JP2009040834A - Polyester resin composition and molded article using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic polyester resin composition which is excellent in melt flowability, is also excellent in mechanical properties such as toughness and stiffness, and further in scratch resistance, and exhibits excellent physical properties for both the flowability and the mechanical properties, which has been difficult conventionally. <P>SOLUTION: Provided is the thermoplastic polyester resin composition comprising (a) a thermoplastic saturated polyester resin and (b) a thermosetting unsaturated polyester resin, characterized in that the content of (b) the thermosetting unsaturated polyester resin is >10 wt.%. A resin molded article prepared by molding the same is also provided. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a thermoplastic saturated polyester resin composition and a resin molded body formed by molding the same. Specifically, the present invention relates to a thermoplastic saturated polyester resin composition excellent in all of fluidity, mechanical properties, hydrolysis resistance, and scratch resistance, and a resin molded body formed by molding the same.

  Thermoplastic polyester resins such as polybutylene terephthalate resin and polyethylene terephthalate resin are easy to process, and are excellent in mechanical properties, electrical properties, heat resistance and other physical and chemical properties.

  Utilizing this property, thermoplastic polyester resins are also used in precision equipment parts such as automobile parts and electrical / electronic equipment parts, and in bath and sanitary fields such as bathrooms, washstands and toilets. In particular, since polybutylene terephthalate resin has a high crystallization speed, it is suitably used for injection molding, and is also used for thin-walled resin moldings such as automobiles or connector parts materials in the electronic field, and is widely used. Yes.

  Since this polybutylene terephthalate resin and polyethylene terephthalate resin do not contain an unsaturated fatty acid as an acid component among alcohol components and acid components that are constituent components of the polyester main chain unit, “(thermoplastic) saturated polyester resin” It is called. On the other hand, those containing unsaturated fatty acids (anhydrides) such as (anhydrous) maleic acid and fumaric acid as acid components are called “unsaturated polyester resins” and are distinguished.

  Now, when the resin molded product formed from the thermoplastic saturated polyester resin composition is a thin part such as a connector, the metal terminal can be securely held with a lance, etc., and the connector cannot be loosened by locking. Etc. are required. Since these parts such as lances and lock mechanisms are thin and many are often taken, in order to perform injection molding and perform the required functions, thermoplastic polyester resin, which is a raw material resin The composition (hereinafter sometimes simply referred to as “raw resin”) requires sufficient fluidity, rigidity, and toughness.

  In general, when fluidity is imparted to a raw material resin, for example, a method of lowering the molecular weight of the raw material resin can be mentioned. On the other hand, however, the toughness of the resulting resin molding is reduced, and cracks are easily generated during molding. Also, reinforcing fillers such as talc are usually added for the purpose of imparting rigidity, but in this case as well, the tensile elongation and toughness are lowered against the improvement of the elastic modulus of the resin molded product, and the lance is reduced. And the lock mechanism was damaged.

  Further, if the surface of the resin molded body is scratched, the scratch becomes a crack starting point, and there is a risk of damage when the terminal is detached. As a method for improving toughness, a method of adding a polyester-based elastomer to a raw material resin has been proposed particularly when the component is a connector (see, for example, Patent Documents 1 and 2). However, this method inevitably reduces fluidity and rigidity, and it is difficult to satisfy mechanical properties, fluidity, and scratch resistance at the same time.

  In addition, as a cause of the lowering of the toughness of the raw material resin, for example, poor adhesion at the interface between the filler and the raw material resin is known. There has been proposed a method for improving the interfacial adhesive strength using a surface treated with a silane coupling agent having an epoxy group or the like (see, for example, Patent Document 3).

  However, even if such a surface treatment filler is used, there is a problem that both the elastic modulus and the toughness are not improved at the same time, although there is a slight physical property improvement effect of the raw material resin. In particular, the flowability of the raw material resin is important in the production of a thin resin molded body such as a connector. However, the flowability of the raw material resin containing a filler treated with a reactive silane coupling agent tends to decrease. There was a problem to say.

In addition, as a saturated polyester resin composition containing a thermosetting unsaturated polyester resin, the thing for the purpose of the surface hardness improvement of a saturated polyester resin is known, for example (refer patent document 4). However, the upper limit of the thermosetting unsaturated polyester resin content in the saturated polyester resin composition is as low as 10% by weight, and it has even been suggested to improve the scratch resistance and fluidity of the saturated polyester resin composition at the same time. There wasn't.
Japanese Patent Publication No. 3-50391 JP-A-9-255857 Japanese Patent Application Laid-Open No. 5-140429 JP-A-6-145487

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a thermoplastic polyester resin composition having not only excellent mechanical properties but also excellent fluidity and scratch resistance. It is in.

  The present inventors have intensively studied to solve the above-described problems. As a result, the thermoplastic saturated polyester resin is reacted with a thermosetting unsaturated polyester resin, that is, an unsaturated polyester resin and a polymerizable unsaturated monomer, to contain a specific amount of a crosslinked thermosetting resin. And found excellent fluidity.

  A thermoplastic resin in which a specific amount of a thermosetting unsaturated polyester resin having a higher heat distortion temperature than that of the saturated polyester resin is contained, and the thermosetting unsaturated polyester resin is dispersed as fine particles in the thermoplastic saturated polyester resin. It has been found that the saturated polyester resin composition exhibits particularly excellent fluidity.

  Furthermore, the resin molded body formed by molding this thermoplastic saturated polyester resin composition is excellent in mechanical properties such as toughness and rigidity, and also in scratch resistance, and has been considered difficult in the past. The present invention was completed by finding that excellent physical properties were exhibited in both of the physical properties.

  That is, the gist of the present invention is a thermoplastic polyester resin containing (a) a thermoplastic saturated polyester resin and (b) a thermosetting unsaturated polyester resin, wherein (b) the thermosetting unsaturated polyester resin content is The present invention relates to a thermoplastic polyester resin composition characterized by exceeding 10% by weight, a method for producing the same, and a resin molded product obtained by molding this resin composition.

  Since the thermoplastic saturated polyester resin composition of the present invention is excellent in fluidity and scratch resistance in addition to mechanical properties (rigidity and toughness), its industrial utility value is extremely high. It can be expected to be used in a wide range of products, various parts, etc. in the fields, automobiles, machinery, medical, daily goods, buses and sanitary.

  Among them, the thermoplastic saturated polyester resin composition of the present invention is excellent in fluidity, so that it can be used not only for thin products such as connectors, but also for bath and sanitary fields (washing bowl, bathtub, toilet seat, tank) ; Components constituting septic tanks, automobiles, railway vehicles, ships, etc .; Artificial marble suitable for kitchen counters; Electric parts such as cooking utensils panels and buttons; Resins that require high scratch resistance and high appearance It can be expected to be used for products, and it can be expected that these resin moldings are produced by an injection molding method with high productivity.

Hereinafter, the present invention will be described in more detail.

<(A) Thermoplastic saturated polyester resin (a)>
The (a) thermoplastic saturated polyester resin used in the present invention is a polyester resin in which the constituent components of the polyester main chain unit are an alcohol component and an acid component, the acid component is a dicarboxylic acid or a derivative thereof, and the alcohol component is a diol. Thus, the main acid component does not contain an unsaturated fatty acid. The thermoplastic saturated polyester resin (a) used in the present invention is not particularly limited as long as it is a thermoplastic saturated polyester resin, and any conventionally known one can be used. The thermoplastic saturated polyester resin (a) may be used alone or in combination of two or more in any proportion.

  The dicarboxylic acid or derivative thereof, which is a component of the thermoplastic saturated polyester resin used in the present invention (a), includes aromatic dicarboxylic acid, alicyclic dicarboxylic acid, aliphatic dicarboxylic acid, and lower alkyl or glycol thereof. Of these esters.

  Specific examples of aromatic dicarboxylic acids include phthalic acid, terephthalic acid, isophthalic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, 4,4′-benzophenone dicarboxylic acid, 4 4,4'-diphenoxyethanedicarboxylic acid, 4,4'-diphenylsulfone dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and esters thereof.

  Specific examples of the alicyclic dicarboxylic acid include 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and the like. Specific examples of the aliphatic dicarboxylic acid include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid, and esters thereof.

  These dicarboxylic acids and derivatives thereof such as esters thereof may be used singly or in combination of two or more in any proportion. Among them, the acid component of the thermoplastic saturated polyester resin used in the present invention is preferably an aromatic dicarboxylic acid, a lower alkyl ester having 1 to 4 carbon atoms, or a glycol ester. Specifically, for example, terephthalic acid And its lower alkyl esters are particularly preferred.

  Specific examples of the diol that is a constituent component of the thermoplastic saturated polyester resin (a) used in the present invention include aliphatic diols, alicyclic diols, and aromatic diols.

  Among these aliphatic diols, aliphatic diols having 2 to 20 carbon atoms are preferable. Specifically, for example, ethylene glycol, 1,4-butanediol, diethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, polypropylene glycol, polytetramethylene glycol, dibutylene glycol, 1,5- Examples include pentanediol, neopentyl glycol, 1,6-hexanediol, and 1,8-octanediol.

  As the alicyclic diol, an alicyclic diol having 2 to 20 carbon atoms is particularly preferable. Specific examples include 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,1-cyclohexanedimethylol, 1,4-cyclohexanedimethylol, and the like.

  As the aromatic diol, an aromatic diol having 6 to 14 carbon atoms is particularly preferable. Specific examples include xylylene glycol, 4,4'-dihydroxybiphenyl, 2,2-bis (4-hydroxyphenyl) propane and bis (4-hydroxyphenyl) sulfone.

  These diols may be used alone or in combination of two or more in any proportion. Among them, the diol component of the thermoplastic saturated polyester resin (a) used in the present invention is preferably an aliphatic diol, particularly preferably ethylene glycol or 1,4 butanediol, and particularly preferably 1,4 butanediol.

  The (a) thermoplastic saturated polyester resin used in the present invention may have a hydroxycarboxylic acid, a monofunctional component, and / or a trifunctional or higher polyfunctional component. Specific examples of the hydroxycarboxylic acid include lactic acid, glycolic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthalenecarboxylic acid, and p-β-hydroxyethoxybenzoic acid. A preferred example is given.

  Specific examples of monofunctional components include alkoxycarboxylic acid, stearyl alcohol, benzyl alcohol, stearic acid, benzoic acid, tert-butylbenzoic acid, and benzoylbenzoic acid.

  Preferred examples of the trifunctional or higher functional component include tricarballylic acid, trimellitic acid, trimesic acid, pyromellitic acid, gallic acid, trimethylolethane, trimethylolpropane, glycerol, and pentaerythritol.

  As the (a) thermoplastic saturated polyester resin used in the present invention, a polybutylene terephthalate resin (PBT resin) is particularly preferable. In the present invention, the PBT resin means that terephthalic acid accounts for 50 mol% or more of the total dicarboxylic acid component, and 1,4-butanediol accounts for 50 mol% or more of the total diol.

  As the PBT resin used in the present invention, the ratio of terephthalic acid in the dicarboxylic acid unit is preferably 70 mol% or more, particularly preferably 90 mol% or more, and the ratio of 1,4-butanediol in the diol unit is preferably It is preferably 70 mol% or more, particularly 90 mol% or more.

  In particular, the (a) thermoplastic saturated polyester resin used in the present invention is a polybutylene terephthalate homopolymer having terephthalic acid as the only dicarboxylic acid unit and 1,4-butanediol as the only diol unit. , Because mechanical properties and heat resistance are further improved.

  The terminal carboxyl group concentration of the PBT resin used in the present invention may be appropriately selected and determined. However, if it is too high, the hydrolysis resistance and fluidity tend to deteriorate, so it is usually 40 μeq / g or less. It is preferable that it is -35microeq / g, especially 5-30microeq / g.

  The terminal carboxyl group concentration was measured by dissolving 0.5 g of PBT resin in 25 ml of benzyl alcohol and titrating with a benzyl alcohol solution having a sodium hydroxide concentration of 0.01 mol / liter. The equivalent carboxyl group equivalent is shown.

  The intrinsic viscosity of the PBT resin used in the present invention may be appropriately selected and determined. However, if it is too low, the mechanical properties deteriorate, and conversely, if it is too high, the fluidity decreases and the molding process becomes difficult. There is a case. Therefore, it is usually 0.5 to 3.0 dl / g, preferably 0.5 to 1.5 dl / g, particularly preferably 0.6 to 1.3 dl / g. Here, the intrinsic viscosity is a measured value under a condition of 30 ° C. in a mixed solvent of tetrachloroethane and phenol 1: 1 (weight ratio).

  Moreover, the PBT resin used for this invention is good also as PBT resin which uses the 2 or more types of different intrinsic viscosity together, and has the intrinsic viscosity mentioned above.

  The method for producing the thermoplastic saturated polyester resin (a) used in the present invention is arbitrary, and any conventionally known one can be used. Specifically, for example, in a method for producing a PBT resin comprising a terephthalic acid component and a 1,4-butanediol component, a direct polymerization method, a transesterification method, and the like can be given.

  The production method of the PBT resin in the direct polymerization method is a method in which terephthalic acid and 1,4-butanediol are directly esterified, and water is generated in the initial esterification reaction. In the transesterification method, dimethyl terephthalate or the like is used as a main raw material, and alcohol is generated by an initial transesterification reaction. Among these, the direct esterification reaction is preferable from the viewpoint of raw material cost.

  In addition, the (a) thermoplastic saturated polyester resin used in the present invention may be produced by either a batch method or a continuous method with respect to the raw material supply or the polymer discharge form. Furthermore, the initial esterification reaction or transesterification reaction is carried out in a continuous operation, and the subsequent polycondensation is carried out in a batch operation. What was obtained by the method of performing by continuous operation may be used.

  (A) When a polymerization catalyst is used in the production of the thermoplastic saturated polyester resin, it is preferable to use a titanium compound and a Group 1 and / or Group 2 metal compound as the polymerization catalyst. Specific examples of the titanium compound include titanium alcoholates, among which tetrabutyl titanate is preferable.

  Specific examples of the Group 1 and / or Group 2 metal compounds include compounds such as lithium, sodium, potassium, magnesium, and calcium from the viewpoint of handling and availability, and catalytic effects. A magnesium compound excellent in the color tone of the obtained PBT resin is preferable. Of the magnesium compounds, magnesium acetate is particularly preferred.

  These polymerization catalysts are usually supplied as a solution of water, 1,4-butanediol or the like. As a supply amount, it is preferable that the titanium compound is 10 ppm or more and 80 ppm or less, particularly 70 ppm or less in terms of each metal atom per theoretical yield of the PBT resin. Further, the Group 1 and / or Group 2 metal compound is preferably 1 ppm or more and 50 ppm or less, and particularly preferably 40 ppm or less.

<(B) Thermosetting unsaturated polyester resin>
The thermosetting unsaturated polyester resin (b) used in the present invention comprises an unsaturated polyester resin and a polymerizable unsaturated monomer component such as a vinyl monomer, and at least one of the polymerizable unsaturated monomer components. The part is crosslinked with the unsaturated polyester resin.

  The unsaturated polyester resin is usually an α, β-unsaturated dicarboxylic acid and, if necessary, dicarboxylic acids having no unsaturated aliphatic group at the α and β positions (hereinafter simply referred to as “saturated dicarboxylic acids”). And a derivative such as a dicarboxylic acid and / or an acid anhydride thereof and a polyhydric alcohol.

  The α, β-unsaturated dicarboxylic acid and / or its acid anhydride may be any of aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and aromatic dicarboxylic acids. Usually, aliphatic dicarboxylic acids are used, and specifically, for example, fumaric acid, itaconic acid (methylene succinic acid), itaconic anhydride, maleic acid, maleic anhydride, particularly fumaric acid, maleic anhydride, itaconic acid are preferred. In particular, fumaric acid is preferred.

  The saturated dicarboxylic acid and / or acid anhydride thereof may be any of aliphatic or alicyclic dicarboxylic acids and aromatic dicarboxylic acids. Specifically, as the aliphatic dicarboxylic acid, succinic acid, malonic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, hydrogenated dimer acid, and alicyclic dicarboxylic acid include cyclohexanedicarboxylic acid, aromatic dicarboxylic acid. Phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic anhydride, 4,4′-biphenyldicarboxylic acid and the like can be mentioned.

  And as unsaturated polyester resin in (b) thermosetting unsaturated polyester resin used for this invention, derivatives, such as dicarboxylic acids and / or its acid anhydride, containing (alpha), (beta) -unsaturated dicarboxylic acid and saturated dicarboxylic acid are used. Is preferably used. In this case, the saturated dicarboxylic acid is preferably an aromatic dicarboxylic acid, and particularly preferably terephthalic acid.

  The content of derivatives such as α, β-unsaturated dicarboxylic acids and acid anhydrides in dicarboxylic acids is more than 0 and 100 mol% or less, and in particular, 15 to 90 mol%, particularly 40 to 80 mol%. Preferably there is. Furthermore, in the unsaturated polyester resin, a monobasic acid such as benzoic acid, a tribasic acid such as trimellitic anhydride, or a polybasic acid such as tetrabasic acid such as pyromellitic anhydride may be used in combination with a dicarboxylic acid. .

  As polyhydric alcohols, diols are usually used. As the diol, any of aliphatic diols, alicyclic diols, and aromatic diols may be used. Examples of the aliphatic diol include aliphatic diols having 2 to 20 carbon atoms. Specific examples include ethylene glycol, 1,4-butanediol, diethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3- Examples include propanediol, polypropylene glycol, polytetramethylene glycol, dibutylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, and 1,8-octanediol.

  Specific examples of the alicyclic and aromatic diols include hydrogenated bisphenol A and bisphenol A propylene oxide adducts. These diols may be used alone or in combination of two or more in any proportion.

  The method for producing the unsaturated polyester resin is arbitrary, and any conventionally known method can be used. Specifically, for example, the method described in Chapter 2 of “Polyester resin handbook” (June 30, 1988, first edition, 1st printing, Nikkan Kogyo Shimbun) can be mentioned.

  The unsaturated polyester resin can be produced from a liquid state to a crystalline solid state. The number average molecular weight may be appropriately selected and determined. However, if the number average molecular weight is too large, the viscosity is remarkably increased and the handleability is lowered, so that the number average molecular weight is usually 500 to 10,000.

  The (b) thermosetting unsaturated polyester resin used in the present invention is a mixture of the unsaturated polyester resin as described above and a polymerizable unsaturated monomer component such as a vinyl monomer, and a curing agent as necessary. As the (polymerization initiator), an organic peroxide catalyst added and partially or completely heat-cured is used. Among these thermoplastic unsaturated polyester resins, a crystalline solid resin is preferable because of excellent handling properties.

  Specific examples of the polymerizable unsaturated monomer include styrene, α-methylstyrene, divinylbenzene, vinyltoluene, paramethylstyrene, t-butylstyrene, diallyl phthalate, methyl (meth) acrylate, and ethylene glycol diester. (Meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 2-hydroxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, trimethylolpropane Examples include tri (meth) acrylate. Of these polymerizable unsaturated monomers, styrene is preferred because it is relatively easily available and is excellent in copolymerizability with unsaturated polyester.

  Specific examples of the polymerization initiator include conventionally known radical polymerizations such as organic peroxides such as t-butylperoxybenzoate and t-butylperoxycarbonate; azo compounds such as azobisisobutyronitrile. An initiator etc. are mentioned.

  In the thermosetting unsaturated polyester resin (b) used in the present invention, the weight ratio between the unsaturated polyester resin and the polymerizable unsaturated monomer may be appropriately selected and determined. If the proportion of the body is too small, the viscosity of the (b) thermosetting unsaturated polyester resin may be increased, and the handleability may be reduced. In some cases, physical properties such as the cured product become brittle.

  Therefore, the weight ratio of the unsaturated polyester resin to the polymerizable unsaturated monomer is usually from 2: 8 to 8: 2, and preferably from 3: 7 to 7: 3. Further, during or after the reaction, a polymerization inhibitor may be added in order to prevent gelation and to adjust the storage stability and curability of the resulting thermosetting unsaturated polyester resin.

  Specific examples of the polymerization inhibitor include hydroquinone, methylhydroquinone, pt-butylcatechol, t-butylhydroquinone, toluhydroquinone, p-benzoquinone, naphthoquinone, hydroquinone monomethyl ether, phenothiazine, and copper naphthenate. Can be mentioned. These polymerization inhibitors may be used alone or in combination of two or more in any proportion.

<(C) Epoxy compound>
In the present invention, in addition to the above-mentioned (a) thermoplastic saturated polyester resin and (b) thermosetting unsaturated polyester resin, it is preferable to further use (c) an epoxy compound. (C) The epoxy compound has reactivity and affinity for (a) thermoplastic saturated polyester resin and (b) thermosetting unsaturated polyester resin, so the thermoplastic saturated polyester resin composition of the present invention. This is preferable because the mechanical strength and hydrolysis resistance are improved.

  As the (c) epoxy resin used in the present invention, any conventionally known one can be used, which may be monofunctional, bifunctional or polyfunctional and may be used in combination. Of these, bifunctional or higher epoxy compounds, that is, compounds having two or more epoxy groups in one molecule are preferable. Moreover, the epoxy equivalent may be appropriately selected and determined, but is usually 100 to 5000 g / eq, and particularly preferably 150 to 2000 g / eq.

  Specific examples of the (c) epoxy compound used in the present invention include, for example, a glycidyl ether type, a diglycidyl ether type, a polyfunctional glycidyl ether type, a glycidyl ester type, a diglycidyl ester type, a glycidyl amine type, and an alicyclic diepoxy compound. And glycidyl imide compounds.

  As glycidyl ether, methyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, phenyl glycidyl ether, butylphenyl glycidyl ether and allyl glycidyl ether are preferable.

  Diglycidyl ethers include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, brominated bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, biphenyl diglycidyl ether, naphthalene diglycidyl ether, neopentyl glycol diglycidyl ether Ethylene glycol diglycidyl ether, glycerin diglycidyl ether and propylene glycol diglycidyl ether are preferred.

  Examples of polyfunctional glycidyl ethers include phenol novolac type epoxy compounds, o-cresol novolac type epoxy compounds, bisphenol novolac type epoxy compounds, trishydroxymethane type (trifunctional) epoxy compounds, tetraphenolethane type (tetrafunctional) epoxy compounds, and the like. preferable.

  As the glycidyl ester, benzoic acid glycidyl ester and sorbic acid glycidyl ester are preferable. As the diglycidyl ester, adipic acid diglycidyl ester, terephthalic acid diglycidyl ester, orthophthalic acid diglycidyl ester and the like are preferable.

  As the glycidylamine, tetraglycidyldiaminodiphenylmethane and triglycidyl isocyanurate are preferable. As the alicyclic diepoxy compound, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexylcarboxylate is preferable. As the glycidyl imide compound, N-glycidyl phthalimide is preferable.

  As the (c) epoxy compound used in the present invention, a glycidyl ether type is preferable, among which (1) bisphenol A diglycidyl ether obtained from the reaction of bisphenol A and epichlorohydrin, and (2) phenol novolak and epichloro. Phenol novolac type epoxy compounds obtained by reaction with hydrin, and (3) o-cresol novolac type epoxy compounds obtained by reaction of o-cresol and epichlorohydrin are preferred.

  The content of the epoxy compound (c) in the present invention may be selected and determined as appropriate. However, if it is too small, the effect of improving the mechanical properties is insufficient, and conversely, if too much, the hydrolysis of the resin is accelerated. However, the strength may decrease.

  Therefore, the content of (c) epoxy compound is usually 0.1 to 100 parts by weight, preferably 0.3 to 50 parts by weight, based on 100 parts by weight of (a) thermoplastic polyester resin.

<Reinforcing filler>
The thermoplastic saturated polyester resin composition of the present invention may contain a reinforcing filler as long as the effects of the present invention are not impaired. The reinforcing filler is not particularly limited, and any conventionally known fibrous, plate-like, granular, and mixtures thereof can be used.

  Specific examples of the fibrous material include glass fibers, carbon fibers, silica alumina fibers, zirconia fibers, boron fibers, boron nitride fibers, silicon nitride fibers, potassium titanate fibers, metal fibers and other inorganic fibers, aromatic polyamides. Examples thereof include organic fibers such as fibers and fluororesin fibers.

  Examples of the plate-like material include glass flakes, mica, and metal foil. Examples of the particulate material include glass beads, wollastonite, talc, clay, zeolite, kaolin, potassium titanate, barium sulfate, calcium carbonate, titanium oxide, silicon oxide, aluminum oxide, and magnesium hydroxide.

  As the reinforcing filler, glass, silicon oxide, and calcium silicate, which have high hardness and are relatively easily available, are preferable. Specifically, glass fiber, glass flake, glass bead, glass powder, silica, quartz, wollastonite and the like can be mentioned, and these may be used alone or in combination of two or more at any ratio. Of these, glass having a high Mohs hardness and having excellent adhesion to a polyester resin by surface treatment is preferable.

  In the thermoplastic saturated polyester resin composition of the present invention, when the mechanical strength is improved, it is preferable to use a fibrous material among the reinforcing fillers as described above, and the thermoplastic saturated polyester resin composition. When it is desired to improve the surface appearance of the resin molded body obtained by molding a product, it is preferable to use a plate-like product or a granular reinforcing filler.

  In the fibrous reinforcing filler, the average fiber diameter may be appropriately selected and determined, but is usually 1 to 100 μm, considering the improvement of the mechanical strength of the obtained resin molded body, among which 2 to 50 μm, Furthermore, it is preferable that it is 3-30 micrometers, especially 5-20 micrometers.

  The average fiber length may be determined by appropriately selecting the desired resin molded body and the physical properties of the resin composition constituting it. If the average fiber length is too short, the reinforcing effect becomes insufficient. Conversely, if the average fiber length is too long, melt-kneading with the thermoplastic polyester resin and moldability of the resin composition (fiber reinforced thermoplastic saturated polyester resin composition) are possible. Since it may fall, it is 0.1-20 mm normally, and it is preferable that it is 1-10 mm especially.

  The reinforcing filler is preferably surface-treated in order to improve the affinity with the saturated or unsaturated polyester resin and the interfacial adhesion, and to reduce the opacity factor due to void formation at the interface. There is no restriction | limiting in particular as a surface treating agent, A conventionally well-known arbitrary thing can be used, Specifically, a silane coupling agent, an epoxy resin, etc. are mentioned as a specific thing specifically, for example.

  Examples of the silane coupling agent include amino silane, epoxy silane, allyl silane, and vinyl silane. Of these, aminosilanes are preferred. Preferred examples of the amino silane coupling agent include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, and γ- (2-aminoethyl) aminopropyltrimethoxysilane. The content of the silane coupling agent in the surface treatment agent may be appropriately selected and determined, but is usually 0.1 to 8% by weight, and preferably 0.5 to 5% by weight.

  The epoxy resin is preferably a polyfunctional epoxy resin such as a phenol novolac type epoxy resin and a cresol novolac type epoxy resin. The content of the epoxy resin in the surface treatment agent may be appropriately selected and determined, but is usually 1 to 20% by weight, and preferably 2 to 10% by weight.

  Among these, as the surface treatment agent, it is preferable to use an amino-based silane coupling agent and a novolac type epoxy resin in combination. By using these in combination, the inorganic functional group of the amino silane coupling agent is on the reinforcing filler surface, the organic functional group of aminosilane is the glycidyl group of the epoxy resin, and the glycidyl group of the epoxy resin is on the polyester resin. Since each of the reactivity is high, the interfacial adhesion between the reinforcing filler and the epoxy resin is improved, and the mechanical properties and hydrolysis resistance of the thermoplastic saturated polyester resin composition of the present invention are improved, which is preferable.

  The surface treatment agent used for the reinforcing filler is within the range not departing from the gist of the present invention, and other Group 1 metal compound and / or Group 2 metal compound components such as urethane resin, acrylic resin, antistatic agent, A lubricant, a water repellent and the like may be contained.

  Any conventionally known surface treatment method can be used. Specifically, for example, a method in which surface treatment is performed in advance with a surface treatment agent, such as the methods described in JP-A Nos. 2001-172055 and 53-106749, and (a) a thermoplastic saturated polyester resin And (b) a method of performing surface treatment by adding an untreated reinforcing filler and a surface treatment agent at the time of melt kneading with a thermosetting unsaturated polyester resin.

  The adhesion amount of the surface treatment agent to the reinforcing filler may be appropriately selected and determined. However, if the amount is too small, the effect of improving the mechanical strength may be insufficient. We cannot expect improvement of effect with increase. Therefore, it is usually 0.01 to 5% by weight, and preferably 0.05 to 2% by weight.

<Other additives>
The resin composition of the present invention may contain other additives without departing from the spirit of the present invention. Specific examples include antioxidants, flame retardants, heat stabilizers, lubricants, mold release agents, catalyst deactivators, crystal nucleating agents, crystallization accelerators, and coloring agents.

  These additives can be added during or after the polymerization of the (a) thermoplastic saturated polyester resin. Furthermore, in order to impart desired performance to the (a) thermoplastic saturated polyester resin, an ultraviolet absorber, a weather resistance stabilizer, an antistatic agent, a foaming agent, a plasticizer, an impact resistance improving agent, and the like may be contained.

  The blending method after the polymerization of the above various additives and resins is not particularly limited, but a method of using a uniaxial or biaxial extruder having equipment capable of devolatilization from the vent port as a kneader is preferable. Each component including an additional component may be supplied to the kneader in a lump or sequentially. Moreover, you may mix the 2 or more types of component chosen from each component including an additional component previously. When blending the reinforcing filler, it is desirable to supply the reinforcing filler from the middle of the extruder in order to prevent the reinforcing filler from being crushed during kneading.

  Antioxidants have the effect of improving heat aging resistance and improving retention such as color tone, tensile strength, and elongation. Examples of the antioxidant include phenolic antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants. These may be used alone or in combination of two or more at any ratio. Content of antioxidant is 0.001-1.5 weight part with respect to 100 weight part of (a) thermoplastic saturated polyester resin, and it is preferable that it is 0.03-1 weight part especially.

  Phenol-based antioxidants include, among others, hindered phenols (one or two carbon atoms adjacent to a carbon atom of an aromatic ring to which a phenolic hydroxyl group is bonded are substituted with a substituent having 4 or more carbon atoms). In addition, the substituent having 4 or more carbon atoms may be bonded to a carbon atom of the aromatic ring by a carbon-carbon bond, or may be bonded via an atom other than carbon.) The antioxidant is preferred. This is because hindered phenolic antioxidants are likely to be stable radicals and are preferred as radical trapping agents. The molecular weight of the hindered phenol antioxidant is usually 200 or more, preferably 500 or more, and the upper limit is usually 3000.

  Specific examples of the phenolic antioxidant include p-cyclohexylphenol, 3-t-butyl-4-methoxyphenol, 4,4′-isopropylidenediphenol, and 1,1-bis (4-hydroxyphenyl). Non-hindered phenolic antioxidants such as cyclohexane, 2-t-butyl-4-methoxyphenol, 2,6-di-t-butyl-p-cresol, 2,4,6-tri-t-butylphenol, 4 -Hydroxymethyl-2,6-di-tert-butylphenol, styrenated phenol, 2,5-di-tert-butylhydroquinone, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate , Triethylene glycol bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propione 1,6-hexanediol bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], pentaerythritol tetrakis [3- (3,5-di-t-butyl-4 -Hydroxyphenyl) propionate], 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (6-t-butyl-4-ethylphenol), 2,2'-methylenebis [4-Methyl-6- (1,3,5-trimethylhexyl) phenol], 4,4′-methylenebis (2,6-di-t-butylphenol), 4,4′-butylidenebis (3-methyl-6) -T-butylphenol), 2,6-bis (2-hydroxy-3-t-butyl-5-methylbenzyl) -4-methylphenol, 1,1,3-tris [ -Methyl-4-hydroxy-5-t-butylphenyl] butane, 1,3,5-trimethyl-2,4,6-tris [3,5-di-t-butyl-4-hydroxybenzyl] benzene, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, tris [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 4,4 ′ -Thiobis (3-methyl-6-tert-butylphenol), 2,2'-thiobis (4-methyl-6-tert-butylphenol), 4,4'-thiobis (2-methyl-6-tert-butylphenol), Examples include hindered phenol antioxidants such as thiobis (β-naphthol).

  The content of the phenolic antioxidant may be appropriately selected and determined. However, if the amount of the antioxidant is too small, the effect of addition becomes insufficient. On the other hand, if the amount is too large, the oxidation heat stability may decrease. In some cases, resin decomposition may occur during melt-kneading. Therefore, usually, it is preferably 0.001 to 1.5 parts by weight, more preferably 0.03 to 1 part by weight, based on 100 parts by weight of (a) the thermoplastic polyester resin.

  Specific examples of the sulfur-based antioxidant include didodecylthiodipropionate, ditetradecylthiodipropionate, dioctadecylthiodipropionate, pentaerythritol tetrakis (3-dodecylthiopropionate), thiobis ( N-phenyl-β-naphthylamine), 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, nickel dibutyldithiocarbamate, nickel isopropylxanthate, trilauryltrithiophosphite, etc. Can be mentioned.

  Peroxy radicals (RCOO.) Generated by the oxidation of polyester extract hydrogen atoms and become hydroperoxides to generate new radicals. Especially, what has a thioether structure is preferable in order to decompose | disassemble this hydroperoxide efficiently. Among them, didodecylthiodipropionate, ditetradecylthiodipropionate, dioctadecylthiodipropionate, and pentaerythritol tetrakis (3-dodecylthiopropionate) are preferable. The molecular weight of the sulfur-based antioxidant is usually 200 or more, preferably 500 or more, and the upper limit is usually 3000.

Among the phosphorus-based antioxidants, P (OR) ₃ (R represents an alkyl group, an alkylene group, an aryl group, or an arylene group, which may be the same or different, and any two Rs are bonded to each other. And may have a ring structure.) Those having a structure are preferred.

  Specific examples of phosphorus antioxidants include triphenyl phosphite, diphenyl decyl phosphite, phenyl diisodecyl phosphite, tri (nonylphenyl) phosphite, and bis (2,4-di-t-butylphenyl). Examples include pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, and the like.

  The content of the sulfur-based antioxidant and the phosphorus-based antioxidant in the thermoplastic saturated polyester resin composition of the present invention may be appropriately selected and determined. However, if it is too small, the effect of addition becomes insufficient, and conversely, Even if it is too much, the oxidation heat stability may be lowered, or the resin may be decomposed during melt-kneading. Therefore, it is usually 0.001 to 1.5 parts by weight with respect to 100 parts by weight of the thermoplastic polyester resin (a), preferably 0.03 to 1 part by weight.

  There is no restriction | limiting in particular as a flame retardant, A conventionally well-known arbitrary thing can be used. Specific examples include organic halogen compounds, antimony compounds, phosphorus compounds, other organic flame retardants, and inorganic flame retardants.

  Examples of the organic halogen compound include brominated polycarbonate, brominated epoxy resin, brominated phenoxy resin, brominated polyphenylene ether resin, brominated polystyrene resin, brominated bisphenol A, pentabromobenzyl polyacrylate and the like. Examples of the antimony compound include antimony trioxide, antimony pentoxide, and sodium antimonate. Examples of the phosphorus compound include phosphate ester, polyphosphoric acid, ammonium polyphosphate, and red phosphorus.

  In addition, specific examples of the organic flame retardant include nitrogen compounds such as melamine and cyanuric acid, and examples of the inorganic flame retardant include aluminum hydroxide, magnesium hydroxide, silicon compound, and boron compound.

  The content of these flame retardants may be appropriately selected and determined. However, if the amount is too small, the effect of addition becomes insufficient. is there. Therefore, it is usually 0.1 to 50 parts by weight with respect to 100 parts by weight of (a) thermoplastic polyester resin.

  The thermoplastic polyester resin composition of the present invention may further contain another resin as long as the effects of the present invention are not impaired. Specifically, for example, polyethylene resin, polypropylene resin, polystyrene resin, polyacrylonitrile resin, polymethacrylate resin, acrylonitrile / butadiene / styrene resin (ABS resin), polycarbonate resin, polyamide resin, polyphenylene sulfide resin, polyacetal resin, polyphenylene Thermoplastic resins such as oxide resins; thermosetting resins such as phenol resins, melamine resins, and silicone resins. These thermoplastic resins and thermosetting resins may be used in combination of two or more at any ratio. The content of these resins is preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of (a) the thermoplastic polyester resin.

<Method for producing thermoplastic saturated polyester resin composition>
The thermoplastic saturated polyester resin composition used in the present invention can be obtained by kneading the aforementioned raw materials by any conventionally known resin kneading technique.

  Among them, in the method for producing the thermoplastic saturated polyester resin composition of the present invention, as the (b) thermosetting unsaturated polyester resin used in the present invention, a mixture of an uncured crystalline resin component and a polymerizable unsaturated monomer is used. It is preferable to knead this with (a) the thermoplastic saturated polyester resin composition by any conventionally known resin kneading method.

  Here, as the uncured crystalline resin component of the thermosetting unsaturated polyester resin, a dicarboxylic acid and / or a derivative thereof such as an acid anhydride thereof containing α, β-unsaturated dicarboxylic acid and saturated dicarboxylic acid is used. Can be obtained. In this case, the saturated dicarboxylic acid is preferably an aromatic dicarboxylic acid, and particularly preferably terephthalic acid. Moreover, by thermosetting this mixture, an uncrosslinked crosslinking point is crosslinked by the polymerizable unsaturated monomer component to obtain a completely cured thermosetting resin composition.

  In the present invention, (a) a thermoplastic saturated polyester resin composition and (b) a partially cured product of a thermosetting unsaturated polyester resin (hereinafter sometimes simply referred to as “partially cured product”) are melt-kneaded. Thus, (a) a resin composition in which a thermoplastic saturated polyester resin composition is a continuous layer and a dispersed layer can be obtained, and this resin composition is melted once and / or The thermoplastic saturated polyester resin composition of the present invention in which the fine particles of (b) thermosetting unsaturated polyester resin are dispersed can be obtained by molding by adding other additives and the like.

  In this way, (a) by dispersing fine particles of (b) thermosetting unsaturated polyester resin in a specific amount or more in the thermoplastic saturated polyester resin, the fine particles can be deformed appropriately when melted. Therefore, unlike the rigid filler, it is considered that the shear stress is absorbed in the low shear rate field.

  In addition, under the high shear rate condition in the molding region, it is considered that the nonlinearity of the stress-shear rate becomes strong and the melt viscosity decreases, as in a general dispersion system. Further, the thermosetting unsaturated polyester resin fine particles have good affinity with the thermoplastic saturated polyester and have a cross-linked structure, so it is considered that the generated cracks are absorbed. From these effects, it is considered that the material exhibits excellent physical properties in both fluidity and mechanical properties, which has been considered difficult in the past.

  In the thermoplastic saturated polyester resin composition of the present invention, it is important that the thermosetting resin (b) is dispersed in the thermoplastic saturated polyester resin (a). The dispersed thermosetting resin (b) preferably has a very small particle size, specifically 500 μm or less.

The blending method of the various additives and resins is not particularly limited, but a method of using a uniaxial or biaxial extruder having equipment capable of devolatilization from the vent port as a kneader is preferable. The above components (a) and (b) and, if necessary, (c) and reinforcing fillers and other additives may be collectively supplied to a kneader, or the resin component (a) Other blending components may be sequentially supplied.
When blending the reinforcing filler, it is desirable to supply it from the middle of the extruder in order to suppress crushing of the reinforcing filler during kneading. Further, two or more kinds of components selected from each component may be mixed and kneaded in advance.

  The molding method of the resin composition of the present invention is not particularly limited, and molding methods generally used for thermoplastic resins, that is, molding methods such as injection molding, hollow molding, extrusion molding, press molding, and the like are applied. Can do. In this case, a particularly preferable molding method is injection molding because of good fluidity. In the injection molding, the resin temperature is preferably controlled to 240 to 280 ° C.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to a following example at all unless the summary is exceeded.

[Various measurement methods]
(1) Fluidity (melt shear viscosity): Using a capillary type rheometer (manufactured by Toyo Seiki Seisakusho: Capillograph 1C), the melt shear viscosity at a temperature of 270 ° C. and a shear rate of 6080 sec ⁻¹ was measured. The smaller the value, the higher the fluidity.

(2) Tensile strength, flexural modulus: Examples 1 to 5 in Table 1 using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd .: model SG-75MIII) at a cylinder temperature of 250 ° C. and a mold temperature of 80 ° C. And the ISO test piece which consists of each resin composition of the composition shown to Comparative Examples 1-3 was produced. The ISO test piece was subjected to a tensile test according to ISO 527 and a bending test according to ISO 178.

  (3) Surface hardness (pencil hardness): The pencil hardness was evaluated according to JIS K5400 using a pencil hardness tester (manufactured by Toyo Seiki Seisakusho).

(4) Hydrolysis resistance: The above ISO test piece is in saturated steam at a temperature of 121 ° C. under a pressure of 203 kPa, and when the ISO test piece does not include a reinforcing filler, the ISO test piece includes a reinforcing filler. In this case, the wet heat treatment was performed for 100 hours. About the ISO test piece before and behind a process, the tensile strength was measured based on ISO527. Moreover, the tensile strength retention was calculated | required according to following Formula.
Tensile strength retention (%) = (Tensile strength after treatment / Tensile strength before treatment) × 100

[Raw material of resin composition]
(A) Thermoplastic saturated polyester resin (a1) Polybutylene terephthalate resin: NOVADURAN (registered trademark) 5008 manufactured by Mitsubishi Engineering Plastics, intrinsic viscosity [η] = 0.85 dl / g

(A2) Polybutylene terephthalate resin: NOVADURAN (registered trademark) 5020 manufactured by Mitsubishi Engineering Plastics, intrinsic viscosity [η] = 1.20 dl / g

(B) Thermosetting unsaturated polyester resin Unsaturated polyester resin: Nippon Iupika Co., Ltd. Viroglass VG-7100 (terephthalic acid (saturated dicarboxylic acid) / fumaric acid (unsaturated dicarboxylic acid) / 1,4 butanediol (each mole) A crystalline thermosetting unsaturated polyester resin comprising a condensate of 30% / 20% / 50%) and an unreacted crosslinking agent.

(C) Epoxy compound: o-cresol novolac type epoxy compound, YDCN-704 manufactured by Toto Kasei Co., Ltd., epoxy equivalent of 195 to 220 g / eq

  Reinforcing filler: Glass fiber (chopped strand with a surface treatment agent not containing novolac type epoxy resin: ECS03T-187 manufactured by Nippon Electric Glass Co., Ltd.), average fiber diameter 13 μm, average fiber length 3 mm, Mohs hardness 6.5

  Antioxidant: Pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], Irganox 1010 manufactured by Ciba Specialty Chemicals

[Examples 1-4, Comparative Examples 1-4]
(A1), (a2) Polybutylene terephthalate resin, (b) thermosetting unsaturated polyester resin, (c) epoxy resin, reinforcing filler (glass fiber) and antioxidant are in the ratios shown in Table 1. The mixture was mixed with a tumbler for 20 minutes. The ratio (% by weight) of (b) is the ratio in the polyester resin combining (a1), (a2) and (b), and (c), the ratio of reinforcing filler and antioxidant (parts by weight) Was the ratio when the polyester resin combined with (a1), (a2) and (b) was taken as 100.

  The obtained raw material mixture was supplied to a hopper and melt-kneaded using a twin-screw extruder (manufactured by Nippon Steel Works: TEX30C, barrel 9 block configuration) with a cylinder temperature set to 250 ° C. When the glass fiber was blended, it was supplied by a side feed system from the fifth block counted from the hopper and melt kneaded. The evaluation mentioned above was performed using the obtained resin composition. The evaluation results are shown in Table 1.

  As is apparent from Table 1, it can be seen that the resin composition of the present invention not only exhibits a sufficiently low melt viscosity, but also the surface of the resulting resin molded body is hard and further exhibits excellent toughness.

Claims (6)

A thermoplastic polyester resin composition comprising (a) a thermoplastic saturated polyester resin and (b) a thermosetting unsaturated polyester resin, wherein (b) the content of the thermosetting unsaturated polyester resin is 10% by weight. A thermoplastic polyester resin composition characterized by exceeding. Furthermore, the thermoplastic polyester resin composition of Claim 1 formed by mix | blending 0.1-100 weight part of (c) epoxy resins with respect to 100 weight part of thermoplastic polyester resins. The thermoplastic polyester resin composition according to claim 1 or 2, wherein the (a) thermoplastic saturated polyester resin is an aromatic polyester resin. The thermoplastic polyester resin composition according to claim 3, wherein the aromatic polyester resin is a polybutylene terephthalate resin. 5. The method according to claim 1, wherein (a) a thermoplastic saturated polyester resin and (b) a thermosetting unsaturated polyester resin containing an uncrosslinked polymerizable unsaturated monomer component are melt-kneaded. A method for producing the thermoplastic polyester resin composition according to claim 1. The resin molding formed by shape | molding the thermoplastic polyester resin composition in any one of Claims 1-4.