JP6822163B2 - Thermoplastic polyester resin compositions and articles - Google Patents

Description

The present invention relates to a thermoplastic polyester resin composition and a molded product obtained by molding the thermoplastic polyester resin composition.

Thermoplastic polyester resins are used in a wide range of fields such as mechanical mechanical parts, electrical / electronic parts, and automobile parts by taking advantage of their excellent injection moldability and mechanical physical characteristics. However, since thermoplastic polyester resin is easily deteriorated by hydrolysis, it has general chemical and physical properties for use as an industrial material such as mechanical mechanical parts, electric parts, electronic parts and automobile parts. In addition to balance, it is required to have long-term hydrolysis resistance. Further, in recent years, due to the increase in the operating temperature of industrial materials such as electric parts, electronic parts and automobile parts, there is a concern about strength decrease and coloring due to oxidative deterioration in a high temperature environment, and oxidative deterioration resistance and color tone. A material with excellent stability is required.

As a method for imparting hydrolysis resistance to a thermoplastic polyester resin, a method of blending an epoxy resin with a thermoplastic polyester resin is known. As such a resin composition, a thermoplastic resin composition obtained by blending a thermoplastic polyester resin with a compound having three or more functional groups and two or more kinds of reactive end-sealing agents (see Patent Document 1). ), A polybutylene terephthalate resin composition (Patent Document 2) is proposed in which a glycidyl group-containing copolymer, an ethylene / α-olefin copolymer, a fiber reinforcing material, and an epoxy compound are blended with a polybutylene terephthalate resin. Has been done.

Further, as a method of imparting color stability and oxidation deterioration resistance to a thermoplastic polyester resin, a method of blending an antioxidant at the time of compounding and a method of blending a compound such as sodium hypophosphite at the time of polymerization are known. ing. As such a resin composition, color enhancement including a core-shell type impact resistance improving material, a bifunctional epoxy compound, a thioester-based stabilizer and phosphite or a phosphonite-based stabilizer and a hindered phenol-based stabilizer in an alkylenearyl polyester. A resin composition containing a stabilizer (see Patent Document 3), an epoxy resin derived from dihydric phenol and epichlorohydrin during the polymerization production of a polyalkylene terephthalate resin, and an alkali metal salt and hypophosphate. A method for producing a polyalkylene terephthalate resin (Patent Document 4) has been proposed in which at least one of the alkali metal salts and the alkali metal salts of aromatic acids is added and polymerized.

JP-A-2009-155478 Japanese Unexamined Patent Publication No. 2014-196484 Japanese Unexamined Patent Publication No. 2005-68422 JP-A-63-227624

However, even with the techniques described in Patent Documents 1 and 2, the hydrolysis resistance of the resin composition was still insufficient. Further, the system to which an antioxidant is added as in Patent Document 3 has insufficient oxidation deterioration resistance and color stability, and the alkali metal salt and hypophosphorous acid alkali metal salt used in Patent Document 4 are deliquescent. Due to its properties, there is a problem that it bleeds out from the molded product when the molded product is subjected to a wet heat treatment.

The present invention provides a thermoplastic polyester resin composition and a molded product thereof, which have excellent mechanical properties and can obtain a molded product having excellent long-term hydrolysis resistance, oxidation deterioration resistance, and color tone stability. The task is to do.

As a result of repeated studies to solve the above problems, the present inventors have (A) a thermoplastic polyester resin, (B) a novolac type epoxy resin having a specific structure, and (C) a reducing phosphorus system having a specific structure. We have found that the above problems can be solved by blending a specific amount of the compound, and have reached the present invention. That is, the present invention has the following configuration.
[1] With respect to 100 parts by weight of (A) thermoplastic polyester resin, (B) 0.05 to 5 parts by weight of novolak type epoxy resin represented by the following general formula (1) and (C) the following general formula (4) A thermoplastic polyester resin composition containing 0.01 to 1 part by weight of a reducing phosphorus compound represented by).

(In the general formula (1), X represents a divalent group represented by the general formula (2) or (3). In the general formulas (1) and (3), R ¹ , R ² , R ⁴ and R ⁵ each independently represent 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 from each other. R ³ is a hydrogen atom and has 1 to 8 carbon atoms. Represents an alkyl group or an aryl group having 6 to 10 carbon atoms. In the above general formula (1), n represents a value greater than 0 and 10 or less. In the above general formulas (1) and (3), a, c, d represents an integer of 0 to 4 independently, and b represents an integer of 0 to 3).

(In the above general formula (4), R ⁶ and R ⁷ are independently hydrogen (except when both R ⁶ and R ⁷ are hydrogen), OM (where O is negatively charged oxygen). It is an atom and M is a positively charged counterion), an alkyl group having 1 to 20 carbon atoms, an alkylene group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an alkyl having 1 to 20 carbon atoms. It is selected from an oxy group, a polyoxyalkylene group composed of an alkylene having 2 to 4 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms. The alkyl group, an alkylene group, an aryl group, an alkyloxy group and a polyoxyalkylene group. , And aryloxy groups may be optionally substituted, and the optionally substituted substituents are independently OH group, halogen, COOH group, COOR ⁸ groups (where R ⁸ is carbon). It is selected from (the number 1 to 4 alkyl groups) and ₂ NH groups. The alkyl group, alkylene group, aryl group, alkyloxy group, polyoxyalkylene group, and aryloxy group are optionally substituted. The number of substitutions in the case is 1 or 2. R ⁶ and R ⁷ can also be linked by cross-linking.)
[2] The thermoplastic polyester resin composition according to [1], wherein the (C) reducing phosphorus compound is a metal salt of phosphorous acid or a metal salt of hypophosphorous acid.
[3] The thermoplastic polyester resin composition according to [1] or [2], wherein the epoxy group concentration in the thermoplastic polyester resin composition is 20 to 150 eq / t.
[4] The thermoplastic polyester resin composition according to any one of [1] to [3], wherein the carboxyl group concentration in the thermoplastic polyester resin composition is 0 to 20 eq / t.
[5] The thermoplastic polyester resin composition according to any one of [1] to [4] , wherein the (A) thermoplastic polyester resin is polybutylene terephthalate.
[6] The thermoplastic polyester according to any one of [1] to [5] , which is obtained by further blending 1 to 100 parts by weight of (E) a fiber reinforcing material with 100 parts by weight of (A) thermoplastic polyester resin. Resin composition.
[7] The heat according to any one of [1] to [6] , which comprises 100 parts by weight of (A) thermoplastic polyester resin and 0.001 to 1 part by weight of (F) reaction accelerator. Plastic polyester resin composition.
[8] A molded product obtained by melt-molding the thermoplastic polyester resin composition according to any one of [1] to [7] .

The thermoplastic polyester resin composition of the present invention is excellent in oxidation deterioration resistance. According to the thermoplastic polyester resin composition of the present invention, it is possible to obtain a molded product having excellent mechanical properties, and also having excellent long-term hydrolysis resistance, oxidation deterioration resistance, and color tone stability.

The thermoplastic polyester resin composition of the present invention will be described in detail.

The thermoplastic polyester resin composition of the present invention comprises (A) 0.05 to 5 parts by weight of the novolak type epoxy resin represented by the general formula (1) and (B) 0.05 to 5 parts by weight of the novolak type epoxy resin represented by the general formula (1) with respect to 100 parts by weight of the thermoplastic polyester resin. C) 0.01 to 1 part by weight of the reducing phosphorus-based compound represented by the general formula (4) is blended. Although the thermoplastic polyester resin (A) is excellent in injection moldability and mechanical properties, the ester bond is easily decomposed by hydrolysis, and as a result, the concentration of carboxyl groups increases. As the carboxyl group concentration increases, the decrease in the molecular weight of the (A) thermoplastic polyester resin is promoted, and the mechanical properties deteriorate. In the present invention, the carboxyl group of the (A) thermoplastic polyester resin generated by hydrolysis by blending (A) the thermoplastic polyester resin with (B) the novolak type epoxy resin represented by the general formula (1). And (B) react with the epoxy groups of the novolak type epoxy resin represented by the general formula (1) to suppress an increase in the carboxyl group concentration, and (A) maintain the high mechanical properties of the thermoplastic polyester resin. Can be done.

Further, in the (A) thermoplastic polyester resin, the ester group is decomposed by oxidative deterioration in a high temperature environment, so that the carboxyl group concentration is increased and the hydrolysis resistance, strength and color tone are deteriorated. Therefore, when exposed to a high temperature environment for a long time or when melted and retained at a high temperature, even if the novolak type epoxy resin represented by the general formula (1) is blended, the hydrolysis resistance is not good. Sometimes it was enough. Therefore, by further blending the (C) reducing phosphorus compound, the organic peroxide generated by oxidative deterioration is reduced by the (C) reducing phosphorus compound, and the increase of the carboxyl group generated as a decomposition product is suppressed. Can be done.

Further, in a resin composition obtained by blending (A) a thermoplastic polyester resin with (C) a reducing phosphorus compound alone, the (C) reducing phosphorus compound bleeds out when it is placed in a moist heat environment. Not preferable. Therefore, by using (B) the novolak type epoxy resin represented by the general formula (1) in combination, (A) post-crystallization of the thermoplastic polyester resin that occurs in a moist heat environment is suppressed, and (C) reducibility. Bleedout of phosphorus-based compounds can be suppressed.

Here, the thermoplastic polyester resin composition of the present invention contains a reaction product obtained by reacting the component (A), the component (B) and the component (C), and the reaction product is produced by a complicated reaction. There are circumstances in which it is not practical to specify the structure. Therefore, the present invention specifies the invention by the components to be blended.

The (A) thermoplastic polyester resin used in the present invention includes (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 polymer or copolymer having at least one residue selected from the group consisting of lactones as a main structural unit. Here, "referred to as a main structural unit" means having at least 50 mol% or more of at least one residue selected from the group consisting of (1) to (3) in all structural units, and those residues. It is a preferable embodiment to have 80 mol% or more of. Among these, (1) a polymer or copolymer having a residue of (1) a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof as a main structural unit is preferable in that it is superior in mechanical properties and heat resistance. ..

Examples of the above-mentioned dicarboxylic acid or ester-forming derivative thereof 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, dodecandione Examples thereof include aliphatic dicarboxylic acids such as acids, malonic acids, glutaric acids and dimer acids, alicyclic dicarboxylic acids such as 1,3-cyclohexanedicarboxylic acids and 1,4-cyclohexanedicarboxylic acids, and ester-forming derivatives thereof. .. Two or more of these may be used.

Examples of the above-mentioned diol or ester-forming derivative thereof include ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, and decamethylene glycol. , Cyclohexanedimethanol, cyclohexanediol, dimerdiol and other aliphatic or alicyclic glycols having 2 to 20 carbon atoms, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol and the like having a molecular weight of 200 to 100,000. Long-chain glycols, 4,4'-dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, bisphenol A, bisphenol S, bisphenol F and other aromatic dioxy compounds and ester-forming derivatives thereof. Two or more of these may be used.

Examples of the polymer or copolymer having a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof as a structural unit include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polypropylene isophthalate, and polybutylene isophthalate. , Polybutylene naphthalate, polypropylene isophthalate / terephthalate, polybutylene isophthalate / terephthalate, polypropylene terephthalate / naphthalate, polybutylene terephthalate / naphthalate, polybutylene terephthalate / decandicarboxylate, polypropylene terephthalate / 5-sodium sulfoisophthalate, poly Butylene terephthalate / 5-sodium sulfoisophthalate, polypropylene terephthalate / polyethylene glycol, polybutylene terephthalate / polyethylene glycol, polypropylene terephthalate / polytetramethylene glycol, polybutylene terephthalate / polytetramethylene glycol, polypropylene terephthalate / isophthalate / polytetramethylene glycol , Polybutylene terephthalate / isophthalate / polytetramethylene glycol, polybutylene terephthalate / succinate, polypropylene terephthalate / adipate, polybutylene terephthalate / adipate, polypropylene terephthalate / sebacate, polybutylene terephthalate / sebacate, polypropylene terephthalate / isophthalate / adipate, poly Examples thereof include aromatic polyester resins such as butylene terephthalate / isophthalate / succinate, polybutylene terephthalate / isophthalate / adipate, and polypropylene terephthalate / isophthalate / sebacate. Here, "/" represents a copolymer.

Among these, from the viewpoint of further improving mechanical properties and heat resistance, a polymer having a residue of an aromatic dicarboxylic acid or an ester-forming derivative thereof and a residue of an aliphatic diol or an ester-forming derivative thereof as a main structural unit. Alternatively, a copolymer is more preferable, and the residue of terephthalic acid, naphthalenedicarboxylic acid or an ester-forming derivative thereof and the residue of an aliphatic diol selected from propylene glycol and butanediol or an ester-forming derivative thereof are the main structural units. Polymers or copolymers are more preferred.

Among them, aromatic polyester resins such as polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polypropylene naphthalate, polybutylene naphthalate, polypropylene isophthalate / terephthalate, polybutylene isophthalate / terephthalate, polypropylene terephthalate / naphthalate and polybutylene terephthalate / naphthalate. Is particularly preferable, polybutylene terephthalate, polypropylene terephthalate and polybutylene naphthalate are more preferable, and polybutylene terephthalate is further preferable in terms of excellent moldability and crystallinity. Further, these two or more kinds can be used at an arbitrary content.

In the present invention, terephthalic acid or terephthalic acid with respect to all dicarboxylic acids constituting the polymer or copolymer having the residue of the above dicarboxylic acid or its ester-forming derivative and the residue of the diol or its ester-forming derivative as the main structural unit. The proportion of the ester-forming derivative is preferably 30 mol% or more, more preferably 40 mol% or more.

In the present invention, as the (A) thermoplastic polyester resin, a liquid crystal polyester resin capable of forming anisotropy at the time of melting can be used. Examples of the structural unit of the liquid crystal polyester resin include aromatic oxycarbonyl unit, aromatic dioxy unit, aromatic and / or aliphatic dicarbonyl unit, alkylenedioxy unit and aromatic iminooxy unit.

The amount of carboxyl terminal groups of the (A) thermoplastic polyester resin used in the present invention is preferably 50 eq / t or less, more preferably 30 eq / t or less in terms of fluidity, hydrolysis resistance and heat resistance. Is. The lower limit of the amount of carboxyl terminal groups is 0 eq / t. Here, the amount of carboxyl terminal groups of (A) the thermoplastic polyester resin is a value measured by dissolving (A) the thermoplastic polyester resin in an o-cresol / chloroform solvent and then titrating with ethanolic potassium hydroxide. ..

The (A) thermoplastic polyester resin used in the present invention preferably has a weight average molecular weight (Mw) of more than 8,000 and more preferably 500,000 or less in terms of further improving mechanical properties. The range is more than 8,000 and less than 300,000, and more preferably more than 8,000 and less than 250,000. In the present invention, the Mw of the (A) thermoplastic polyester resin is a value converted to polymethylmethacrylate (PMMA) measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent.

The (A) thermoplastic polyester resin used in the present invention can be produced by a known polycondensation method, ring-opening polymerization method, or the like. The production method may be either batch polymerization or continuous polymerization, and either a transesterification reaction or a reaction by direct polymerization can be applied, but from the viewpoint of productivity, continuous polymerization is preferable, and direct polymerization is preferable. More preferably used.

When the (A) thermoplastic polyester resin used in the present invention is a polymer or copolymer obtained by a condensation reaction containing a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof as main components. Can be produced by subjecting a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof to an esterification reaction or an ester exchange reaction, and then a polycondensation reaction.

In order to effectively proceed with the esterification reaction or the transesterification reaction and the polycondensation reaction, it is preferable to add a polymerization reaction catalyst during these reactions. Specific examples of the polymerization reaction catalyst include methyl ester of titanium acid, tetra-n-propyl ester, tetra-n-butyl ester, tetraisopropyl ester, tetraisobutyl ester, tetra-tert-butyl ester, cyclohexyl ester and phenyl ester. Organic titanium compounds such as benzyl esters, trill esters or mixed esters thereof, dibutyltin oxide, methylphenyltin oxide, tetraethyltin, hexaethyldistin oxide, cyclohexahexyl distin oxide, didodecyltin oxide, triethyltin hydrooxide, Triphenyltin Hydrooxide, Triisobutyltin Acetate, Dibutyltin Diacetate, Diphenyltin Dilaurate, Monobutyltin Trichloride, Dibutyltin Dichloride, Tributyltin Chloride, Dibutyltin Sulfide, Butylhydroxytin Oxide, Methylstannoic Acid, Ethylstannoic Acid, Butylstannon Examples thereof include tin compounds such as alkylstannonic acid such as acids, zirconia compounds such as zirconiumtetra-n-butoxide, and antimony compounds such as antimony trioxide and antimonate acetate. Two or more of these may be used.

Among these polymerization reaction catalysts, an organic titanium compound and a tin compound are preferable, and a tetra-n-butyl ester of titanium acid is more preferably used. The amount of the polymerization reaction catalyst added is preferably in the range of 0.01 to 0.2 parts by weight with respect to 100 parts by weight of the thermoplastic polyester resin.

The thermoplastic polyester resin composition of the present invention is characterized by blending (A) a thermoplastic polyester resin with (B) a novolak type epoxy resin represented by the following general formula (1). As described above, the thermoplastic polyester resin tends to be deteriorated by hydrolysis, but (B) the hydrolysis resistance is improved by blending the novolak type epoxy resin represented by the following general formula (1). Can be made to. Further, by selecting the (B) novolak type epoxy resin having a specific structure, it is possible to suppress the bleed-out of the (C) reducing phosphorus compound in a moist heat environment. Two or more of these may be blended.

In the general formula (1), X represents a divalent group represented by the general formula (2) or (3). In the above general formulas (1) and (3), R ¹ , R ² , R ⁴ and R ⁵ independently represent an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms, and they may be the same. It may be different. R ³ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms. In the above general formula (1), n represents a value greater than 0 and 10 or less. In the general formulas (1) and (3), a, c, and d independently represent an integer of 0 to 4, and b represents an integer of 0 to 3.

From the viewpoint of further improving the long-term hydrolysis resistance, 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 a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and the like. Of 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 or 1 in terms of reactivity.

In the present invention, the blending amount of the novolak type epoxy resin represented by (B) the general formula (1) is 0.05 to 5 parts by weight with respect to 100 parts by weight of (A) the thermoplastic polyester resin. When the blending amount of the component (B) is less than 0.05 parts by weight, the long-term hydrolysis resistance is lowered. On the other hand, when the blending amount of the component (B) exceeds 5 parts by weight, the heat resistance is lowered and the retention stability is deteriorated.

Further, in the present invention, (B) the preferable range of the blending amount of the novolak type epoxy resin represented by the general formula (1) is (B) the epoxy of the novolak type epoxy resin represented by the general formula (1). It can be set according to the equivalent amount. For example, (A) blended in the thermoplastic polyester resin composition with respect to the amount of carboxyl terminal groups derived from the thermoplastic polyester resin (B) novolak represented by the general formula (1). The ratio of the amount of epoxy groups derived from the type epoxy resin (epoxy group compounding amount (eq / g) / carboxyl group compounding amount (eq / g)) is preferably 1 to 7. When the (epoxy group compounding amount (eq / g) / carboxyl group compounding amount (eq / g)) is 1 or more, the long-term hydrolysis resistance can be further improved. 2 or more is preferable. Further, when (the amount of epoxy group compounded (eq / g) / the amount of carboxyl group compounded (eq / g)) is 7 or less, retention stability, heat resistance, and mechanical properties can be compatible at a higher level. 6 or less is preferable, and 5 or less is more preferable.

In the present invention, the amount of the carboxyl terminal group derived from the (A) thermoplastic polyester resin to be blended in the thermoplastic polyester resin composition is the concentration of the carboxyl terminal group of the component (A) and the total amount of the thermoplastic polyester resin composition. It can be obtained from the blending ratio of the component (A). The carboxyl end group concentration of the (A) thermoplastic polyester resin is 1% bromophenol blue, which is a solution of the (A) thermoplastic polyester resin dissolved in an o-cresol / chloroform (2/1, vol / vol) mixed solution. Can be calculated by titrating with 0.05 mol / L ethanolic potassium hydroxide using the above as an indicator.

The thermoplastic polyester resin composition of the present invention is characterized by further blending (A) a thermoplastic polyester resin with (C) a reducing phosphorus compound represented by the following general formula (4). As described above, in the polyester composition containing the novolak type epoxy resin represented by (B) the general formula (1), the carboxyl group increases due to oxidative deterioration in a high temperature environment, and the hydrolysis resistance decreases. However, by further blending (C) a reducing phosphorus compound represented by the following general formula (4), an increase in carboxyl groups due to oxidative deterioration is suppressed even in a high temperature environment, and excellent hydrolysis resistance is achieved. Can maintain sex. At the same time, the color tone of the resin composition can be maintained.

(In the above general formula (4), R ⁶ and R ⁷ are independently hydrogen (except when both R ⁶ and R ⁷ are hydrogen), OM (where O is negatively charged oxygen). It is an atom and M is a positively charged counterion), an alkyl group having 1 to 20 carbon atoms, an alkylene group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an alkyl having 1 to 20 carbon atoms. It is selected from an oxy group, a polyoxyalkylene group composed of an alkylene having 2 to 4 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms. The alkyl group, an alkylene group, an aryl group, an alkyloxy group and a polyoxyalkylene group. , And aryloxy groups may be optionally substituted, and the optionally substituted substituents are independently OH group, halogen, COOH group, COOR ⁸ groups (where R ⁸ is carbon). It is selected from (the number 1 to 4 alkyl groups) and ₂ NH groups. The alkyl group, alkylene group, aryl group, alkyloxy group, polyoxyalkylene group, and aryloxy group are optionally substituted. The number of substitutions in the case is 1 or 2. R ⁶ and R ⁷ can also be linked by cross-linking.)

(C) Specific examples of the reducing phosphorus compound represented by the general formula (4) include a phosphonate compound and a phosphinate compound.

Examples of the phosphonate compound include phosphonic acid, phosphonic acid alkyl ester, phosphonic acid aryl ester, and metal salts thereof. Specific examples thereof include dimethyl phosphonate, diethyl phosphonate, diphenyl phosphonate, and metal salts of phosphonic acid.

Examples of the phosphinate compound include hypophosphorous acid, hypophosphorous acid alkyl ester, hypophosphorous acid aryl ester, alkylated hypophosphorous acid, arylated hypophosphorous acid, their alkyl ester or aryl ester, and them. Metal salts and the like. Specifically, phosphinic acid, methylphosphinic acid, ethylphosphinic acid, propylphosphinic acid, isopropylphosphinic acid, butylphosphinic acid, phenylphosphinic acid, tolylphosphinic acid, xsilylphosphinic acid, biphenylylphosphinic acid, naphthylphosphinic acid, Examples thereof include anthrylphosphinic acid, alkyl esters or aryl esters thereof, and metal salts thereof.

Among these, in addition to suppressing oxidative deterioration of (A) thermoplastic polyester resin, (B) suppressing oxidative deterioration of novolak type epoxy resin represented by the general formula (1), hydrolysis resistance of molded products A metal salt of phosphorous acid or a metal salt of hypophosphorous acid is preferable, a metal salt of hypophosphorous acid is more preferable, and a sodium salt of hypophosphorous acid is particularly preferable because the sex and color tone can be further improved. ..

The amount of the reducing phosphorus compound represented by (C) the general formula (4) is 0.01 to 1 part by weight with respect to 100 parts by weight of the thermoplastic polyester resin (A). If the blending amount of the reducing phosphorus compound (C) is less than 0.01 parts by weight, the effect of improving the oxidation deterioration resistance cannot be obtained. It is more preferably 0.02 parts by weight or more, and further preferably 0.05 parts by weight or more. On the other hand, when the blending amount of the (C) reducing phosphorus compound exceeds 1 part by weight, the mechanical properties tend to decrease and the hydrolysis resistance tends to decrease. It is more preferably 0.5 parts by weight or less, and further preferably 0.3 parts by weight or less.

In the present invention, as the first factor for imparting hydrolysis resistance that could not be achieved by the conventional technique, (B) the novolak type epoxy resin represented by the general formula (1) and (C) the above. It is important to reduce the carboxyl group originally present in the (A) thermoplastic polyester resin by the reaction by blending the reducing phosphorus compound represented by the general formula (4). From this point of view, it is represented by the carboxyl group concentration in the thermoplastic polyester resin composition after melt-kneading, that is, (A) the thermoplastic polyester resin, (A) the thermoplastic polyester resin, and (B) the general formula (1). (A) Thermoplasticity with respect to the total amount of the reaction product with the novolak type epoxy resin and the reaction product with (A) the thermoplastic polyester resin and (C) the reducing phosphorus compound represented by the general formula (4). The concentration of carboxyl groups derived from the polyester resin, the concentration of carboxyl groups derived from the reaction product of (A) the thermoplastic polyester resin and (B) the novolak type epoxy resin represented by the general formula (1), and (A) the thermoplastic polyester. The concentration of carboxyl groups derived from the reactant of the resin and the reducing phosphorus compound represented by the general formula (4) is preferably as low as possible, preferably 20 eq / t or less, and further 15 eq / t or less. Is particularly preferable. The most preferred embodiment is 0 eq / t. In the thermoplastic polyester resin composition, (A) a thermoplastic polyester resin, (A) a reaction product of (A) a thermoplastic polyester resin and (B) a novolak type epoxy resin represented by the general formula (1), and ( (A) Concentration of carboxyl groups derived from the thermoplastic polyester resin with respect to the total amount of the reaction product of (A) the thermoplastic polyester resin and (C) the reducing phosphorus compound represented by the general formula (4), (A). The carboxyl group concentration derived from the reaction product of the thermoplastic polyester resin and (B) the novolak type epoxy resin represented by the general formula (1), and (A) the thermoplastic polyester resin and (C) the general formula (4). The carboxyl group concentration derived from the reaction product with the reducing phosphorus compound represented by is determined by the solution obtained by dissolving the thermoplastic polyester resin composition in an o-cresol / chloroform (2/1, vol / vol) mixed solution. It can be calculated by titrating with 0.05 mol / L ethanolic potassium hydroxide using 1% bromophenol blue as an indicator. As described above, the amount of carboxyl groups can be reduced by blending (B) the novolak type epoxy resin represented by the general formula (1) with (A) the thermoplastic polyester resin, but further ( C) By blending the reducing phosphorus compound represented by the general formula (4), oxidative deterioration of the (A) thermoplastic polyester resin during melt-kneading can be suppressed, and the amount of carboxyl groups can be further reduced. ..

As a second factor for imparting hydrolysis resistance, which could not be achieved by the conventional technique, the carboxyl group newly generated by the hydrolysis of the thermoplastic polyester resin is reacted with the epoxy group to suppress the increase of the carboxyl group. It is important to. From this point of view, the epoxy group concentration in the thermoplastic polyester resin composition after melt-kneading is preferably 20 eq / t or more, more preferably 30 eq / t or more, and particularly preferably 40 eq / t or more. Further, when the epoxy group concentration in the thermoplastic polyester resin composition is 150 eq / t or less, long-term hydrolysis resistance, retention stability at high temperature, and mechanical properties can be compatible at a higher level, which is preferable. More preferably 130 eq / t or less. The epoxy group concentration in the thermoplastic polyester composition is determined by dissolving the thermoplastic polyester resin composition in an o-cresol / chloroform (2/1, vol / vol) mixed solution, and then acetic acid and triethylammonium bromide /. It can be calculated by adding an acetic acid solution and performing potential differential titration with 0.1 mol / L acetic acid perchlorate.

In the thermoplastic polyester resin composition of the present invention, it is preferable that (A) the thermoplastic polyester resin is further mixed with (D) an epoxy compound having two epoxy functional groups per molecule. As described above, the thermoplastic polyester resin composition containing the novolak type epoxy resin represented by (B) the general formula (1) deteriorates the retention stability due to the cross-linking of the molecular chains at the melt processing temperature of 270 ° C. or higher. However, by further blending (D) an epoxy compound having two epoxy functional groups per molecule, it is difficult to form a crosslinked structure that leads to deterioration of retention stability, thereby preventing hydrolysis. Deterioration of retention stability at high temperature can be suppressed while further improving the property.

The epoxy compound (D) used in the present invention having two epoxy functional groups per molecule is a compound containing two epoxy groups in the molecule, and a liquid or solid compound can be used. For example, it is a polycondensate of epichlorohydrin and a phenol compound such as bisphenol A, resorcinol, hydroquinone, pyrocatechol, bisphenol F, saligenin, bisphenol S, 4,4'-dihydroxybiphenyl, 1,5-dihydroxynaphthalene, cashew phenol. Examples thereof include glycidyl ether-based epoxy compounds, glycidyl ester-based epoxy compounds such as phthalic acid glycidyl ester, and glycidyl amine-based epoxy compounds such as N, N'-methylenebis (N-glycidyl aniline). Two or more of these may be blended. Of these, glycidyl ether-based epoxy compounds are preferable because they can suppress decomposition during melt processing, and by further improving the surface free energy of the resin composition and preventing permeation into chemicals such as industrial lubricating oil and grease. A bisphenol-type epoxy compound, which is a polycondensate of bisphenol A and epichlorohydrin, is preferable because it can improve chemical resistance, which is resistance to deterioration due to contact with high-temperature chemicals. Further, the component (D) used in the present invention does not contain a novolak type epoxy compound.

Further, among the bisphenol type epoxy compounds, a bisphenol A type epoxy resin having an epoxy value of 300 to 3000 g / eq is preferable. When the epoxy value of the bisphenol type epoxy compound is 300 g / eq or more, the amount of gas during melt processing can be suppressed. More preferably, it is 500 g / eq or more. Further, when the epoxy value of the bisphenol type epoxy compound is 3000 g / eq or less, both long-term hydrolysis resistance and melt retention stability at high temperature can be achieved at a higher level. It is more preferably 2000 g / eq or less.

The amount of the epoxy compound (D) having two epoxy functional groups per molecule is preferably 0.05 to 10 parts by weight with respect to 100 parts by weight of the thermoplastic polyester resin (A). (D) When the blending amount of the epoxy compound having two epoxy functional groups per molecule is 0.05 parts by weight or more, the effect of improving the heat aging property can be obtained. It is more preferably 0.5 parts by weight or more, and further preferably 1.0 part by weight or more. On the other hand, (D) by setting the blending amount of the epoxy compound having two epoxy functional groups per molecule to 10 parts by weight or less, the deterioration of mechanical properties can be suppressed. It is more preferably 5.0 parts by weight or less, and further preferably 3.0 parts by weight or less.

Further, in the present invention, (D) a preferable range of the blending amount of the epoxy compound having two epoxy functional groups per molecule is (B) blending of the novolak type epoxy resin represented by the general formula (1). It can be set according to the amount. For example, when producing a thermoplastic polyester resin composition, (B) the blending amount of the novolak type epoxy resin represented by the general formula (1) and (D) the epoxy having two epoxy functional groups per molecule. Ratio of compounding amount of compound (((A) parts by weight of epoxy compound having 2 epoxy functional groups per molecule to 100 parts by weight of (A) thermoplastic polyester resin) / ((A) thermoplastic polyester resin 100 The (B) weight portion of the novolak type epoxy resin represented by the general formula (1))) with respect to the weight portion is preferably 0.5 to 4. (B) When the ratio of the blending amount of the novolak type epoxy resin represented by the general formula (1) and the epoxy compound having 2 epoxy functional groups per molecule (D) is 0.5 or more, retention Stability can be further improved. 1 or more is more preferable. Further, when the ratio of the compounding amount of (B) the novolak type epoxy resin represented by the general formula (1) and the epoxy compound having 2 epoxy functional groups per molecule (D) is 4 or less, it is long-term. Hydrolysis resistance, retention stability at high temperature, and mechanical properties can be achieved at a higher level. 3 or less is preferable, and 2.5 or less is more preferable.

It is preferable to further add (E) a fiber reinforcing material to the thermoplastic polyester resin composition of the present invention. (E) The fiber reinforced material can further improve the mechanical strength and heat resistance.

Specific examples of the (E) fiber reinforcing material include glass fiber, aramid fiber, carbon fiber and the like. The above-mentioned glass fibers are chopped strand type or roving type glass fibers and have a common weight composed of a silane coupling agent such as an aminosilane compound or an epoxysilane compound and / or an acrylic acid such as urethane or an acrylic acid / styrene copolymer. Contains a copolymer composed of maleic anhydride such as a coalescence, methyl acrylate / methyl methacrylate / maleic anhydride copolymer, and one or more epoxy compounds such as vinyl acetate, bisphenol A diglycidyl ether and novolak epoxy compound. The glass fiber treated with the sizing agent is preferably used, and the glass fiber treated with the converging agent containing a copolymer composed of maleic anhydride is more preferable because the hydrolysis resistance can be further improved. The silane coupling agent and / or the focusing agent may be mixed with the emulsion solution and used. The fiber diameter is usually 1 to 30 μm, preferably 5 to 15 μm. Further, although the fiber cross section is usually circular, a fiber reinforcing material having an arbitrary cross section such as an elliptical glass fiber having an arbitrary aspect ratio, a flat glass fiber, and an eyebrows-shaped glass fiber can also be used, and injection molding is possible. It is characterized by improved fluidity over time and the ability to obtain molded products with less warpage.

The amount of the fiber reinforcing material (E) blended is preferably 1 to 100 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin. By blending 1 part by weight or more of the fiber reinforcing material (E), the mechanical strength and heat resistance can be further improved. 2 parts by weight or more is more preferable, and 3 parts by weight or more is further preferable. On the other hand, by blending 100 parts by weight or less of the (E) fiber reinforcing material, the mechanical strength and heat resistance can be further improved. It is more preferably 95 parts by weight or less, and further preferably 90 parts by weight or less.

It is preferable to further add (F) a reaction accelerator to the thermoplastic polyester resin composition of the present invention. Depending on (F) the reaction accelerator, (A) the carboxyl end group of the thermoplastic polyester resin, (B) the epoxy group of the novolak type epoxy resin represented by the general formula (1), and (D) the epoxy functionality per molecule. The reaction of the epoxy compound having two groups with the epoxy group can be promoted, and the long-term hydrolysis resistance can be greatly improved.

The (F) reaction accelerator used in the present invention includes (A) a carboxyl end group of a thermoplastic polyester resin, (B) an epoxy group of a novolak type epoxy resin represented by the general formula (1), and (D) one. It is not particularly limited as long as it promotes the reaction of the epoxy group of the epoxy compound having 2 epoxy functional groups per molecule, and is not particularly limited, for example, tertiary amine, amidin compound, organic metal compound, organic phosphine and The salts, imidazoles, boron compounds, etc. are available. Two or more of these may be blended.

Examples of the tertiary amine include benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (diaminomethyl) phenol, 2,4,6-tris (diaminomethyl) phenol, and tri. Examples thereof include a salt with -2-ethylhexylic acid.

Examples of the amidine compound include 1,8-diazabicyclo (5,4,0) undecene-7, 1,5-diazabicyclo (4,3,0) nonene-5,5,6-dibutylamino-1,8 diazabicyclo. Examples thereof include (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 or tetraphenylborate.

Examples of the organic metal compound include metal stearate salts such as sodium stearate, magnesium stearate, calcium stearate, potassium stearate, and lithium stearate, acetylacetonate chromium, acetylacetonate zinc, acetylacetonate nickel, and triethanol. Examples include amine titanate and tin octylate.

Examples of organic phosphine and salts thereof include triparaphosphine, tris-4-methoxyphenylphosphine, tetrabutylphosphonium bromide, butyltriphenylphosphonium bromide, tetraphenylphosphonium tetraphenylbolate, triphenylphosphine, and triphenylphosphine tri. Examples thereof include phenylborane and triphenylphosphine 1,4-benzoquinone adducts.

Examples of the imidazole include 2-methylimidazole, 2-aminoimidazole, 2-methyl-1-vinylimidazole, 2-ethyl-4-methylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-undecylimidazole. , 1-allyl imidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-undecylimidazolium trimerite, 1-benzyl-2-methylimidazole, 1- Cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazolium trimerite, 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-diaza-2, 4-Cyclopentadiene, 1-cyanoethyl-2-phenyl-4,5-di (cyanoethoxymethyl) imidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole , 2,4-Diamino-6- [2-undecylimidazolyl- (1)] ethyl-S-triazine and the like.

Examples of the boron compound include boron trifluoride-n-hexylamine, boron trifluoride-monoethylamine, boron trifluoride-benzylamine, boron trifluoride-diethylamine, boron trifluoride-piperidin, and trifluoride. Boron-Triethylamine, Boron Trifluoride-Aniline, Boron Trifluoride-n-Hexylamine, Boron Trifluoride-Monoethylamine, Boron Trifluoride-benzylamine, Boron Trifluoride-Diethylamine, Boron Trifluoride-Piperidine , Boron trifluoride-triethylamine, boron trifluoride-aniline and the like.

As the reaction accelerator, the reactivity between the carboxyl end group of the thermoplastic polyester resin (A) and the novolak type epoxy resin represented by the general formula (1) is further promoted, and long-term hydrolysis resistance is obtained. It is preferable to contain nitrogen or phosphorus, and an amidine compound, an organic phosphine and a salt thereof, an imidazole and the like are preferable, and an organic phosphine is more preferable.

In the present invention, the blending amount of the (F) reaction accelerator is preferably 0.001 to 1 part by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin. When the blending amount of the component (F) is 0.001 part by weight or more, the long-term hydrolysis resistance can be further improved. On the other hand, when the blending amount of the component (F) is 1 part by weight or less, the long-term hydrolysis resistance can be further improved while maintaining the mechanical properties.

Further, in the present invention, the preferable range of the blending amount of (F) the reaction accelerator is (B) a novolak type epoxy resin represented by the general formula (1) and (D) two epoxy functional groups per molecule. It can be set according to the blending amount of the epoxy compound. For example, (B) the amount of epoxy groups derived from the novolak type epoxy resin represented by the general formula (1) to be blended in the thermoplastic polyester resin composition and (D) the epoxy having two epoxy functional groups per molecule. Ratio of (F) compounding concentration of reaction accelerator ((F) compounding concentration of reaction accelerator (eq / g) / (B) component in the thermoplastic polyester resin composition to the sum of the amounts of epoxy groups derived from the compound The sum of the amount of epoxy groups derived from (C) and the amount of epoxy groups derived from component (C) (eq / g), hereinafter sometimes referred to as "reaction accelerator compounding concentration / epoxy group concentration") is 0. .005-0.2 is preferable. When the compounding concentration of the reaction accelerator / the epoxy group concentration is 0.005 or more, the long-term hydrolysis resistance can be further improved. It is more preferably 0.01 or more, and even more preferably 0.015 or more. On the other hand, when the compounding concentration of the reaction accelerator / the epoxy group concentration is 0.2 or less, long-term hydrolysis resistance, retention stability, and mechanical properties can be achieved at a higher level. More preferably, it is 0.1 or less.

It should be noted that (B) the amount of epoxy groups derived from the novolak type epoxy resin represented by the general formula (1), and (D) one molecule to be blended in the thermoplastic polyester resin composition. The amount of epoxy group derived from the epoxy compound having 2 epoxy functional groups per unit is the concentration of the epoxy group in the component (B) alone and the component (D) alone, and the component (B) in the entire thermoplastic polyester resin composition. And (D) can be obtained from the blending ratio of the component, respectively. The epoxy group concentration of the component (B) alone and the component (D) alone is according to JISK7236: 2001, (B) the novolak type epoxy resin represented by the general formula (1), and (D) the epoxy functionality per molecule. It can be calculated by adding acetic acid and triethylammonium bromide / acetic acid solution to a solution in which each epoxy compound having two groups is dissolved in chloroform, and performing potential differential titration with 0.1 mol / L acetic acid perchlorate. ..

Further, the blending concentration of the (F) reaction accelerator in the thermoplastic polyester resin composition can be calculated from the molecular weight of the reaction accelerator and the blending ratio of the component (F) in the entire thermoplastic polyester resin composition.

In the thermoplastic polyester resin composition of the present invention, a reinforcing material other than the fiber reinforcing material can be blended as long as the effect of the present invention is not impaired, and for example, an inorganic filler can be blended. By blending an inorganic filler, some parts such as crystallization characteristics, arc resistance, anisotropy, mechanical strength, flame retardancy or thermal deformation temperature of the molded product can be improved, and in particular, anisotropy. Since it is effective in, a molded product with less warpage can be obtained.

Examples of the reinforcing material other than the fiber reinforcing material include needle-like, granular, powder-like and layered inorganic fillers, and specific examples thereof include glass beads, milled fibers, glass flakes, potassium silicate whisker, and calcium sulfate. Whisker, Wallastinite, Silica, Kaolin, Tarku, Calcium Carbonate, Zinc Oxide, Magnesium Oxide, Aluminum Oxide, Mixture of Magnesium Oxide and Aluminum Oxide, Fine Silicic Acid, Aluminum Silica, Silicon Oxide, Smectite Clay Minerals (Montmorillonite, Hect) Light), vermiculite, mica, fluorine teniolite, zirconium phosphate, titanium phosphate, and dolomite. Two or more of these may be blended. When milled fiber, glass flakes, kaolin, talc and mica are used, a molded product with less warpage can be obtained because it has an effect on anisotropy. Further, calcium carbonate, zinc oxide, magnesium oxide, aluminum oxide, a mixture of magnesium oxide and aluminum oxide, fine powder silicic acid, aluminum silicate and silicon oxide were added from 0.01 to 100 parts by weight of the (A) thermoplastic polyester resin. When blended in the range of 1 part by weight, the retention stability can be further improved.

Further, the inorganic filler other than the fiber reinforcing material may be subjected to surface treatment such as a coupling agent treatment, an epoxy compound, or an ionization treatment. Further, the average particle size of the granular, powdery and layered inorganic filler is preferably 0.1 to 20 μm, particularly preferably 0.2 to 10 μm from the viewpoint of impact strength. In addition, the blending amount of the inorganic filler other than the fiber reinforced material is combined with the blending amount of the fiber reinforced 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. It is preferably 100 parts by weight or less 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. When the blending amount of the inorganic filler other than the fiber reinforced material 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 further preferable. On the other hand, if the blending amount of the inorganic filler other than the fiber reinforcing material is 50 parts by weight or less, the mechanical strength can be improved.

The resin composition of the present invention may contain one or more arbitrary additives such as an ultraviolet absorber, a light stabilizer, a plasticizer and an antistatic agent as long as the object of the present invention is not impaired.

The thermoplastic polyester resin composition of the present invention preferably further contains a phosphorus-based stabilizer as a phosphorus-based compound other than the reducing phosphorus-based compound represented by the general formula (4) (C). (B) The novolak type epoxy resin represented by the general formula (1) reacts with the carboxyl group in the thermoplastic polyester resin composition and also with the epoxy group at a high temperature of 270 ° C. or higher. , It causes a decrease in retention stability due to cross-linking. In the present invention, by blending (B) a novolak type epoxy resin represented by the general formula (1) and a phosphorus-based stabilizer, (B) a novolak type epoxy resin represented by the general formula (1). It is possible to suppress the cross-linking reaction between the two and further improve the retention stability at a high temperature of 270 ° C. or higher.

The phosphorus-based stabilizer in the present invention is a compound having a structure represented by the following structural formula (5), that is, a structure containing two or more oxygen atoms bonded to a phosphorus atom having an unshared electron pair. is there. By having such a structure, it is possible to coordinate with phenoxy radicals and quinones, which are the causes of coloring derived from the novolak type epoxy resin, and to decompose or make them colorless. In a general phosphorus compound, the upper limit of oxygen atoms that can be bonded to a phosphorus atom having an unshared electron pair is three from the valence of the phosphorus atom.

The phosphorus-based stabilizer used in the present invention includes a phosphonite compound as a compound containing a structure in which two oxygen atoms are bonded to a phosphorus atom having an unshared electron pair, and three phosphorus atoms having an unshared electron pair. As a compound containing a structure in which an oxygen atom of the above is bonded to a phosphorus atom, a phosphite compound and the like can be mentioned.

Phosphonite compounds include, for example, phosphonic acid compounds such as phenyl subphosphonic acid and 4,4'-biphenylrange subphosphonic 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. Specifically, bis (2,4-di-t-butyl-5-methylphenyl) -phenylphosphonite, tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4'. Examples thereof include -biphenylenediphosphonite, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylenediphosphonite and the like.

Among them, from the viewpoint of heat stability of phosphorus-based stabilizers, tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-) Di-t-butylphenyl) -4,4'-biphenylenediphosphonite is preferred.

Phosphorous compounds include, for example, phosphorous acid, fatty alcohols having 4 to 25 carbon atoms, polyhydric alcohols such as glycerol and pentaerythritol, and / or 2,6-di-t-butylphenol and 2,4-di. Examples thereof include condensates with phenol compounds such as -t-butylphenol. Specifically, triisodecylphosphite, trisnonylphenylphosphite, diphenylisodecylphosphite, phenyldiisodecylphosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octylphosphite, 4 , 4'-butylidenebis (3-methyl-6-t-butylphenyl) ditridecylphosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (2-t-butyl-4-methylphenyl) ) Phosphite, Tris (2,4-di-t-amylphenyl) phosphite, Tris (2-t-butylphenyl) phosphite, Tris [2- (1,1-dimethylpropyl) -phenyl] phosphite, Tris (alkylaryl) phosphite, such as tris [2,4- (1,1-dimethylpropyl) -phenyl] phosphite (however, the alkyl group in this case is a branched alkyl group having 3 to 6 carbon atoms), Bis (2-t-butylphenyl) phenylphosphite, tris (2-cyclohexylphenyl) phosphite, tris (2-t-butyl-4-phenylphenyl) phosphite, bis (octyl) pentaerythritol diphosphite, bis (Octadecyl) pentaerythritol diphosphite, bis (2,4-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) penta Bis (alkylaryl) pentaerythritol diphosphite such as erythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite (however, the alkyl group in this case has 3 carbon atoms). (It is an alkyl group of ~ 9) and the like. Two or more of these may be used.

Of these, bis (alkylaryl) pentaerythritol diphosphite is preferable, and bis (2,4-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite is preferable from the viewpoint of heat stability of phosphorus-based stabilizers. , Bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite is more preferred.

In the present invention, the blending amount of the phosphorus-based stabilizer can be adjusted according to (B) the type and blending amount of the novolak type epoxy resin represented by the general formula (1), but (A) the thermoplastic polyester resin. 0.01 to 1 part by weight is preferable with respect to 100 parts by weight. The color tone can be improved by setting the blending amount of the phosphorus-based stabilizer to 0.01 parts by weight or more. On the other hand, by setting the blending amount of the phosphorus-based stabilizer to 1 part by weight or less, long-term hydrolysis resistance and mechanical properties can be further improved. More preferably, it is 0.5 parts by weight or less.

The resin composition of the present invention may contain a thermoplastic resin other than the component (A) as long as the object of the present invention is not impaired, and may improve moldability, dimensional accuracy, molding shrinkage, toughness, and the like. Can be done. Examples of the thermoplastic resin other than the component (A) include olefin resin, vinyl resin, polyamide resin, polyacetal resin, polyurethane resin, aromatic or aliphatic polyketone resin, polyphenylene sulfide resin, polyether ether ketone resin, and polyimide. Resin, thermoplastic starch resin, polyurethane resin, aromatic polycarbonate resin, polyarylate resin, polysulfone resin, polyethersulfone resin, phenoxy resin, polyphenylene ether resin, poly-4-methylpentene-1, polyetherimide resin, cellulose acetate Examples thereof include resins and polyvinyl alcohol resins. Specific examples of the olefin-based resin include ethylene / propylene copolymer, ethylene / propylene / non-conjugated diene copolymer, ethylene-butene-1 copolymer, ethylene / glycidyl methacrylate copolymer, and ethylene / butene-1. / Maleic anhydride copolymer, ethylene / propylene / maleic anhydride copolymer, ethylene / maleic anhydride copolymer and the like can be mentioned. Specific examples of the vinyl-based resin include methyl methacrylate / styrene resin (MS resin), methyl methacrylate / acrylonitrile resin, polystyrene resin, acrylonitrile / styrene resin (AS resin), styrene / butadiene resin, and styrene / N-. Vinyl-based (co) polymers such as phenylmaleimide resin, styrene / acrylonitrile / N-phenylmaleimide resin, acrylonitrile / butadiene / styrene resin (ABS resin), acrylonitrile / butadiene / methyl methacrylate / styrene resin (MABS resin), high Impact-A styrene resin modified with a rubber polymer such as polystyrene resin, a block copolymer such as styrene / butadiene / styrene resin, styrene / isoprene / styrene resin, styrene / ethylene / butadiene / styrene resin, and core shell rubber. As a multi-layer structure of dimethylsiloxane / butyl acrylate polymer (core layer) and methyl methacrylate polymer (shell layer), dimethylsiloxane / butyl acrylate polymer (core layer) and acrylonitrile / styrene copolymer (shell layer). ) Multi-layer structure, multi-layer structure of butandien / styrene polymer (core layer) and methyl methacrylate polymer (shell layer), butandien / styrene polymer (core layer) and acrylonitrile / styrene copolymer (shell layer) Examples include a multilayer structure.

Among them, it is preferable to add an olefin resin having high hydrolysis resistance from the viewpoint of improving the toughness and hydrolysis resistance of the resin composition.

The blending amount of the olefin resin is preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin. When the blending amount is 0.1 parts by weight or more, the toughness and hydrolysis resistance are further improved. The blending amount is more preferably 0.5 parts by weight or more, still more preferably 1 part by weight or more. On the other hand, when the blending amount is 20 parts by weight or less, the mechanical properties are further improved. The blending amount is more preferably 30 parts by weight or less, still more preferably 10 parts by weight or less.

The resin composition of the present invention contains a polyhydric alcohol compound having three or four functional groups and containing one or more alkylene oxide units (hereinafter, may be referred to as "polyhydric alcohol compound"). can do. By blending such a compound, the fluidity during molding processing such as injection molding can be improved. The polyhydric alcohol compound may be a low molecular weight compound or a polymer. Examples of the functional group include a hydroxyl group, an aldehyde group, a carboxylic acid group, a sulfo group, an amino group, a glycidyl group, an isocyanate group, a carbodiimide group, an oxazoline group, an oxazine group, an ester group, an amide group, a silanol group and a silyl ether group. Can be mentioned. Among these, it is preferable to have the same or different 3 or 4 functional groups, and particularly in terms of further improving fluidity, mechanical properties, durability, heat resistance and productivity, 3 or 4 identical functional groups are used. It is more preferable to have four.

Moreover, a preferred example of the alkylene oxide unit is an aliphatic alkylene oxide unit having 1 to 4 carbon atoms. Specific examples include methylene oxide unit, ethylene oxide unit, trimethylene oxide unit, propylene oxide unit, tetramethylene oxide unit, 1,2-butylene oxide unit, 2,3-butylene oxide unit, isobutylene oxide unit and the like. it can.

In the present invention, it is particularly preferable to use a compound containing an ethylene oxide unit or a propylene oxide unit as the alkylene oxide unit in that it is excellent in fluidity, recyclability, durability, heat resistance and mechanical properties. In addition, it is particularly preferable to use a compound containing a propylene oxide unit in that it is excellent in long-term hydrolysis resistance and toughness (tensile elongation at break). Regarding the number of alkylene oxide units, the number of alkylene oxide units per functional group is preferably 0.1 or more, more preferably 0.5 or more, still more preferably 1 or more, in terms of being more excellent in fluidity. is there. On the other hand, in terms of being more excellent in mechanical properties, the number of alkylene oxide units per functional group is preferably 20 or less, more preferably 10 or less, still more preferably 5 or less.

Further, the polyhydric alcohol compound may be introduced into the main chain and / or side chain of the component (A) by reacting with the (A) thermoplastic polyester resin, and the resin may be introduced without reacting with the component (A). The structure at the time of compounding may be maintained in the composition.

In the present invention, the blending amount of the polyhydric alcohol compound is preferably 0.01 to 3 parts by weight, more preferably 0.1 to 1.5 parts by weight, based on 100 parts by weight of the (A) thermoplastic polyester resin.

A flame retardant can be added to the thermoplastic polyester resin composition of the present invention as long as the effects of the present invention are not impaired. Examples of the flame retardant include a phosphorus flame retardant, a halogen flame retardant such as a bromine flame retardant, a salt of a triazine compound and cyanuric acid or isocyanuric acid, a silicone flame retardant and an inorganic flame retardant. .. Two or more of these may be blended.

A mold release agent can be added to the resin composition of the present invention. By blending a mold release agent, the mold release property at the time of injection molding can be improved. Examples of the release agent include fatty acid amides such as ethylene bisstearyl amide, fatty acid amides composed of ethylenediamine and stearic acid and sebacic acid polycondensates, or phenylenediamine and stearic acid and sebacic acid polycondensates, and polyalkylene waxes. , Acid anhydride-modified polyalkylene wax and known mold release agents for plastics such as the above-mentioned lubricant and a mixture of a fluororesin or a fluorocompound.

The amount of the release agent to be blended is preferably 0.01 to 1 part by weight, more preferably 0.03 to 0.6 parts by weight, based on 100 parts by weight of the (A) thermoplastic polyester resin.

The resin composition of the present invention can further contain one or more of carbon black, titanium oxide and pigments and dyes of various colors, and can be toned to various colors, and has weather resistance (light) resistance and conductivity. It is also possible to improve. Examples of carbon black 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 is 50~400cm ³ / 100g is preferably used. As the titanium oxide, titanium oxide having a crystal form such as a rutile type or anatase type and having an average particle size of 5 μm or less is preferably used.

These carbon blacks, titanium oxides and pigments and dyes of various colors may be treated with aluminum oxide, silicon oxide, zinc oxide, zirconium oxide, polyols, silane coupling agents and the like. Further, in order to improve the dispersibility of the resin composition of the present invention and the handleability at the time of production, it may be used as a melt-blended or simply blended mixed material with various thermoplastic resins.

The blending amount of the pigment or dye is preferably 0.01 to 3 parts by weight, more preferably 0.03 to 1 part by weight, based on 100 parts by weight of the (A) thermoplastic polyester resin.

The thermoplastic polyester resin composition of the present invention can be obtained, for example, by melt-kneading the above-mentioned components (A) to (C) and, if necessary, other components.

Examples of the melt-kneading method include (A) a thermoplastic polyester resin, (B) a novolac type epoxy resin represented by the general formula (1), and (C) a reducing property represented by the general formula (4). A method of premixing a phosphorus-based compound, (D) an epoxy compound having two epoxy functional groups per molecule, and various additives, if necessary, and supplying the mixture to an extruder or the like for sufficient melt-kneading. , A method of supplying each component to a predetermined amount of an extruder or the like using a quantitative feeder such as a weight feeder and sufficiently melting and kneading the components. By performing such melt-kneading, a thermoplastic polyester resin composition having an epoxy group concentration in the above-mentioned preferable range and a thermoplastic polyester resin composition having a carboxyl group concentration in the above-mentioned preferable range can be obtained.

Examples of the above-mentioned premixing include a method of dry blending and a method of mixing using a mechanical mixing device such as a tumbler, a ribbon mixer and a Henschel mixer. Further, (E) an inorganic filler other than the fiber reinforced material and the fiber reinforced material may be added by installing a side feeder in the middle of the feeding portion and the vent portion of the multi-screw extruder such as a twin-screw extruder. .. In the case of liquid additives, a method of adding a liquid addition nozzle in the middle of the breech loader and vent of a multi-screw extruder such as a twin-screw extruder and using a plunger pump, or the breech loader A method of supplying from a unit or the like with a metering pump may be used.

The thermoplastic polyester resin composition of the present invention is preferably pelletized and then molded. Strands can be pelletized using, for example, single-screw extruders, twin-screw extruders, triple-screw extruders, conical extruders and kneader-type kneaders equipped with "unimelt" or "dalmage" type screws. There is a method of discharging in a shape and cutting with a strand cutter.

By melt-molding the thermoplastic polyester resin composition of the present invention, molded products of films, fibers and other various shapes can be obtained. Examples of the melt molding method include injection molding, extrusion molding, blow molding and the like, and injection molding is particularly preferably used.

As the injection molding method, gas assist molding, two-color molding, sandwich molding, in-mold molding, insert molding, injection press molding and the like are known in addition to the usual injection molding method, but any molding method can be applied. it can.

The molded product of the present invention can be used as a molded product of mechanical mechanical parts, electric parts, electronic parts and automobile parts utilizing the features of long-term hydrolysis resistance, mechanical properties such as tensile strength and elongation, and excellent heat resistance. it can. Further, the molded product of the present invention is particularly useful for exterior parts because it is excellent in long-term hydrolysis resistance.

Specific examples of mechanical mechanical parts, electrical parts, electronic parts and automobile parts include breakers, electromagnetic switches, focus cases, flyback transformers, molded products for fixing machines of copying machines and printers, general household appliances, and OA. Housing for equipment, variable condenser case parts, various terminal boards, transformers, printed wiring boards, housings, terminal blocks, coil bobbins, connectors, relays, disk drive chassis, transformers, switch parts, outlet parts, motor parts, sockets, plugs , Condenser, various cases, resistors, electrical / electronic parts incorporating metal terminals and conductors, computer-related parts, audio parts such as acoustic parts, lighting parts, telegraph equipment-related parts, telephone equipment-related parts, air conditioner parts, VTR Examples include home appliance parts such as televisions, copying machine parts, facsimile parts, optical equipment parts, automobile ignition device parts, automobile connectors, and various electric parts for automobiles.

Next, the effect of the thermoplastic polyester resin composition of the present invention will be specifically described with reference to Examples. The raw materials used in Examples and Comparative Examples are shown below. Here,% and parts all represent% by weight and parts by weight, and "/" in the resin name below means copolymerization.

(A) Thermoplastic Polyester Resin <A-1> Polybutylene terephthalate resin: A polybutylene terephthalate resin manufactured by Toray Corporation and having a carboxyl terminal group concentration of 30 eq / t was used.
<A-2> Polyethylene terephthalate resin: A polyethylene terephthalate resin manufactured by Toray Industries, Inc. and having a carboxyl terminal group concentration of 40 eq / t was used.

(B) Novolac type epoxy resin represented by the general formula (1) <B-1> Novolac type epoxy resin having an epoxy equivalent of 253 g / eq represented by the following general formula (6): manufactured by Nippon Kayaku Co., Ltd. XD-1000 ”was used.

N in the above general formula (6) represents a value of 1 to 3.
<B-2> A novolak type epoxy resin having an epoxy equivalent of 290 g / eq represented by the following general formula (7): “NC-3000H” manufactured by Nippon Kayaku Co., Ltd. was used.

N in the above general formula (7) represents a value of 2 to 4.

(B') Novolac type epoxy resin other than the general formula (1) <B'-1> Novolac type epoxy resin having an epoxy equivalent of 211 g / eq represented by the following general formula (8): manufactured by Nippon Kayaku Co., Ltd. EOCN-102S ”was used.

N in the above general formula (8) represents a value of 3 to 5.

(C) The reducing phosphorus compound <C-1> disodium phosphite represented by the general formula (4): disodium phosphite (reagent) manufactured by Tokyo Chemical Industry Co., Ltd. was used.
<C-2> Sodium hypophosphite: Sodium hypophosphite (reagent) manufactured by Tokyo Chemical Industry Co., Ltd. was used.
<C-3> Calcium hypochlorite: Calcium hypophosphate (reagent) manufactured by Tokyo Chemical Industry Co., Ltd. was used.
<C-4> Diphenylhydrogen phosphite: Diphenylhydrogen phosphite (reagent) manufactured by Tokyo Chemical Industry Co., Ltd. was used.
<C-5> 9,10-Dihydro-9-oxa-10-phospphenanthrene-10-oxide: HCA manufactured by Sanko Co., Ltd. was used.

(C') Phosphorus compounds other than the reducing phosphorus compounds represented by the general formula (4) <C'-1> 2-carboxyethyl (phenyl) phosphinic acid: 2-2-manufactured by Tokyo Chemical Industry Co., Ltd. Carboxyethyl (phenyl) phosphinic acid (reagent) was used.
<C'-2> Di (2-ethylhexyl) phosphate: Di (2-ethylhexyl) phosphate (reagent) manufactured by Tokyo Chemical Industry Co., Ltd. was used.
<C'-3> Triphenylphosphine: Triphenylphosphine (reagent) manufactured by Tokyo Chemical Industry Co., Ltd. was used.
<C'-4> Aluminum diethylphosphinate: "Exolit" (registered trademark) OP1240 manufactured by Clariant Japan Co., Ltd. was used.

(D) Epoxy compound having two epoxy functional groups per molecule <D-1> Epoxy equivalent 192 g / eq Bisphenol A type epoxy: "jER" (registered trademark) 819 manufactured by Mitsubishi Chemical Corporation is used. There was.
<D-2> Bisphenol A type epoxy having an epoxy equivalent of 906 g / eq: “jER” (registered trademark) 1004 manufactured by Mitsubishi Chemical Corporation was used.

(E) Fiber Reinforcing Material <E-1> Glass fiber treated with a sizing agent containing an epoxy compound: Glass fiber ECS03T-187 manufactured by Nippon Electric Glass Co., Ltd., having a cross-sectional diameter of 13 μm and a fiber length of 3 mm was used.
<E-2> Glass fiber treated with a sizing agent containing a copolymer composed of maleic anhydride: ECS03T-253 manufactured by Nippon Electric Glass Co., Ltd., having a cross-sectional diameter of 13 μm and a fiber length of 3 mm was used.

(F) Reaction Accelerator <F-1> Organic phosphine and its salt: Tetraphenylphosphonium bromide, tetraphenylphosphonium bromide (reagent) manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 419.3 was used.

(G) Other Additives <G-1> Olefin resin: Ethylene / glycidyl methacrylate copolymer, "Rotader" (registered trademark) AX8840 (trade name) manufactured by Elf Atchem was used.

[Measurement method for each characteristic]
In Examples and Comparative Examples, the characteristics were evaluated by the measurement method described below.

1. 1. (A) Amount of carboxyl group derived from component (A) A solution prepared by dissolving a thermoplastic polyester resin in an o-cresol / chloroform (2/1, vol / vol) mixed solution, using 1% bromophenol blue as an indicator. , 0.05 mol / L ethanolic potassium hydroxide was titrated, and the carboxyl group concentration was calculated by the following formula. The end point of the titration was blue (color tone D55-80 (2007 Dpackettype Japan Paint Manufacturers Association)).
Carboxyl group concentration [eq / g] = (0.05 mol / L ethanolic potassium hydroxide required for titration of o-cresol / chloroform (2/1, vol / vol) mixed solution in which component (A) is dissolved [ ml] -o-cresol / chloroform (2/1, vol / vol) 0.05 mol / L ethanolic potassium hydroxide [ml]) required for titration of the mixed solution × 0.05 mol / L ethanolic potassium hydroxide Concentration [mol / ml] × 1 / Collection amount of component (A) used for titration [g].

From the carboxyl group concentration of the component (A) calculated by the above titration and the total amount of the thermoplastic polyester resin composition, the amount of the carboxyl group derived from (A) derived in the thermoplastic polyester resin composition was calculated by the following formula.
(A) -derived carboxyl group compounding amount [eq / g] = ((A) component carboxyl group concentration [eq / g] × (A) component compounding amount [parts by weight]) in the thermoplastic polyester resin composition / Total amount of thermoplastic polyester resin composition [parts by weight].

2. 2. (B) Amount of Epoxy Group Derived from Ingredients According to JISK7236: 2001, (B) acetic acid and triethylammonium bromide / acetic acid were added to a solution of the novolak type epoxy resin represented by the general formula (1) in chloroform. The solution was added, and the potential difference was titrated with 0.1 mol / L acetic acid perchlorate, and the epoxy group concentration was calculated by the following formula.
Epoxy group concentration [eq / g] = (0.1 mol / L perchlorine required for titration of the solution to which acetic acid and triethylammonium bromide / acetic acid solution were added after dissolving the component (B) in the dissolved chloroform. Acetic acid acid [ml] -0.1 mol / L acetic acid perchlorate [ml]) x 0.1 mol / L acetic acid perchlorate required for titration of a solution of acetic acid and triethylammonium bromide / acetic acid solution added to chloroform. Concentration [mol / ml] × 1 / Collection amount of component (B) used for titration [g]).

From the epoxy group concentration of the component (B) calculated by the potentiometric titration described above and the total amount of the thermoplastic polyester resin composition, the amount of the epoxy group derived from (B) in the thermoplastic polyester resin composition was calculated by the following formula. ..
(B) -derived epoxy group compounding amount [eq / g] = ((B) component epoxy group concentration [eq / g] × (B) component compounding amount [parts by weight]) in the thermoplastic polyester resin composition / Total amount of thermoplastic polyester resin composition [parts by weight].
For reference, when a novolak type epoxy resin other than the (B') general formula (1) was used, (B') was read as (B) for calculation.

3. 3. Mechanical properties (tensile strength and tensile elongation)
When polybutylene terephthalate resin is used as the component (A) using an IS55EPN injection molding machine manufactured by Toshiba Machine Co., Ltd., the molding temperature is 250 ° C. and the mold temperature is 80 ° C., and the polyethylene terephthalate resin is used as the component (A). When the above is used, the test piece thickness is 1/8 inch (1/8 inch) under the molding cycle condition of molding temperature 270 ° C. and mold temperature 80 ° C., injection time and holding pressure time totaling 10 seconds, and cooling time 10 seconds. A test piece for evaluating the tensile properties of the ASTM No. 1 dumbbell having a thickness of about 3.2 mm was obtained. Using the obtained test piece for evaluating tensile properties, the maximum tensile strength (tensile strength) and the maximum tensile elongation (tensile elongation) were measured according to ASTMD638 (2005). The value was the average value of the three measured values. Materials with large tensile strength and tensile elongation were judged to have excellent toughness.

4. Long-term hydrolysis resistance (tensile strength retention)
Using the IS55EPN injection molding machine manufactured by Toshiba Machine Co., Ltd., the above 3. Under the same injection molding conditions as the preparation conditions for the test piece for evaluation of tensile physical characteristics in the above item, a test piece for evaluation of tensile physical properties of ASTM No. 1 dumbbell having a thickness of 1/8 inch (about 3.2 mm) was obtained. The obtained ASTM No. 1 dumbbell was put into an advanced accelerated life test device EHS-411 manufactured by Espec Co., Ltd., which was set to a temperature and humidity of 121 ° C. × 100% RH, and subjected to moist heat treatment for 96 hours (4 days). It was. (F) The thermoplastic polyester resin composition containing the reaction accelerator was further subjected to a wet heat treatment for 96 hours (4 days) (total 192 hours (8 days)). Regarding the molded product after the wet heat treatment, the above 3. The maximum tensile strength was measured under the same conditions as the tensile test described in the above section, and the average value of the three measured values was obtained. From the maximum tensile strength after the wet heat treatment and the maximum tensile strength without the wet heat treatment, the tensile strength retention rate was calculated by the following formula.
Tensile strength retention rate (%) = (Maximum tensile strength after wet heat treatment ÷ Maximum tensile strength without wet heat treatment) x 100

It was judged that a material having a tensile strength retention rate of less than 50% was inferior in hydrolysis resistance, and a material having a larger tensile strength retention rate was judged to be superior in hydrolysis resistance.

5. Retention stability (rate of change in melt viscosity index)
Using C501DOS manufactured by Toyo Seiki Co., Ltd., the 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 325 g.

Further, after the thermoplastic polyester resin composition was allowed to stay in the cylinder for 30 minutes, the melt viscosity index was measured under the same conditions, and the difference between the melt viscosity index before and after the stay (change rate (%)). ) Was asked. The rate of change (%) calculated here is an absolute value and was calculated as a positive value. When the rate of change of the melt viscosity index exceeds 50%, it is judged that the retention stability is inferior, and the smaller the difference, the better the retention stability.

6. Color and color stability (Yellowness (YI))
Using the IS55EPN injection molding machine manufactured by Toshiba Machine Co., Ltd., the above 3. Under the same injection molding conditions as the preparation conditions for the test piece for evaluation of tensile physical characteristics in the above item, a test piece for color tone evaluation of ASTM No. 1 dumbbell having a thickness of 1/8 inch (about 3.2 mm) was obtained. The color tone of the obtained ASTM No. 1 dumbbell was measured with a spectrum color meter SE2000 manufactured by Nippon Denshoku Kogyo, and the yellowness (YI value) was calculated. When the yellowness (YI value) exceeds 30, it is judged that the color tone is inferior, and it is judged that the material having a smaller yellowness (YI value) has a better color tone.

Further, the ASTM No. 1 dumbbell was left for 500 minutes in an ESPEC hot air oven PVH-222 set at a temperature of 150 ° C. as a dry heat treatment, and then taken out. Similarly, for the taken-out test, the color tone was measured by the above method, and the yellowness (YI value) was calculated. When the yellowness of the test piece after the dry heat treatment exceeds 3.0, it is judged that the color tone stability is inferior, and it is judged that the material having the smaller yellowness (YI value) of the test piece after the dry heat treatment has a better color tone.

7. Concentration of carboxyl group A reaction product of (A) a thermoplastic polyester resin, (A) a thermoplastic polyester resin and (B) a novolak type epoxy resin represented by the general formula (1) in the thermoplastic polyester resin composition. And (A) the concentration of carboxyl groups derived from the thermoplastic polyester resin with respect to the total amount of the reactants of (A) the thermoplastic polyester resin and (C) the reducing phosphorus compound represented by the general formula (4). A) Concentration of carboxyl groups derived from the reaction product of the thermoplastic polyester resin and (B) the novolak type epoxy resin represented by the general formula (1), and (A) the thermoplastic polyester resin and (C) the general formula (C) The carboxyl group concentration derived from the reaction product with the reducing phosphorus compound represented by 4) is a solution obtained by dissolving 2 g of the composition in 50 mL of an o-cresol / chloroform (2/1, vol / vol) mixed solution. Using 1% bromophenol blue as an indicator, titration with 0.05 mol / L ethanolic potassium hydroxide, calculating the concentration of carboxyl groups in the composition, and then multiplying by the compounding ratio of (A) thermoplastic polyester resin. I asked.

8. Epoxy group concentration The epoxy group concentration in the thermoplastic polyester composition is 20 mL of acetic acid and odor after dissolving 2 g of the thermoplastic polyester resin composition in a 30 mL mixed solution of o-cresol / chloroform (2/1, vol / vol). It was calculated by adding 10 mL of a 20 wt% solution of triethylammonium bolic acid / acetic acid and performing potential differential titration with 0.1 mol / L acetic acid perchlorate.

9. Deterioration resistance (carboxyl group concentration increase rate)
Using the IS55EPN injection molding machine manufactured by Toshiba Machine Co., Ltd., the above 3. Under the same injection molding conditions as the preparation conditions for the test piece for evaluation of tensile physical characteristics in the above item, a test piece for evaluation of tensile physical properties of ASTM No. 1 dumbbell having a thickness of 1/8 inch (about 3.2 mm) was obtained. The obtained ASTM No. 1 dumbbell was taken out after being left on aluminum foil for 15 minutes in an ESPEC hot air oven PVH-222 set at a temperature of 270 ° C. as an oxidative deterioration treatment. After cooling the taken-out test piece to room temperature, the above 8. The carboxyl group concentration was measured under the same conditions as above.

From the carboxyl group concentration of the molded product after oxidative deterioration and the untreated carboxyl group concentration, the carboxyl group concentration increase rate was calculated by the following formula.
Carboxylic group concentration increase rate (%) = (Carboxylic acid concentration of oxidatively deteriorated molded product-Carboxylic acid concentration of untreated molded product / Carboxylic acid concentration of untreated molded product) x 100
It was judged that the material having a carboxyl group concentration increase rate of 70% or less was excellent in oxidation deterioration resistance, and further, the material having a carboxyl group concentration increase rate of 3.0% or less was judged to be particularly excellent.

10. Bleed-out resistance Using the IS55EPN injection molding machine manufactured by Toshiba Machine Co., Ltd., the above 3. Under the same injection molding conditions as the preparation conditions for the test piece for evaluation of tensile physical characteristics in the above item, a test piece for bleed-out evaluation of ASTM1 dumbbell having a thickness of 1/8 inch (about 3.2 mm) was obtained. The obtained ASTM No. 1 dumbbell was put into the highly accelerated life test device EHS-3.11 manufactured by Espec Co., Ltd., which was set to a temperature and humidity of 121 ° C. × 100% RH, for 96 hours (4 days) and subjected to moist heat treatment. It was. The appearance of the molded product after the wet heat treatment was visually observed, and the bleed-out was determined according to the following criteria.
◯: No liquid or white powder bleed-out is observed in the molded product.
X: Liquid or white powder bleed-out is observed in a part or everywhere of the molded product.

[Examples 1 to 23], [Comparative Examples 1 to 9]
Using a twin-screw extruder (manufactured by Japan Steel Works, TEX-30α) with a screw diameter of 30 mm and L / D35 with a unidirectional rotating vent, (A) thermoplastic polyester resin, (B) or (B') novolak type epoxy Tables 1 to 4 show resins, (C) reducing phosphorus compounds, (D) epoxy compounds having two epoxy functional groups per molecule, (F) reaction accelerators, and other materials as needed. It was mixed with the content composition shown in the above, and added from the main filling part of the twin-screw extruder. The glass fiber (E) was added by installing a side feeder in the middle of the filling portion and the vent portion. Further, the mixture was melt-mixed under extrusion conditions of a kneading temperature of 260 ° C. and a screw rotation of 150 rpm, discharged in a strand shape, passed through a cooling bath, and pelletized by a strand cutter.

The obtained pellets were dried in a hot air dryer at a temperature of 110 ° C. for 6 hours, evaluated by the above method, and the results are shown in Tables 1 to 4. A reaction product of (A) a thermoplastic polyester resin, (A) a thermoplastic polyester resin and (B) a novolak type epoxy resin represented by the general formula (1) in a thermoplastic polyester resin composition, and (A). (A) Concentration of carboxyl groups derived from the thermoplastic polyester resin with respect to the total amount of the reaction product of the thermoplastic polyester resin and (C) the reducing phosphorus compound represented by the general formula (4), (A) thermoplasticity. The carboxyl group concentration derived from the reaction product of the polyester resin and (B) the novolak type epoxy resin represented by the general formula (1), and (A) the thermoplastic polyester resin and (C) the general formula (4). The carboxyl group concentration derived from the reaction product with the reducing phosphorus compound to be obtained is indicated as "carboxyl group concentration" in the table.

Further, the compounding concentration of the reaction accelerator in Example 17 / the compounding concentration of the epoxy group was 0.039.

From the comparison between Examples 1 to 6 and 8 to 13 and Comparative Examples 1 to 7 and 9, the amount of the component (B) and the amount of the component (C) are within a specific range of hydrolysis resistance and oxidation deterioration resistance. , A material having excellent bleed-out resistance was obtained.

From the comparison between Examples 2 and 6 and Comparative Example 3, a material having excellent hydrolysis resistance can be obtained while maintaining the retention stability by using the novolak type epoxy resin represented by (B) the general formula (1). It was.

From the comparison between Examples 1 to 3 and Examples 4 and 5, a metal salt of phosphorous acid or a metal salt of hypophosphorous acid is used as the reducing phosphorus compound represented by (C) general formula (4). As a result, a material having an excellent balance of hydrolysis resistance, oxidation deterioration resistance and color stability was obtained.

From the comparison of Examples 2 and 9 to 10 and Example 8, the material having the epoxy group concentration in the thermoplastic polyester resin composition in the range of 20 to 150 eq / t is particularly long-term hydrolysis resistance and at 270 ° C. Excellent for materials with excellent balance of retention stability.

From the comparison between Examples 14, 15 and 16 and Examples 1 and 2, (D) when a specific amount of the epoxy compound having 2 epoxy functional groups per molecule was blended, the hydrolysis resistance and 270 ° C. A material having excellent retention stability was obtained.

From the comparison between Example 14 and Example 15, a material having a further excellent retention stability at 270 ° C. was obtained by using (D) a bisphenol A type epoxy resin having a specific epoxy value.

From the comparison between Example 17 and Example 2, when a specific amount of the (F) reaction accelerator was blended, a material having an excellent balance between mechanical characteristics, long-term hydrolysis resistance, color tone stability, and oxidative decomposition resistance could be obtained. It was.

From the comparison between Example 2 and Example 7, when polybutylene terephthalate resin was used as the component (A), a material having an excellent balance between mechanical strength and long-term hydrolysis resistance was obtained.

From the comparison between Examples 18, 19, 21, 22 and Example 2, by further blending (E) the fiber reinforcing material, the balance between mechanical properties, long-term hydrolysis resistance, color tone stability, and oxidation decomposition resistance can be achieved. An excellent material was obtained.

From the comparison of Examples 19 and 22 and Examples 18 and 21, by using (E) a glass fiber treated with a sizing agent containing a copolymer composed of maleic anhydride as a fiber reinforcing material, mechanical properties and long-term properties are obtained. An excellent material was obtained due to the balance of hydrolysis resistance, color stability, and oxidative decomposition resistance.

Comparing Examples 20 and 23 with Examples 19 and 22, (G) a material having an excellent balance of toughness and heat resistance, long-term hydrolysis resistance and color tone by further blending an olefin resin as an additive. was gotten.

Claims (8)

With respect to 100 parts by weight of (A) thermoplastic polyester resin, (B) 0.05 to 5 parts by weight of novolak type epoxy resin represented by the following general formula (1) and (C) represented by the following general formula (4). A thermoplastic polyester resin composition containing 0.01 to 1 part by weight of the reducing phosphorus compound.
(In the general formula (1), X represents a divalent group represented by the general formula (2) or (3). In the general formulas (1) and (3), R ¹ , R ² , R ⁴ and R ⁵ each independently represent 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 from each other. R ³ is a hydrogen atom and has 1 to 8 carbon atoms. Represents an alkyl group or an aryl group having 6 to 10 carbon atoms. In the above general formula (1), n represents a value greater than 0 and 10 or less. In the above general formulas (1) and (3), a, c, d represents an integer of 0 to 4 independently, and b represents an integer of 0 to 3).
(In the above general formula (4), R ⁶ and R ⁷ are independently hydrogen (except when both R ⁶ and R ⁷ are hydrogen), OM (where O is negatively charged oxygen). It is an atom and M is a positively charged counterion), an alkyl group having 1 to 20 carbon atoms, an alkylene group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an alkyl having 1 to 20 carbon atoms. It is selected from an oxy group, a polyoxyalkylene group composed of an alkylene having 2 to 4 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms. The alkyl group, an alkylene group, an aryl group, an alkyloxy group and a polyoxyalkylene group. , And aryloxy groups may be optionally substituted, and the optionally substituted substituents are independently OH group, halogen, COOH group, COOR ⁸ groups (where R ⁸ is carbon). It is selected from (the number 1 to 4 alkyl groups) and ₂ NH groups. The alkyl group, alkylene group, aryl group, alkyloxy group, polyoxyalkylene group, and aryloxy group are optionally substituted. The number of substitutions in the case is 1 or 2. R ⁶ and R ⁷ can also be linked by cross-linking.) (C) The thermoplastic polyester resin composition according to claim 1, wherein the reducing phosphorus compound represented by the general formula (4) is a metal salt of phosphorous acid or a metal salt of hypophosphorous acid. The thermoplastic polyester resin composition according to claim 1 or 2, wherein the epoxy group concentration in the thermoplastic polyester resin composition is 20 to 150 eq / t. The thermoplastic polyester resin composition according to any one of claims 1 to 3, wherein the carboxyl group concentration in the thermoplastic polyester resin composition is 0 to 20 eq / t. The thermoplastic polyester resin composition according to any one of claims 1 to 4 , wherein the thermoplastic polyester resin (A) is polybutylene terephthalate. The thermoplastic polyester resin composition according to any one of claims 1 to 5 , wherein 1 to 100 parts by weight of the fiber reinforcing material (E) is further added to 100 parts by weight of the thermoplastic polyester resin (A). The thermoplastic polyester resin composition according to any one of claims 1 to 6 , wherein 0.001 to 1 part by weight of the reaction accelerator (F) is further added to 100 parts by weight of the thermoplastic polyester resin (A). .. A molded product obtained by melt-molding the thermoplastic polyester resin composition according to any one of claims 1 to 7 .