the copolymer of α-olefin, unsaturated glycidyl compound and butyl acrylate is α-olefin: 50 to 94.5 mass%, unsaturated glycidyl compound: 0. The thermoplastic polyester resin composition according to the above [1], which is 5 to 20% by mass and butyl acrylate: 5 to 49.5% by mass.
[3] The thermoplastic polyester resin composition according to the above [1] or [2], wherein the release agent (F) is polyethylene wax.
[4] The thermoplastic polyester resin composition according to any one of [1] to [3], wherein (D) the epoxy compound is a bisphenol A type epoxy compound.
[5] The thermoplastic polyester resin composition according to any one of [1] to [4], wherein (A) the thermoplastic polyester resin is polyalkylene terephthalate.

In the thermoplastic polyester resin composition of the present invention, the alkali resistance is remarkably improved. Specifically, the time until crack generation in a 10% by weight NaOH aqueous solution immersion condition in an insert molded product is 300 hours or more. A very high alkali resistance can be achieved. It also has excellent impact resistance.
Therefore, the thermoplastic polyester resin composition of the present invention can be applied to a wide range of fields such as the field for vehicles (particularly, the field of automobiles), the field of electrical and electronics, and the field of building materials. In particular, it has excellent alkali resistance and impact resistance as molded parts for automotive parts such as connectors, distributor parts, ignition coil parts, control unit parts, and sensor parts.

It is a schematic diagram of the rectangular parallelepiped iron insert used for evaluation in the Examples. It is a cross-sectional explanatory drawing of the mold cavity with which the insert thing was supported by the support pin. It is a schematic diagram of an insert molded product in which two weld lines are generated in the support pin mark.

  Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

[Summary of Invention]
The thermoplastic polyester resin composition of the present invention comprises (B) 10-80 parts by mass of polyamide resin, (C) α-olefin, unsaturated glycidyl compound, and butyl acrylate with respect to 100 parts by mass of (A) thermoplastic polyester resin. 13 to 60 parts by mass of a copolymer, (D) 1 to 15 parts by mass of an epoxy compound, (E) 30 to 100 parts by mass of a reinforcing filler treated with a novolac type epoxy compound, and (F) a release agent 0.1. It contains ~ 3 parts by mass.

[(A) Thermoplastic polyester resin]
The thermoplastic polyester resin (A) which is the main component of the thermoplastic polyester resin composition of the present invention is a polycondensation of a dicarboxylic acid compound and a dihydroxy compound, a polycondensation of an oxycarboxylic acid compound or a polycondensation of these compounds. The resulting polyester may be a homopolyester or a copolyester.

(A) As a dicarboxylic acid compound which comprises a thermoplastic polyester resin, aromatic dicarboxylic acid or its ester-forming derivative is used preferably.
Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, biphenyl-2,2′-dicarboxylic acid, Biphenyl-3,3′-dicarboxylic acid, biphenyl-4,4′-dicarboxylic acid, diphenyl ether-4,4′-dicarboxylic acid, diphenylmethane-4,4′-dicarboxylic acid, diphenylsulfone-4,4′-dicarboxylic acid Diphenylisopropylidene-4,4′-dicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4′-dicarboxylic acid, anthracene-2,5-dicarboxylic acid, anthracene-2,6-dicarboxylic acid, p -Terphenylene-4,4'-dicarboxylic acid, pyridine-2,5-dicarboxylic acid, etc. Refutaru acid can be preferably used.

These aromatic dicarboxylic acids may be used as a mixture of two or more. As is well known, these can be used in polycondensation reactions as ester-forming derivatives such as dimethyl esters in addition to free acids.
If the amount is small, together with these aromatic dicarboxylic acids, aliphatic dicarboxylic acids such as adipic acid, azelaic acid, dodecanedioic acid, sebacic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid and 1 One or more alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid can be mixed and used.

(A) Examples of the dihydroxy compound constituting the thermoplastic polyester resin include ethylene glycol, propylene glycol, butanediol, hexylene glycol, neopentyl glycol, 2-methylpropane-1,3-diol, diethylene glycol, and triethylene glycol. Examples thereof include aliphatic diols, alicyclic diols such as cyclohexane-1,4-dimethanol, and mixtures thereof. If the amount is small, one or more kinds of long-chain diols having a molecular weight of 400 to 6,000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, and the like may be copolymerized.
In addition, aromatic diols such as hydroquinone, resorcin, naphthalenediol, dihydroxydiphenyl ether, and 2,2-bis (4-hydroxyphenyl) propane can also be used.

  In addition to the above-mentioned bifunctional monomers, trifunctional monomers such as trimellitic acid, trimesic acid, pyromellitic acid, pentaerythritol, and trimethylolpropane are introduced to introduce a branched structure, and fatty acids are used for molecular weight control. A small amount of a monofunctional compound can be used in combination.

  As the (A) thermoplastic polyester resin, usually, a resin mainly composed of polycondensation of a dicarboxylic acid and a diol, that is, a resin comprising 50% by mass, preferably 70% by mass or more of the entire resin, is composed of this polycondensate. The dicarboxylic acid is preferably an aromatic carboxylic acid, and the diol is preferably an aliphatic diol.

(A) Polyalkylene terephthalate resin is particularly preferable as the thermoplastic polyester resin. Here, the polyalkylene terephthalate resin refers to a resin containing 50 mol% or more of alkylene terephthalate structural units in all the structural units, and may be a copolymer of an alkylene terephthalate structural unit and other structural units. The alkylene terephthalate structural unit is preferably 60 mol%, more preferably 70 mol% or more, still more preferably 80 mol%, and particularly preferably 90 mol% or more. Particularly, 95% by mole or more of the acid component is terephthalic acid, and 95% by weight or more of the alcohol component is polyalkylene terephthalate which is an aliphatic diol. Typical examples thereof are polybutylene terephthalate and polyethylene terephthalate. These are preferably those close to homopolyester, that is, those in which 95% by mass or more of the total resin is composed of a terephthalic acid component and 1,4-butanediol or ethylene glycol component.
The main component of the thermoplastic polyester resin (A) of the present invention is preferably polybutylene terephthalate. Here, a main component means the ratio of 60 mass% or more in (A) thermoplastic polyester resin. (A) The proportion of polybutylene terephthalate in the thermoplastic polyester resin is more preferably 70% by mass or more, further preferably 80% by mass or more, particularly preferably 90% by mass or more, and most preferably (A) All of the thermoplastic polyester resin is polybutylene terephthalate.
Moreover, what copolymerized polyalkylene glycols, such as isophthalic acid, a dimer acid, polytetramethylene glycol (PTMG), is preferable. These copolymers are those having a copolymerization amount of 1 mol% or more and less than 50 mol% in all segments of polybutylene terephthalate. Among them, the copolymerization amount is preferably 2 to 50 mol%, more preferably 3 to 40 mol%, and particularly preferably 5 to 30 mol%.

  (A) The intrinsic viscosity of the thermoplastic polyester resin is preferably 0.5 to 2 dl / g, and in terms of moldability and mechanical properties, the intrinsic viscosity is in the range of 0.6 to 1.5 dl / g. What has a viscosity is more preferable. When a material having an intrinsic viscosity lower than 0.5 dl / g is used, the resulting molded product of the resin composition tends to have a low mechanical strength. On the other hand, if it is higher than 2 dl / g, the fluidity of the resin composition may deteriorate and the moldability may deteriorate. In addition, the intrinsic viscosity of (A) thermoplastic polyester resin shall be measured at 30 degreeC in the 1: 1 (mass ratio) mixed solvent of tetrachloroethane and phenol.

  (A) The terminal carboxyl group content of the thermoplastic polyester resin may be appropriately selected and determined, but is preferably 50 eq / ton or less, more preferably 40 eq / ton or less, and 30 eq / ton or less. More preferably it is. By setting it to 50 eq / ton or less, gas is less likely to be generated during melt molding of the resin composition in the present invention. The lower limit of the content of the terminal carboxyl group is not particularly defined, but is usually 5 eq / ton, preferably 10 eq / ton in consideration of the productivity of production of the thermoplastic polyester resin.

  (A) The content of the terminal carboxyl group of the thermoplastic polyester resin was measured by dissolving 0.5 g of polyalkylene terephthalate in 25 mL of benzyl alcohol and titrating with a 0.01 mol / L benzyl alcohol solution of sodium hydroxide. It refers to the value obtained. As a method for adjusting the content of the terminal carboxyl group, a conventionally known arbitrary method such as a method for adjusting a polymerization condition such as a raw material charge ratio at the time of polymerization, a polymerization temperature, a pressure reduction method, a method for reacting a terminal blocking agent, etc. Just do it.

[(B) Polyamide resin]
The (B) polyamide resin in the present invention is obtained by polycondensation of a lactam ring-opening polymer, a polymer obtained by polycondensation of diaminocarboxylic acid, an amine and a dibasic acid, or an equivalent compound thereof. Refers to polymers. Examples of the lactams include propiolactam, α-pyrrolidone, ε-caprolactam, enantolactam, ω-laurolactam, cyclododecalactam, and the like. Examples of the diaminocarboxylic acid include aminocaproic acid, 7-aminoheptanoic acid, 11- Examples thereof include aminoundecanoic acid and 9-aminononanoic acid. Examples of amines include hexamethylenediamine, metaxylylenediamine, and paraxylylenediamine, and examples of dibasic acids include terephthalic acid, isophthalic acid, adipic acid, sebacic acid, dodecanedioic acid, and glutaric acid. It is done.

  More specifically, polyamide 4, polyamide 6, polyamide 7, polyamide 8, polyamide 11, polyamide 12, polyamide 6 · 6, polyamide 6 · 9, polyamide 6 · 10, polyamide 6 · 11, polyamide 6 · 12, polyamide 6T, polyamide 6/6 · 6, polyamide 6/12, polyamide 6 / 6T, polyamide 6 / 6I, polyamide 6I / 6T, polycondensate of metaxylylenediamine and adipic acid (polyamide MXD6), metaxylylenediamine And a polycondensate (polyamide MP6) of a mixed diamine and adipic acid composed of paraxylylenediamine and the like. The polyamide resin may be used alone or as a mixture of two or more. Among these, (A) the melting point of the thermoplastic polyester resin and (B) the melting point of the polyamide resin are preferable, and in the case of a polybutylene terephthalate resin, both polyamide 6 and polyamide 6/6 · 6 are used. Polymerization or polyamide 66 and polyamide MXD6 are preferable, and aliphatic polyamide resins such as polyamide 6 and polyamide 6 · 6 are preferable, and polyamide 6 is most preferable.

  The (B) polyamide resin preferably has a specific range of polymerization degree, that is, a specific range of viscosity. That is, in accordance with the ISO 307 standard, those having a viscosity number of 70 to 200 ml / g measured at a temperature of 25 ° C. in 96 mass% sulfuric acid at a polyamide resin concentration of 0.5 mass% are preferable. When the viscosity number is 70 ml / g or more, the mechanical properties are improved, and conversely, when the viscosity number is 200 ml / g or less, the moldability tends to be improved. A more preferable range of the viscosity number is 90 to 150 ml / g, and a particularly preferable range is 100 to 130 ml / g.

  (B) The terminal carboxyl group content of the polyamide resin may be appropriately selected and determined, but is preferably 35 μeq / g or more, more preferably 40 μeq / g or more, still more preferably 45 μeq / g or more, and particularly preferably 50 μeq / g. g or more. The upper limit is usually 140 μeq / g, preferably 130 μeq / g, more preferably 120 μeq / g. The terminal amino group content is preferably 10 μeq / g or more, more preferably 15 μeq / g or more, and further preferably 20 μeq / g or more. The upper limit is usually 100 μeq / g, preferably 80 μeq / g, more Preferably, it is 70 μeq / g. By setting such end group content, alkali resistance and heat shock resistance tend to be improved, which is preferable.

  (B) The terminal carboxyl group content of the polyamide resin can be measured by dissolving the polyamide resin in benzyl alcohol and titrating with 0.01N sodium hydroxide. The terminal amino group can be measured by dissolving a polyamide resin in phenol and titrating with 0.01N hydrochloric acid. Methods for adjusting the terminal carboxyl group content and the terminal amino group content are conventionally known, such as a method for adjusting polymerization conditions such as a raw material charge ratio during polymerization, a polymerization temperature, a pressure reduction method, and a method for reacting a terminal blocking agent. Any method may be used.

  (B) The polyamide resin is contained in a range of 10 to 80 parts by mass, preferably 14 to 65 parts by mass, and more preferably 18 to 60 parts by mass with respect to 100 parts by mass of the (A) thermoplastic polyester resin. To do. If the amount is less than 10 parts by mass, the effect of improving the alkali resistance intended by the present invention cannot be obtained. If the amount exceeds 80 parts by mass, the (B) polyamide resin is not sufficiently dispersed. This is not preferable because the mechanical properties are likely to deteriorate.

[(C) Copolymer of α-olefin, unsaturated glycidyl compound and butyl acrylate]
Next, the copolymer of (C) α-olefin, unsaturated glycidyl compound and butyl acrylate used as component (C) in the present invention is a ternary copolymer of α-olefin, unsaturated glycidyl compound and butyl acrylate. A quaternary or higher multi-component copolymer composed of an α-olefin, an unsaturated glycidyl compound, butyl acrylate, and other monomers may be used.

Examples of the α-olefin in the copolymer (C) include α-olefins having about 2 to 8 carbon atoms such as ethylene, propylene, 1-butene and 1-pentene, but ethylene is particularly preferable.
The unsaturated glycidyl compound is preferably glycidyl (meth) acrylate or unsaturated glycidyl ether such as vinyl glycidyl ether, allyl glycidyl ether, 2-methylallyl glycidyl ether, etc., and particularly glycidyl (meth) acrylate. That is, glycidyl acrylate or glycidyl methacrylate is preferred.

  Other monomers that can be a component of the quaternary or higher multi-component copolymer include methyl acrylate, ethyl acrylate, propyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, and methacrylic acid. (Meth) acrylates such as methyl, ethyl methacrylate, propyl methacrylate, butyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, dimethyl maleate, diethyl maleate, vinyl acetate, propion Examples thereof include vinyl esters such as vinyl acid, acrylonitrile, styrene, carbon monoxide, maleic anhydride and the like.

(C) In the copolymer of α-olefin, unsaturated glycidyl compound and butyl acrylate, the preferred content of each structural unit is that when the mass of the entire component (C) is 100% by mass, the α-olefin is 50 to 94.5 mass%, more preferably 52 to 85 mass%, still more preferably 55 to 75 mass%, and the unsaturated glycidyl compound is 0.5 to 20 mass%, more preferably 1 to 18 mass%, More preferably, it is 2-15 mass%, Most preferably, it is 3-10 mass%, A butyl acrylate is 5-49.5 mass%, More preferably, it is 7-45 mass%, More preferably, it is 10-40 mass %, Particularly preferably 15 to 35% by mass, and other monomers other than those described above are 0 to 49.5% by mass, more preferably 0.5 to 40% by mass, and still more preferably 1 to 35%. Those copolymerized in a mass% range are preferred.
If the content of the unsaturated glycidyl compound is too small, the heat resistance of the thermoplastic polyester resin composition may be impaired. On the other hand, if the amount is too large, the resin viscosity will rapidly increase and molding will be difficult. And may cause problems such as gel formation in the composition. Moreover, it becomes easy to give favorable softness | flexibility to a thermoplastic polyester resin composition by using what copolymerized butyl acrylate in the said range.

  (C) The copolymer of α-olefin, unsaturated glycidyl compound and butyl acrylate may be a random copolymer or a graft copolymer, but it is preferable to use a random copolymer. . Such a random copolymer can be obtained, for example, by radical copolymerization under high temperature and high pressure.

  (C) The copolymer of an α-olefin, an unsaturated glycidyl compound, and butyl acrylate has a melt flow rate (based on JIS K7210-1999, measured at 190 ° C. under a 2.16 kg load) of 0.01 to 1000 g / It is preferable to use 10 min, further 0.1 to 200 g / 10 min, particularly 1 to 70 g / 10 min.

  The content of the copolymer of (C) α-olefin, unsaturated glycidyl compound and butyl acrylate is in the range of 13 to 60 parts by mass, preferably 100 parts by mass of (A) thermoplastic polyester resin. It is the range of 15-50 mass parts. If the amount is less than 13 parts by mass, the effect of improving alkali resistance, which is the object of the present invention, cannot be obtained.

[(D) Epoxy compound]
The (D) epoxy compound used in the present invention is for suppressing that the thermoplastic polyester resin is hydrolyzed by water vapor or the like, causing a decrease in molecular weight and at the same time reducing mechanical strength. By containing, the synergistic effect of the copolymer of (B) polyamide resin, (C) α-olefin, unsaturated glycidyl compound and butyl acrylate is promoted, and the alkali resistance can be further improved.

(D) As an epoxy compound, what has one or more epoxy groups in one molecule should just be mentioned, and usually a glycidyl compound which is a reaction product of alcohol, phenols, carboxylic acid, etc. and epichlorohydrin, A compound obtained by epoxidizing an olefinic double bond may be used.
(D) As an epoxy compound, for example, bisphenol A type epoxy compound, bisphenol F type epoxy compound, resorcinol type epoxy compound, novolac type epoxy compound, alicyclic epoxy compound, glycidyl ethers, glycidyl esters, epoxidized butadiene heavy Examples include coalescence.

Examples of the bisphenol A type epoxy compound include bisphenol A-diglycidyl ether and hydrogenated bisphenol A-diglycidyl ether. Examples of the bisphenol F type epoxy compound include bisphenol F-diglycidyl ether and hydrogenated bisphenol F-diglycidyl ether. Examples of the resorcin type epoxy compound include resorcin diglycidyl ether.
Moreover, as a novolak-type epoxy compound, a phenol novolak-type epoxy resin, a cresol novolak-type epoxy resin, etc. can be illustrated.

  Examples of alicyclic epoxy compounds include vinylcyclohexene dioxide, dicyclopentadiene oxide, 3,4-epoxycyclohexyl-3,4-cyclohexylcarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene di Examples thereof include epoxide and 3,4-epoxycyclohexyl glycidyl ether.

  Specific examples of glycidyl ethers include monoglycidyl ethers such as methyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, phenyl glycidyl ether, butylphenyl glycidyl ether, and allyl glycidyl ether; Examples include diglycidyl ethers such as pentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, glycerin diglycidyl ether, propylene glycol diglycidyl ether, and bisphenol A diglycidyl ether. Examples of the glycidyl esters include monoglycidyl esters such as benzoic acid glycidyl ester and sorbic acid glycidyl ester; diglycidyl esters such as adipic acid diglycidyl ester, terephthalic acid diglycidyl ester, and orthophthalic acid diglycidyl ester. .

  Examples of the epoxidized butadiene polymer include epoxidized polybutadiene, epoxidized styrene-butadiene copolymer, and epoxidized hydrogenated styrene-butadiene copolymer.

  The (D) epoxy compound may be a copolymer having a glycidyl group-containing compound as one component. For example, a copolymer of glycidyl ester of α, β-unsaturated acid and one or two or more monomers selected from the group consisting of α-olefin, acrylic acid, acrylic ester, methacrylic acid, methacrylic ester It is done.

  Among the above-described compounds, the (D) epoxy compound is preferably a bisphenol A type epoxy compound or a novolak type epoxy compound obtained from the reaction of bisphenol A or novolak with epichlorohydrin. Among them, the bisphenol A type epoxy compound is preferable because it has good reactivity with the polyamide resin, and the polyamide resin tends to disperse easily and the alkali resistance tends to be improved, and is also preferable from the viewpoint of hydrolysis resistance.

  (D) As the epoxy compound, an epoxy compound having an epoxy equivalent of 100 to 10,000 g / eq and a mass average molecular weight of 8000 or less is preferable. When the epoxy equivalent is less than 100 g / eq, the viscosity of the resin composition is high because the amount of the epoxy group is too large. Conversely, when the epoxy equivalent exceeds 10000 g / eq, the amount of the epoxy group decreases. The effect of improving the alkali resistance of the thermoplastic polyester resin composition tends to be hardly exhibited. The epoxy equivalent is more preferably 300 to 7000 g / eq, and further preferably 500 to 6000 g / eq. Moreover, the thing with a mass average molecular weight exceeding 8000 has a tendency for compatibility with (A) thermoplastic polyester resin to fall, and for the mechanical strength of a molded article to fall. The mass average molecular weight is more preferably 7000 or less, and still more preferably 6000 or less.

  (D) Content of an epoxy compound is 1-15 mass parts with respect to 100 mass parts of (A) thermoplastic polyester resins, 3 mass parts or more are preferable, 4 mass parts or more are more preferable, 4.5 mass parts The above is more preferable. Moreover, 13 mass parts or less, Especially 12 mass parts or less are preferable. (D) When the content of the epoxy compound is less than 1 part by mass, a decrease in alkali resistance or a decrease in hydrolysis resistance due to poor dispersion of the polyamide resin occurs. The fluidity becomes worse.

  Furthermore, it is preferable that the equivalent ratio (epoxy group / COOH group) of the epoxy group of (D) epoxy compound with respect to the terminal COOH group of (A) thermoplastic polyester resin exists in the range of 0.2-2.7. If the equivalent ratio is less than 0.2, the hydrolysis resistance tends to be poor, and if it exceeds 2.7, the moldability tends to be unstable. The epoxy group / COOH group is more preferably 0.3 or more and 2.5 or less.

[(E) Reinforcing filler treated with novolac epoxy compound]
The thermoplastic polyester resin composition of the present invention contains (E) a reinforcing filler treated with a novolac-type epoxy compound in a range of 30 to 100 parts by mass with respect to 100 parts by mass of (A) the thermoplastic polyester resin. . By treating the surface of the reinforcing filler with a novolac type epoxy compound, the alkali resistance and hydrolysis resistance are improved, and the adhesiveness at the interface with the resin component is improved, so that the mechanical properties are easily improved. (E) 40 mass parts or more are preferable, as for content of a reinforcement filler, 50 mass parts or more are more preferable, 90 mass parts or less are preferable, and 85 mass parts or less are more preferable. In the present invention, the reinforcing filler refers to a material that is contained in a resin component to improve strength and rigidity, and may be in any form such as fibrous, plate-like, granular, and amorphous.

  (E) When the form of the reinforcing filler is fibrous, it may be inorganic or organic. For example, glass fiber, carbon fiber, silica / alumina fiber, zirconia fiber, boron fiber, boron nitride fiber, silicon nitride potassium titanate fiber, metal fiber, organic fiber such as wollastonite, fluorine resin fiber, aramid fiber, etc. Fiber is included. (E) When the reinforcing filler is fibrous, inorganic fibers are preferable, and among these, glass fibers are particularly preferable. (E) The reinforcing filler may be a single type or a mixture of two types.

  (E) When the form of the reinforcing filler is fibrous, the average fiber diameter, average fiber length, and cross-sectional shape are not particularly limited, but the average fiber diameter is preferably selected, for example, in the range of 1 to 100 μm. The length is preferably selected in the range of 0.1 to 20 mm, for example. The average fiber diameter is more preferably about 1 to 50 μm, more preferably about 5 to 20 μm. The average fiber length is preferably about 0.12 to 10 mm. In addition, when the fiber cross section is a flat shape such as an oval, an ellipse, or a bowl, the flatness ratio (major axis / minor axis ratio) is preferably 1.4 to 10, more preferably 2 to 6. 5 to 5 is more preferable. It is preferable to use glass fibers having such an irregular cross section because dimensional stability such as warpage of the molded product and anisotropy of the shrinkage rate is easily improved.

Further, (E) the reinforcing filler may be treated with a sizing agent or a surface treating agent other than the novolac epoxy compound in addition to the novolac epoxy compound. Other sizing agents include, for example, epoxy compounds other than novolak epoxy compounds such as bisphenol A type epoxy compounds, acrylic compounds, and surface treatment agents include isocyanate compounds, silane compounds, titanate compounds, and the like. These functional compounds are mentioned.
(E) The reinforcing filler may be previously surface-treated with the above-described novolak-type epoxy compound, or when the thermoplastic polyester resin composition of the present invention is prepared, the novolak-type epoxy compound may be added to the surface treatment. Good.

  In addition to the fibrous reinforcing filler described above, other reinforcing fillers in the form of plates, granules, or amorphous can also be contained. The plate-like inorganic filler exhibits a function of reducing anisotropy and warping, and examples thereof include glass flakes, talc, mica, mica, kaolin, and metal foil. Among the plate-like inorganic fillers, glass flakes are preferable.

  Other inorganic fillers that are granular or amorphous include ceramic beads, asbestos, clay, zeolite, potassium titanate, barium sulfate, titanium oxide, silicon oxide, aluminum oxide, magnesium hydroxide, and the like.

[(F) Release agent]
The thermoplastic polyester resin composition of the present invention contains (F) a release agent in the range of 0.1 to 3 parts by mass with respect to (A) 100 parts by mass of the thermoplastic polyester resin. As the mold release agent, known mold release agents usually used for polyester resins can be used. Among them, a polyolefin compound, a fatty acid ester compound, and a silicone compound are selected from the viewpoint of good alkali resistance. One or more release agents are preferred, and polyolefin compounds are particularly preferred.

  Examples of the polyolefin compound include compounds selected from paraffin wax and polyethylene wax. Among them, those having a mass average molecular weight of 700 to 10,000, more preferably 900 to 8,000 are preferable.

  Examples of the fatty acid ester compounds include saturated or unsaturated aliphatic monovalent or divalent carboxylic acid esters, glycerin fatty acid esters, sorbitan fatty acid esters and the like, partially saponified products thereof, and the like. Among these, mono- or di-fatty acid esters composed of fatty acids and alcohols having 11 to 28 carbon atoms, preferably 17 to 21 carbon atoms are preferable.

Aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, mellicic acid, tetrariacontanoic acid, montanic acid, adipic acid, azelaic acid Etc. The aliphatic carboxylic acid may be an alicyclic carboxylic acid.
Examples of the alcohol include saturated or unsaturated monovalent or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, a monovalent or polyvalent saturated alcohol having 30 or less carbon atoms is preferable, and an aliphatic saturated monohydric alcohol or polyhydric alcohol having 30 or less carbon atoms is more preferable. Here, aliphatic includes alicyclic compounds.
Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol, and the like. Is mentioned.
In addition, said ester compound may contain aliphatic carboxylic acid and / or alcohol as an impurity, and may be a mixture of a some compound.

  Specific examples of the fatty acid ester compounds include glycerin monostearate, glycerin monobehenate, glycerin dibehenate, glycerin-12-hydroxy monostearate, sorbitan monobehenate, pentaerythritol monostearate, pentaerythritol di Examples include stearate, stearyl stearate, and ethylene glycol montanate.

  Moreover, as a silicone type compound, the compound modified | denatured from points, such as compatibility with a polyester resin, is preferable. Examples of the modified silicone oil include silicone oil in which an organic group is introduced into the side chain of polysiloxane, silicone oil in which an organic group is introduced into both ends and / or one end of polysiloxane, and the like. Examples of the organic group to be introduced include an epoxy group, an amino group, a carboxyl group, a carbinol group, a methacryl group, a mercapto group, and a phenol group, and preferably an epoxy group. As the modified silicone oil, a silicone oil in which an epoxy group is introduced into the side chain of polysiloxane is particularly preferable.

  (F) As mentioned above, the content of the release agent is 0.1 to 3 parts by mass with respect to 100 parts by mass of (A) thermoplastic polyester resin, but 0.2 to 2.5 parts by mass. It is preferable that If the amount is less than 0.1 parts by mass, the surface property tends to deteriorate due to defective mold release at the time of melt molding. On the other hand, if it exceeds 3 parts by mass, the kneading workability of the resin composition decreases, and molding is also performed. Cloudiness may be seen on the body surface. The content of the release agent is more preferably 0.5 to 2 parts by mass.

[Stabilizer]
It is preferable that the thermoplastic polyester resin composition of the present invention contains a stabilizer because it has effects of improving thermal stability and preventing deterioration of mechanical strength, transparency and hue. As the stabilizer, a sulfur stabilizer and a phenol stabilizer are preferable.

  As the sulfur stabilizer, any conventionally known sulfur atom-containing compound can be used, and among these, thioethers are preferred. Specifically, for example, didodecylthiodipropionate, ditetradecylthiodipropionate, dioctadecylthiodipropionate, pentaerythritol tetrakis (3-dodecylthiopropionate), thiobis (N-phenyl-β-naphthylamine) ), 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, nickel dibutyldithiocarbamate, nickel isopropylxanthate, trilauryltrithiophosphite. Among these, pentaerythritol tetrakis (3-dodecylthiopropionate) is preferable.

  Examples of the phenol-based stabilizer include pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), octadecyl-3- (3,5-di-tert-butyl-4) -Hydroxyphenyl) propionate, thiodiethylenebis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), pentaerythritol tetrakis (3- (3,5-di-neopentyl-4-hydroxyphenyl) ) Propionate) and the like. Among these, pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionate is preferred.

  One type of stabilizer may be contained, or two or more types may be contained in any combination and ratio.

  The content of the stabilizer is preferably 0.001 to 2 parts by mass with respect to 100 parts by mass of (A) the thermoplastic polyester resin. When the content of the stabilizer is less than 0.001 part by mass, it is difficult to expect an improvement in the thermal stability and compatibility of the resin composition, and a decrease in molecular weight and hue deterioration during molding are likely to occur. When it exceeds, it will become excess amount and there exists a tendency for generation | occurrence | production of silver and a hue deterioration to occur further easily. The content of the stabilizer is more preferably 0.01 to 1.5 parts by mass, and still more preferably 0.1 to 1 part by mass.

[Carbodiimide compound]
The thermoplastic polyester resin composition of the present invention preferably contains a carbodiimide compound for the purpose of improving heat shock resistance and further improving alkali resistance. A carbodiimide compound is a compound having a carbodiimide group (—N═C═N—) in one molecule.

  In the carbodiimide compound, the group bonded to the carbodiimide group is not particularly limited, and an aliphatic group, an alicyclic group, an aromatic group, or a group to which these organic groups are bonded (for example, benzyl group, phenethyl group, 1, 4 -Xylylene group, etc.). Examples of the carbodiimide compound preferably used in the present invention include an aliphatic carbodiimide compound in which an aliphatic group is linked to a carbodiimide group, an alicyclic carbodiimide compound in which an alicyclic group is linked to a carbodiimide group, and an aromatic to a carbodiimide group. Examples include aromatic carbodiimide compounds in which a group or a group containing an aromatic group is linked. Among these, from the viewpoint of the degree of expression of alkali resistance effect and heat shock resistance, it is more preferable to use an aromatic carbodiimide compound. preferable.

Examples of the aliphatic carbodiimide compound include mono- or dicarbodiimide compounds such as diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, t-butylisopropylcarbodiimide, di-t-butylcarbodiimide, and polycarbodiimide compounds.
Examples of the alicyclic carbodiimide compound include dicarbodiimides such as dicyclohexylcarbodiimide, and polycarbodiimides such as poly (4,4′-dicyclohexylmethanecarbodiimide).
Aromatic carbodiimide compounds include diphenylcarbodiimide, di-β-naphthylcarbodiimide, di-2,6-dimethylphenylcarbodiimide, N-tolyl-N′-phenylcarbodiimide, di-p-nitrophenylcarbodiimide, di-p-amino. Phenylcarbodiimide, di-p-hydroxyphenylcarbodiimide, di-p-chlorophenylcarbodiimide, di-p-methoxyphenylcarbodiimide, di-3,4-dichlorophenylcarbodiimide, di-2,5-chlorophenylcarbodiimide, di-o-chlorophenylcarbodiimide P-phenylene-bis-di-o-tolylcarbodiimide, p-phenylene-bis-dicyclohexylcarbodiimide, p-phenylene-bis-di-chlorophenylcarbodiimide, ethyl Mono- or dicarbodiimide compounds such as bis-diphenylcarbodiimide, and poly (4,4′-diphenylmethanecarbodiimide), poly (3,5′-dimethyl-4,4′-diphenylmethanecarbodiimide), poly (p-phenylenecarbodiimide) ), Poly (m-phenylenecarbodiimide), poly (naphthylenecarbodiimide), poly (1,3-diisopropylphene to lencarbodiimide), poly (1-methyl-3,5-diisopropylphenylenecarbodiimide), poly (1,3 , 5-triethylphenylenecarbodiimide), polycarbodiimide compounds such as poly (triisopropylphenylenecarbodiimide), and the like.

  In the present invention, as the carbodiimide compound, it is more preferable to use a polycarbodiimide compound having two or more carbodiimide groups in the molecule, and it is more preferable to use an aromatic polycarbodiimide compound. A polycarbodiimide compound having two or more carbodiimide groups is obtained by, for example, subjecting a polyvalent isocyanate compound having at least two isocyanate groups in the molecule to a decarbonization condensation reaction (carbodiimidization reaction) in the presence of a carbodiimidization catalyst. Can be manufactured. The carbodiimidization reaction can be performed by a known method. Specifically, the isocyanate is dissolved in an inert solvent, or phosphorene is dissolved in an inert gas stream such as nitrogen or bubbling without solvent. By adding a carbodiimidization catalyst such as an organic phosphorus compound typified by oxides and heating and stirring in a temperature range of 150 to 200 ° C., a condensation reaction (carbodiimidization reaction) accompanied by decarbonation can be advanced. .

As a preferable polyvalent isocyanate compound, a bifunctional isocyanate having two isocyanate groups in the molecule is particularly suitable, but an isocyanate compound having three or more isocyanate groups can be used in combination with a diisocyanate. The polyvalent isocyanate compound may be any of aliphatic isocyanate, alicyclic isocyanate, and aromatic isocyanate.
Specific examples of the polyvalent isocyanate include hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, xylylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,12-diisocyanate dodecane, norbornane diisocyanate 2,4-bis- ( 8-isocyanate octyl) -1,3-dioctylcyclobutane, 4,4′-dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, 2,4,6-triisopropylphenyl diisocyanate, 4,4′-diphenylmethane diisocyanate ( MDI), tolylene diisocyanate (TDI), hydrogenated tolylene diisocyanate and the like, but are not limited thereto.

When the carbodiimide compound is a polycarbodiimide compound, the molecular weight is preferably 2,000 g / mol or more. By using such a polycarbodiimide compound having a molecular weight, it tends to suppress the generation of gas and odor during melt-kneading and molding. The molecular weight is preferably 3,000 to 50,000 g / mol, more preferably 8,000 to 40,000 g / mol, and particularly preferably 10,000 to 30,000 g / mol.
The carbodiimide compound preferably has a carbodiimide equivalent of 200 to 5,000 g / mol, more preferably 500 to 4,000 g / mol, and still more preferably 1,000 to 3,000 g / mol. By setting the carbodiimide equivalent in such a range, it becomes easy to effectively improve both heat shock resistance and alkali resistance.

  Among the carbodiimide compounds, di-2,6-dimethylphenylcarbodiimide, poly (4,4′-diphenylmethanecarbodiimide), poly (phenylenecarbodiimide), poly (4,4′-dicyclohexylmethanecarbodiimide), poly (triisopropylphenylene) Carbodiimide) and poly (diisopropylphenylcarbodiimide) are preferable, and poly (4,4′-dicyclohexylmethanecarbodiimide) and poly (triisopropylphenylenecarbodiimide) are particularly preferable.

  It is preferable that content of a carbodiimide compound is 0.1-2 mass parts with respect to 100 mass parts of (A) thermoplastic polyester resin. When the content of the carbodiimide compound is in the above range, the heat shock resistance is easily improved, and the alkali resistance is further easily improved. When the content exceeds the upper limit, gelation products and carbides are easily generated during melt-kneading and molding, and mechanical properties such as tensile strength and bending strength may be lowered. In addition, a rapid decrease in strength under wet heat tends to occur. The content of the carbodiimide compound is more preferably 0.2 to 1.5 parts by mass, and still more preferably 0.3 to 1 part by mass.

[Flame retardants]
The thermoplastic polyester resin composition of the present invention can contain a flame retardant in order to impart flame retardancy. Examples of the flame retardant include organic halogen compounds, antimony compounds, phosphorus compounds, nitrogen compounds, and other organic and inorganic compounds. Specific examples of the organic halogen compound include brominated polycarbonate, brominated epoxy resin, brominated phenoxy resin, brominated polyphenylene ether resin, brominated polystyrene resin, brominated bisphenol A, pentabromobenzyl polyacrylate and the like.

  Examples of the antimony compound include antimony trioxide, antimony pentoxide, and sodium antimonate. Examples of the phosphorus compound flame retardant include phosphoric acid ester, polyphosphoric acid, melamine polyphosphate, ammonium polyphosphate, phosphinic acid metal salt, and red phosphorus. Examples of the nitrogen flame retardant include melamine cyanurate and phosphazene. Examples of organic flame retardants and inorganic flame retardants other than the above include inorganic compounds such as aluminum hydroxide, magnesium hydroxide, silicon compounds, and boron compounds.

[Other ingredients]
The thermoplastic polyester resin composition of the present invention may contain conventionally known various resin additives as long as the effects of the present invention are not impaired as required. Various resin additives include antioxidants, ultraviolet absorbers, weathering stabilizers, colorants such as dyes and pigments, catalyst deactivators, antistatic agents, foaming agents, plasticizers, (C) α-olefins and unsaturated Examples thereof include impact resistance improvers, crystal nucleating agents, crystallization accelerators other than the glycidyl compound and butyl acrylate copolymer.

  The thermoplastic polyester resin composition of the present invention can contain other thermoplastic resins, thermosetting resins, and the like as long as they do not impair the effects of the present invention. Examples of the other thermoplastic resins include polyethylene resins, polypropylene resins, acrylic resins, polycarbonate resins, polyacetal resins, polyphenylene oxide resins, polyphenylene sulfide resins, liquid crystal polyester resins, and the like. Thermosetting resins include phenol resins, A melamine resin, a silicone resin, an epoxy resin, etc. are mentioned. These may be one type or two or more types.

  The method for producing the thermoplastic polyester resin composition of the present invention is not limited to a specific method, but is preferably based on a melting / kneading method. The melting / kneading method can be a method usually employed for thermoplastic resins.

Examples of the melting / kneading method include (A) thermoplastic polyester resin, (B) polyamide resin, (C) a copolymer of α-olefin, unsaturated glycidyl compound and butyl acrylate, (D) epoxy compound, ( E) Reinforcing filler treated with novolac type epoxy compound and (F) release agent are uniformly mixed with a Henschel mixer, ribbon blender, V-type blender, tumbler, etc., and then uniaxial or multi-axial kneading extruder, roll And a method of melting and kneading with a Banbury mixer, a Laboplast mill (Brabender), or the like. If necessary, it is preferable that the reinforcing filler (E) is supplied from the side feeder of the kneading extruder so that breakage of the reinforcing filler can be suppressed and dispersed.
The temperature and kneading time for melting and kneading can be selected according to the type of components constituting the resin component, the ratio of the components, the type of melting and kneading machine, etc., but the temperature for melting and kneading is 200 to 300. A range of ° C is preferred. When the temperature exceeds 300 ° C., thermal deterioration of (A) thermoplastic polyester resin, (B) polyamide resin, (C) copolymer of α-olefin, unsaturated glycidyl compound and butyl acrylate becomes a problem. The physical properties may deteriorate or the appearance may deteriorate.

  The method for producing the desired molded product from the thermoplastic polyester resin composition of the present invention is not particularly limited, and molding methods conventionally employed for thermoplastic resins, that is, injection molding methods, insert molding methods, A hollow molding method, an extrusion molding method, a compression molding method, or the like can be used. Molded products that can be manufactured include, for example, various storage containers, electrical / electronic parts, office automate (OA) equipment parts, home appliance parts, mechanical mechanism parts, building material parts, other precision equipment parts, automotive mechanism parts, sanitary Applicable to parts. In particular, it can be suitably used for in-vehicle parts, motor parts, various sensor parts, connector parts, switch parts, breaker parts, relay parts, coil parts, transformer parts, lamp parts, and the like. Especially, cases, covers or housings for storing various electric and electronic parts, molded parts for in-vehicle parts around automobile engines, for example, various sensors, connectors, distributor parts, ignition coil parts, and in-vehicle parts such as cases and casings It is suitable as a resin material.

  In particular, the molded product of the thermoplastic polyester resin composition of the present invention is such that, in the alkali resistance test, the time until the occurrence of cracks when the insert molded product is immersed in a 10% by weight NaOH aqueous solution is 300 hours or more. Since extremely high alkali resistance can be achieved, it has excellent characteristics particularly with respect to the characteristics required for in-vehicle components.

EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example and a comparative example, this invention is limited to the following description examples, and is not interpreted.
The raw material components used in Examples and Comparative Examples are as shown in Table 1 below.

[Examples 1-8 and Comparative Examples 1-12]
<Manufacture of a thermoplastic polyester resin composition>
Among the components shown in Table 1, each component other than glass fiber was blended in the proportions (all parts by mass) shown in Tables 2 to 4, and this was blended into a 30 mm vent type twin screw extruder (Japan). Glass fiber is supplied from a side feeder using a twin-screw extruder TEX30α) manufactured by Steelworks Co., Ltd., melt kneaded at a barrel temperature of 270 ° C., extruded into strands, pelletized with a strand cutter, and polybutylene terephthalate. A pellet of the resin composition was obtained.

<Molding of test piece for measurement evaluation>
The obtained pellets were subjected to an ISO test piece for measuring Charpy impact strength and alkali resistance under the conditions of a cylinder temperature of 250 ° C. and a mold temperature of 80 ° C. using an injection molding machine (model NEX80-9E) manufactured by Nissei Plastic Industry Co., Ltd. A test specimen for evaluation was molded, and performance evaluation was performed by the following test method.

[Measurement evaluation method]
Measurement and evaluation of various physical properties / performances in Examples and Comparative Examples were carried out by the following methods.
(A) Charpy impact strength (unit: kJ / m ² ):
The notched Charpy impact strength was measured according to ISO179.

(B) Alkali resistance evaluation:
Using a TH60 R5VSE vertical injection molding machine manufactured by Nissei Plastic Industrial Co., Ltd., a cylinder-shaped iron (SUS) insert 1 (length 16 mm × width 33 mm × width) at a cylinder temperature of 250 ° C. and a mold temperature of 80 ° C. As shown in FIG. 2, the thickness 3 mm) was inserted into the mold cavity 4 with the support pins 2 and inserted (insert iron piece 3). The insert molded product (length 18 mm × width 35 mm × thickness 5 mm) shown in FIG. 3 was produced by insert molding. The thickness of the resin part of this insert molded product is 1 mm. In the insert molded product, two weld lines 6 are generated in the support pin mark 5.
This insert molded article was immersed in a 10% by mass NaOH aqueous solution at room temperature. After the immersion, the presence or absence of cracks was visually confirmed periodically, and the time (hr) until cracks occurred was measured. In addition, visual observation was performed until 600 hours passed, and when no crack was generated after 600 hours passed, “≧ 600” was described in the table. The longer this time, the better the alkali resistance.

(B) Heat shock resistance test:
A DTS-30 heat shock test manufactured by Irie Manufacturing Co., Ltd. was performed using the insert molded product obtained in the same manner as in the test for evaluating the alkali resistance (b). The conditions of the heat shock test are a cycle of 60 minutes at −40 ° C. → 30 minutes at 130 ° C. The average value of the number of cycles in which cracks occur in a total of 10 weld lines in 5 molded products. Displayed.
The above evaluation results are shown in Tables 2 to 4 below.

  The thermoplastic polyester resin composition of the present invention can achieve extremely high alkali resistance and is excellent in impact resistance. Therefore, the automotive field, in particular, automotive electrical components, sensor components, and automotive components around the engine. It is an extremely useful material for manufacturing, and is further useful in a wide range of fields such as electrical and electronic parts, building material parts, sanitary parts, and machine parts.

1. Insert iron piece 2. 2. Support pin 3. Insert iron pieces inserted into the mold Cavity 5. 5. Support pin mark Weld line

Claims (3)

(A) 10 to 60 parts by mass of (B) polyamide resin, (C) 15 to 50 parts by mass of copolymer of α-olefin, unsaturated glycidyl compound and butyl acrylate, with respect to 100 parts by mass of polybutylene terephthalate resin , D) 1 to 15 parts by mass of an epoxy compound, (E) 30 to 100 parts by mass of a reinforcing filler treated with a novolac type epoxy compound, and (F) 0.1 to 3 parts by mass of a release agent , (C) The content of each constituent unit of the copolymer of α-olefin, unsaturated glycidyl compound and butyl acrylate is α-olefin: 50 to 94.5 mass%, unsaturated glycidyl compound: 0.5 to 20 mass%, Butyl acrylate: A thermoplastic polyester resin composition characterized by being 5 to 49.5% by mass . (F) The thermoplastic polyester resin composition according to claim 1, wherein the release agent is polyethylene wax. (D) The thermoplastic polyester resin composition according to claim 1 or 2 , wherein the epoxy compound is a bisphenol A type epoxy compound.

Images