WO2004106434A1 - Resin composition - Google Patents

Abstract

A resin composition obtained by incorporating an epoxy-modified polyolefin obtained by the reaction of an epoxy compound with a polyolefin into a resin composition comprising a modified polyphenylene sulfide resin comprising polyphenylene sulfide and an epoxidized polyolefin and, incorporated therein in a given amount, a modified polyester resin comprising a polyester, an epoxidized polyolefin, and a polyolefin containing no epoxy group. The resin composition gives a molded article which at least partly has a phase structure in which the resins have separated into different phases so that the modified polyphenylene sulfide resin constitutes a continuous phase and the modified polyester resin constitutes a dispersed phase. The resin composition is excellent in impermeability, impact resistance especially at low temperatures, and moldability.

Description

 Itoda »

 Resin composition

 Technical field

 The present invention relates to a resin composition having excellent gas and / or liquid permeation resistance, and in particular, to a modified polyphenylene sulfide resin, a modified polyester resin, and an epoxy resin obtained by reacting an epoxy compound with a polyolefin. The present invention relates to a resin composition having specific permeation resistance, impact resistance, and moldability obtained by forming a compatibilizer into a specific phase structure.

 Background technology

 Polyester resins are used in a wide range of fields, including mechanical and mechanical components, electrical and electronic components, and automotive components, due to their excellent mechanical and chemical properties.

 However, although the polyester resin has a better gas barrier property against oxygen and carbon dioxide than polyethylene and polypropylene, it is still insufficient. For example, there is a demand for a further improvement in gas barrier properties in applications such as packaging of easily oxidizable contents such as foods containing fats and oils and applications in which filling gas leakage must be prevented such as carbonated beverages. As a method of improving the gas barrier properties of polyester resins, resins having better gas barrier properties than polyester resins, such as ethylene-vinyl acetate copolymer (EVOH), polyamide (PA), and polyvinylidene chloride (PVDC), are used. Among these, c has been considered to be used as a mixture. C) Polyester resin is mixed with polymethaxylylene adipamide (Nymouth MXD6), which is obtained from adipic acid and metaxylylenediamine, which has excellent gas barrier properties. Attempts have been made to improve gas barrier properties.

 However, the gas barrier properties of EVOH and PA (nylon MXD 6, etc.) are susceptible to the effects of humidity, and have the disadvantage that the gas barrier properties are greatly reduced in high-temperature and high-humidity conditions. The barrier properties at the time of moisture absorption were not always satisfactory even if mixed. In addition, polyester resins have a problem of poor hydrolysis resistance, and their use is often limited due to durability problems such as a decrease in mechanical strength under high temperature and high humidity.

Polyphenylene sulfide resin, on the other hand, is used in chemicals such as automotive oils and water. It is known that they exhibit extremely high barrier properties, and blow molded hollow containers and tubular bodies using the same have also been proposed (US Pat. No. 4,866,669, European Patent No. No. 2,022,199, U.S. Pat. No. 5,089,209). However, since polyphenylene sulfide resin has insufficient eyebrow adhesion to other resins, co-extrusion with other resin materials, including polyolefin-based materials such as polyethylene and polypropylene, etc. It was difficult.

 A means for improving the impact resistance by adding an impact modifier to a polyester resin and a polyphenylene sulfide resin and melting and kneading the resin is disclosed in Japanese Patent Publication No. Hei 6-2330000, Patent No. 3067. Although disclosed in Japanese Patent Application Laid-Open No. 2-14, these conventional techniques are still insufficient particularly in balance between low-temperature impact resistance and permeation resistance. In Japanese Patent Application Laid-Open No. 2002-692773, by controlling the phase structure of a polyester resin and a polyphenylene sulfide resin, high barrier properties can be exhibited even under high temperature and high humidity. However, in this case as well, there are cases where the balance between impact resistance at low temperatures is not sufficient, and there are cases in which materials that highly and stably satisfy various properties such as barrier properties and impact resistance are disclosed. Development is required.

 Disclosure of the invention

 An object of the present invention is to achieve a high balance between the mechanical strength and toughness of a polyester resin and the low water absorption and permeation resistance of a polyphenylene sulfide resin. In particular, it is an object of the present invention to provide a resin composition stably exhibiting impact resistance and moldability at low temperatures.

 Accordingly, the present inventors have studied to achieve the above object, and as a result, a modified polyphenylene sulfide resin, a modified polyester resin, and a resin composition obtained from an epoxy-modified polyolefin obtained by reacting an epoxy compound with polyolefin. The resin phase separation structure of the molded article obtained by molding the resin composition is controlled so as to be a dispersed structure in which the modified polyphenylene sulfide resin forms a continuous or partially continuous phase. The inventors have found that the problem is solved, and arrived at the present invention.

That is, the resin composition according to the present invention is a modified polyphenylene sulfide resin containing polyphenylene sulfide (al) and epoxy group-containing polyolefin (a 2). (a) A modified polyester resin (b) containing 100 parts by weight of a polyester (b 1), an epoxy group-containing polyolefin (b 2), and a polyolefin (b 3) other than an epoxy group-containing polyolefin. ) 100 to 100 parts by weight of a resin composition containing 40 to 250 parts by weight, 0.5 to 20 parts by weight of an epoxy-modified polyolefin (c) obtained by reacting an epoxy compound with a polyolefin. Part of the resin composition, wherein a molded article of the resin composition has a resin phase separation structure observed by an electron microscope, a modified polyphenylene sulfide resin (a) having a continuous phase, and a modified polyester. The resin (b) is characterized in that the resin (b) forms at least a part thereof as a dispersed structure.

 In this resin composition, the modified polyphenylene sulfide resin (a) has a continuous phase and a modified phase in a resin phase separation structure observed by an electron microscope in a molded product obtained by processing the resin composition. The dispersed phase of the modified polyester resin (b) is formed to have a phase structure in which the polyester resin (b) is a dispersed phase, and the dispersed phase of the modified polyester resin (b) has an average particle size of 5 m or less. The epoxy group-containing polyolefin (b 2) and the polyolefin (b 3) other than the epoxy group-containing polyolefin preferably have a dispersed structure in which the average dispersed particle size is 1 zm or less. Further, the epoxy group-containing polyolefins (a2) and (b2) are preferably a copolymer containing a monoolefin and an epoxy group-containing monomer.

Further, the epoxy-modified polyolefin (c) is preferably an epoxy-modified polyolefin obtained by reacting an epoxy compound with a polyolefin having a density of 0.940 cm ³ or less.

 Examples of the epoxy-modified polyolefin (c) include, for example, a modified ethylene monoolefin copolymer obtained by grafting at least one selected from ethylenically unsaturated carboxylic acids and derivatives thereof on an ethylene norolefin copolymer. Epoxy-modified polyolefin obtained by reaction with a compound can be used.

In addition, as the epoxy-modified polyolefin (c), at least one selected from ethylenically unsaturated carboxylic acids and derivatives thereof is added to an ethylene-free olefin copolymer together with an epoxy compound in the presence of a radical generator. Obtained by heating Epoxy-modified polyolefins can also be used.

 As the modified polyphenylene sulfide resin (a), for example, 1 to 50 parts by weight of an epoxy group-containing polyolefin (a 2) is added to 100 parts by weight of a polyphenylene sulfide (a 1). What it contains can be used.

 Further, as the modified polyphenylene sulfide resin (a), 100 parts by weight of a composition composed of polyphenylene sulfide (a1) and epoxy group-containing polyolefin (a2), Those containing 1 to 50 parts by weight of a polyolefin (a 3) other than the polyolefin can be used.

 The modified polyphenylene sulfide resin (a) preferably has an Izod impact strength of at least 300 JZm.

 Further, as the modified polyester resin (b), for example, 100 to 100 parts by weight of the polyester (b1), 100 to 80 parts by weight of the epoxy group-containing polyolefin (b2) and other than the epoxy group-containing polyolefin Polyolefin (b3) containing 10 to 80 parts by weight can be used.

 The modified polyester resin (b) preferably has an Izod impact strength of 500 J / m or more.

 The resin composition according to the present invention has a high balance between the mechanical strength and toughness of the polyester resin and the low water absorption and permeation resistance of the polyphenylene sulfide resin. In particular, the resin composition can stably exhibit impact resistance and moldability at low temperatures. The molded article obtained by molding this resin composition has excellent barrier properties, particularly excellent impact resistance at low temperatures, and also has excellent adhesive properties under moisture absorption.

 Brief explanation of drawings

 Figure 1 shows a dispersion in which the modified PPS resin component forms a continuous phase, the polyester of the modified polyester resin becomes the dispersed phase, and the polyolefin other than the epoxy group-containing polyolefin and the epoxy group-containing polyolefin is further dispersed in the polyester. It is a model diagram of the structure (one island, one lake structure).

 [Explanation of symbols]

1: Modified PPS resin 2: Polyester

 3: Polyolefin other than epoxy group-containing polyolefin and epoxy group-containing polyolefin

 Best mode for carrying out the invention

 Hereinafter, the present invention will be described in detail with preferred embodiments. In the following description, “weight” means “mass”.

 The modified polyphenylene sulfide resin (a) (hereinafter sometimes abbreviated as a modified PPS resin) used in the resin composition according to the present invention is a polyphenylene sulfide resin (a1) (hereinafter abbreviated as PPS). This is a thermoplastic resin obtained by melt-kneading an epoxy group-containing polyolefin (a2) and, if necessary, a polyolefin (a3) other than the epoxy group-containing polyolefin.

 Preferred PPS (a1) is a polymer having a repeating unit represented by the following structural formula 1.

 (Structural formula 1)

As the polymer having the repeating unit represented by the above structural formula 1, from the viewpoint of heat resistance, a polymer containing 70 mol% or more, more preferably 90 mol% or more of the repeating unit represented by the above structural formula is preferable. Further, in the PPS, less than 30 mol% of the repeating unit may be constituted by a repeating unit represented by the following structural formula 2, or the like. Of these, p-phenylene sulfide / m-phenylene sulfide copolymer (m-phenylene sulfide unit 20% or less) is preferably used because it has both moldability and barrier properties. Can be (Structural formula 2)

The melt viscosity of the PPS (a 1) used in the present invention is not particularly limited as long as melt kneading is possible, but it is usually 5 to 200 Pas (32 ° C., shear rate 1 The ones with a duration of 100 sec are used, and the range of 10 to 500 Pas (same as above) is more preferable.

Such PPS is usually prepared by a known method, that is, a method of obtaining a polymer having a relatively small molecular weight as described in JP-B-45-33668, or a method of obtaining a polymer having a relatively small molecular weight. It can be produced by a method for obtaining a polymer having a comparatively large molecular weight, as described in Japanese Patent Application Laid-Open No. 0-86 and Japanese Patent Application Laid-Open No. 61-73332. In the present invention, the PPS obtained as described above is crosslinked / polymerized by heating in air, heat-treated in an atmosphere of an inert gas such as nitrogen or under reduced pressure, and washed with an organic solvent, hot water, an acid aqueous solution, or the like. Of course, it is also possible to use after being subjected to various treatments such as activation with a functional group-containing compound such as an acid anhydride, an amine, an isocyanate, or a functional group-containing disulfide compound. Cross-linking by heating PP s The specific method for increasing the molecular weight is as follows: in an atmosphere of an oxidizing gas such as air or oxygen, or in a mixed gas atmosphere of the oxidizing gas and an inert gas such as nitrogen or argon. An example is a method in which heating is performed at a predetermined temperature in a heating vessel until a desired melt viscosity is obtained. The heat treatment temperature is generally selected from 170 to 280 ° C, and preferably from 200 to 270 ° C. The heat treatment time is generally selected from 0.5 to 100 hours, and preferably from 2 to 50 hours. By controlling both of them, the target viscosity level can be obtained. The heating device may be an ordinary hot air dryer or a rotary or a heating device with stirring blades. For efficient and more uniform treatment, use a heating device with a rotary or stirring blade. Is more preferred.

 As a specific method for heat-treating PPS in an inert gas atmosphere such as nitrogen or under reduced pressure, the heat treatment temperature is 150 to 280 ° C in an inert gas atmosphere such as nitrogen or under reduced pressure. Preferably, the heat treatment is performed at 200 to 270 ° C., and the heating time is 0.5 to 100 hours, preferably 2 to 50 hours. The heating device may be an ordinary hot-air dryer or a rotary heating device or a heating device with a stirring blade, but for efficient and more uniform treatment, a heating device with a rotary or stirring blade is used. It is more preferable to use

 The PPS (a 1) used in the present invention is preferably deionized PPS. Specific examples of such deionization treatment include acid aqueous solution washing treatment, hot water washing treatment, and organic solvent washing treatment, and these treatments may be used in combination of two or more methods.

The following method can be exemplified as a specific method for washing PPS with an organic solvent. That is, the organic solvent used for washing is not particularly limited as long as it does not have an action of decomposing PPS. For example, a nitrogen-containing polar solvent such as N-methylpyrrolidone, dimethylformamide, dimethylacetamide, and dimethyl Sulfoxides such as sulfoxide and dimethyl sulfone; sulfone solvents; ketone solvents such as acetone, methylethyl ketone, getyl ketone, and acetophenone; ether compounds such as dimethyl ether, dipropyl ether, and tetrahydrofuran Solvent, liquid form, methylene chloride, trichloroethylene, ethylene dichloride, dichlor Halogen solvents such as ethane, tetrachloroethane, and chlorobenzene, alcohols such as methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol, and polyethylene glycol, phenol solvents, benzene, Examples include aromatic hydrocarbon solvents such as toluene and xylene. Of these organic solvents, use of N-methyl virolidone, acetone, dimethylformamide, and chloroform is preferred. These organic solvents are used singly or as a mixture of two or more. As a method for washing with an organic solvent, there is a method such as immersing PPS in an organic solvent, and it is also possible to appropriately stir or heat as necessary. There is no particular limitation on the washing temperature when washing PPS with an organic solvent, and any temperature from room temperature to about 300 ° C can be selected. The higher the washing temperature, the higher the washing efficiency tends to be. However, in general, a normal temperature to 15 (TC washing temperature is sufficient to obtain the effect. It is preferable to wash several times with water or warm water to remove the water.

 The following method can be exemplified as a specific method for washing the PPS with hot water. That is, the water used is preferably distilled water or deionized water in order to exhibit a favorable chemical modification effect of PPS by hot water washing. The operation of the hot water treatment is usually performed by charging a predetermined amount of water into a predetermined amount of water, and heating and stirring the mixture at normal pressure or in a pressure vessel. The proportion of PPS to water is preferably as high as possible, but usually a bath ratio of less than 200 g of PPS per liter of water is selected.

The following method can be exemplified as a specific method for washing PPS with an aqueous acid solution. That is, there is a method of immersing PPS in an acid or an aqueous solution of an acid, or the like, and if necessary, stirring or heating can be performed. The acid used is not particularly limited as long as it does not have the action of decomposing PPS.Halo-substituted fats such as aliphatic saturated monocarboxylic acids such as formic acid, acetic acid, propionic acid and butyric acid, and chloroacetic acid and dichloroacetic acid. Aliphatic unsaturated monocarboxylic acids such as aromatic saturated carboxylic acid, acrylic acid and crotonic acid, aromatic carboxylic acids such as benzoic acid and salicylic acid, dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, phthalic acid and fumaric acid And inorganic acidic compounds such as sulfuric acid, phosphoric acid, phosphoric acid, hydrochloric acid, carbonic acid, and silicic acid. Acetic acid and hydrochloric acid More preferably used. The acid-treated PPS is preferably washed several times with water or hot water in order to remove residual acids or salts. Further, the water used for washing is preferably distilled water or deionized water in the sense that the effect of the preferred chemical modification of PPS by acid treatment is not impaired.

 The epoxy-containing polyolefin (a 2) used as a component of the modified PPS resin (a) used in the present invention is a polyolefin having an epoxy group in the molecule, and is preferably a one-year-old olefin and an epoxy group. It is a copolymer containing contained monomers. More preferably, a copolymerized polyolefin comprising -olefin and glycidyl ester of yS-unsaturated acid can be used. The monoolefin is specifically ethylene, propylene, 1-butene, etc., and preferably ethylene. The glycidyl ester of <<, 3-unsaturated acid is a compound represented by the following structural formula 3 (wherein R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), and specifically, acrylic acid Glycidyl, glycidyl methacrylate, glycidyl ethacrylate, and the like, and particularly, glycidyl methacrylate is preferably used. The copolymerization amount of glycidyl ester of S-unsaturated acid is 1 to 50% by weight, preferably 3 to 50% by weight. A range of 40% by weight is appropriate.

 (Structural formula 3)

Ch = C-C-1 0-CH ₂ -CH-CH ₂

 -I II \ /

 R 0 0

The content of the epoxy group-containing polyolefin (a 2) is preferably 1 to 50 parts by weight, more preferably 1 to 40 parts by weight, based on 100 parts by weight of P P S (a 1). When the content of the epoxy group-containing polyolefin exceeds 50 parts by weight, it is not preferable because the barrier property and the fluidity are reduced. On the other hand, if the content of the epoxy group-containing polyolefin is less than 1 part by weight, it is not preferable because it becomes difficult to develop the high impact property which is a feature of the present invention.

In the modified PPS resin (a) used in the present invention, a polyolefin (a 3) other than the epoxy group-containing polyolefin which can be used as an additional component may be used. preferable. Specific examples thereof include homopolymers such as polyethylene, polypropylene, polystyrene, polyacrylate, polymethacrylate, poly 1-butene, poly 1-pentene, and polymethylpentene, ethylene-one-year-old olefin copolymer, A vinyl alcohol ester homopolymer, a polymer obtained by hydrolyzing at least a part of a vinyl alcohol ester homopolymer, [at least a part of a copolymer of ((ethylene and or propylene) and a vinyl alcohol ester) Polymer obtained by hydrolysis], [Copolymer of (ethylene and / or propylene) and (unsaturated carboxylic acid and / or unsaturated carboxylic acid ester)], [(ethylene and / or propylene) and (un Saturated carboxylic acids and unsaturated carboxylic acids A) a copolymer in which at least a portion of the carboxyl group of the copolymer is metallized, a block copolymer of a conjugated gen and a vinyl aromatic hydrocarbon, and a hydride of the block copolymer. Is used.

 Among them, polyethylene, polypropylene, ethylene-olefin copolymers, [copolymers of (ethylene and propylene or propylene) with (unsaturated carboxylic acid and phenol or unsaturated carboxylic acid ester)], [(ethylene And propylene) and (unsaturated carboxylic acid and / or unsaturated carboxylic acid ester) are preferred.

Further, the ethylene one-year-old olefin copolymer referred to herein is a copolymer of ethylene and at least one or more —3-olefins having 3 to 20 carbon atoms. Specific examples of olefins include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, and 1- Tridecene, 1—Tetradecene, 1—Pentadecene, 1—Hexadecene, 1—Heptadecene, 1-year-old Kutadecene, 1—Nonadecene, 1—Eicosene, 3-Methyl-1—Butene, 3—Methyl-1-—Pentene, 3— 1-pentene, 4-methyl-1- 1-pentene, 4-methyl-1-hexene, 4, 4-dimethyl-1-hexene, 4, 4-dimethyl-1-pentene, 4-ethyl-1— Ki Down, 3 - Echiru 1 - hexene, 9-methyl-1 Desen, 1 1 - methyl one 1 - dodecene, 1 2 Echiru 1 - tetradecene Contact And combinations thereof. Among these α-year-old fins, carbon number

Copolymers using 3 to 12 monoolefins are preferred from the viewpoint of improving mechanical strength. The ethylene-one-year-old olefin-based copolymer preferably has an α-year-old olefin content of 1 to 30 mol%, more preferably 2 to 25 mol%, and still more preferably 3 to 20 mol%. .

 1,4-hexadiene, dicyclopentadiene, 2,5-norpolnagen, 5-ethylidene norbornene, 5-ethyl-1-2,5-norbornadiene, 5- (1'-probenyl) 1-2 At least one non-conjugated gen such as norbornene may be copolymerized.

 The content of the polyolefin (a3) other than the epoxy group-containing polyolefin per 100 parts by weight of the modified PPS resin (a) is preferably 1 to 50 parts by weight, more preferably 5 to 40 parts by weight. is there.

 As long as the purpose of the present invention is not impaired, the modified PPS resin (a) in the present invention may contain other resins other than those described above.

 The modified polyester resin (b) in the present invention is obtained by melt-kneading a polyester (b1), a polyolefin (b2) containing an epoxy group, and a polyolefin (b3) other than the polyolefin containing an epoxy group as essential components. The resulting thermoplastic resin.

 The preferred polyester (bl) is a polymer having an ester bond in the main chain. Preferable is a thermoplastic polyester having an aromatic ring in the chain unit of the polymer. Specifically, usually, an aromatic dicarboxylic acid (or an ester-forming derivative thereof) and a diol (or an ester-forming derivative thereof) are usually used. And a polymer or copolymer obtained by a condensation reaction containing Z or hydroxycarboxylic acid as a main component.

Aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracenedicarboxylic acid, 4,4'- Diphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-1,4,4'-dicarboxylic acid, 5-sodium sulfoisophthalic acid and ester-forming derivatives thereof Can be Two or more of these aromatic dicarboxylic acids can be used in combination. Aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid and dodecandionic acid; alicyclic dicarboxylic acids such as 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid; Ester-forming derivatives can also be used in combination.

 Examples of the diol include aliphatic diols having 2 to 20 carbon atoms, ie, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, and 1,6-hexanediol. , Decamethylene glycol, cyclohexanedimethanol, cyclohexanediol and the like, and ester-forming derivatives thereof. Two or more of these diols can be used in combination.

 Specific examples of the polyester (b 1) preferably used in the present invention include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexane dimethylene terephthalate, and polyhexylene terephthalate. In addition to alkylene terephthalate, polyethylene-1,2,6-naphthalenedicarboxylate, polybutylene-1,2,6-naphthalenedicarboxylate, polyethylene-1,2, bis (phenoxy) ethane-1,4,4'-dicalpoxylate , Polyethylene isophthalate terephthalate, polybutylene isophthalate Z terephthalate, polybutylene terephthalate decane dicarboxylate, poly (ethylene terephthalate Z cyclohexane dimethylene) And non-liquid crystalline polyesters such as polyethylene-1,4'-dicarboxylate / terephthalate and mixtures thereof.

 More preferred are polyethylene terephthalate, polybutylene terephthalate, and polyethylene 1,2,6-naphthalenedicarboxylate, and particularly preferred is polyethylene terephthalate. It is practically suitable to use it as a mixture depending on the required properties such as heat resistance, heat resistance, toughness, and surface properties.

Although the degree of polymerization of these polyesters is not limited, for example, the intrinsic viscosity measured at 25 ° C. in a 0.5% 0-chlorophenol solution is in the range of 0.35 to 2.00, In particular, those having a range of 0.50 to 1.50 are preferable.

 Further, for example, in the case of polybutylene terephthalate, the amount of C OH H terminal group is 1 to 5 when the amount of C OH H terminal group obtained by potentiometric titration of m-cresol solution with an alkaline solution is 1 to

Those having a range of 50 eq / t (terminal group amount per ton of polymer) can be preferably used from the viewpoint of durability and anisotropic suppression effect.

 The epoxy group-containing polyolefin (b 2) used as an essential component of the modified polyester resin (b) used in the present invention, like the modified PPS resin (a) component, is a polyolefin having an epoxy group in the molecule, and is preferable. Is a copolymer containing a naphthalene and an epoxy group-containing monomer. Further, a copolymerized polyolefin comprising α-olefin and glycidyl α, monounsaturated acid is preferred. More preferred is a copolymer of ethylene and glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate, and particularly preferred is a copolymer of ethylene glycidyl methacrylate. The copolymerization amount of the / 3_unsaturated glycidyl ester is suitably 1 to 50% by weight, preferably 3 to 40% by weight.

 The content of the epoxy group-containing polyolefin (b2) based on 100 parts by weight of the polyester (bl) is preferably from 10 to 80 parts by weight, and more preferably from 10 to 80 parts by weight.

60 parts by weight. If the content of the epoxy group-containing polyolefin is more than 80 parts by weight, it is not preferable because the barrier property and the fluidity are reduced. Further, if the content of the epoxy group-containing polyolefin is less than 10 parts by weight, it is difficult to develop the high impact property, which is a feature of the present invention, which is not preferable.

The polyolefin (b 3) other than the epoxy group-containing polyolefin used as an essential component of the modified polyester resin (b) used in the present invention is used as an additional component in the modified PPS resin (a) (a 3) And preferably selected from polyethylene, polypropylene, ethylene / α-olefin copolymer, [(ethylene and / or propylene) and (unsaturated carboxylic acid and Ester) and [(ethylene and or propylene) and (unsaturated carboxylic acid and di- or unsaturated carboxylic acid ester) copolymers in which at least a part of the carboxyl groups of the copolymer are metallized And particularly preferably an ethylene / α-refined olefin copolymer. The content of the polyolefin (b3) other than the epoxy group-containing polyolefin is preferably 10 to 80 parts by weight, more preferably 10 to 100 parts by weight, based on 100 parts by weight of the polyester (b1). 60 parts by weight. If the content of the polyolefin resin other than the epoxy group-containing polyolefin exceeds 80 parts by weight, the barrier property is lowered, which is not preferable. On the other hand, if the content is less than 10 parts by weight, it is difficult to develop the high impact characteristic which is a feature of the present invention, which is not preferable.

 The modified polyester resin (b) in the present invention may contain other resins as long as the object of the present invention is not impaired.

 The content of the modified polyester resin (b) in the modified PPS resin (a) of 100 parts by weight in the resin composition of the present invention is from 40 to 250 parts by weight, preferably from 50 to 180 parts by weight. It is. If the content of the modified polyester resin (b) exceeds 250 parts by weight, it becomes difficult for the modified PPS resin (a), which is a feature of the present invention, to form a continuous phase, which is not preferable. On the other hand, if the content is less than 40 parts by weight, it is not preferable because it is difficult to exhibit the high impact characteristic of the present invention.

 The epoxy-modified polyolefin (c) obtained by the reaction between the epoxy compound and the polyolefin used in the present invention is an acid-modified polyolefin (c1) obtained by graft polymerization of an ethylenically unsaturated carboxylic acid or a derivative thereof to polyolefin. ) And a polyfunctional epoxy compound (c 2), a polyolefin, an ethylenically unsaturated carboxylic acid or a derivative thereof, an organic peroxide, or a multifunctional epoxy compound. Obtained by the method. The polyolefin used herein is obtained by polymerizing at least one of olefins selected from ethylene and α-olefins having 3 to 20 carbon atoms.

Specifically, in addition to ethylene, alpha-olefins with 3 to 20 carbon atoms include propylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, and 1-hexene. , 4-Methyl 1-pentene, 3-Methyl 1-pentene, 3-Ethyl 1-pentene, 4, 4-dimethyl-1-pentene, 4-methyl-1-hexene, 4, 4--dimethyl 1 — hexene, 4 — ethyl 1 1 hexene, 3 — ethyl 1 1 hexene, 1 — octene, 1 — decene, 1 — dodecene, 1 — tradece And olefins such as 1-hexadecene, 1-octadecene, and 1-eicosene. These homopolymers or copolymers can be used alone or in combination of two or more.

 Among them, polyolefins containing at least one polymer or copolymer of an olefin selected from ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene are preferred.

 Further, among these, a polyolefin containing a copolymer of at least one selected from ethylene and α-olefin having 3 to 20 carbon atoms is more preferable in that it has good impact resistance. Here, propylene, 1-butene, 4-methyl-11-pentene, 1-hexene and 1-octene are particularly preferred as α-olefins to be copolymerized with ethylene.

 The density of the polyolefin used in the present invention is usually 0.940 g / cc or less, preferably 0.920 g / cc or less, more preferably 0.895 gZc c or less.

 The melt flow rate (MFR; ASTM D 1238, 190 ° C, load 2.16 kg) of polyolefins is usually between 0.01 and 500 gZ10 min, preferably 0.0 It is 5 to 200 minutes, more preferably 0.1 to 100 gZ10 minutes.

 The weight average molecular weight (Mw) of the polyolefin measured by gel permeation chromatography (GPC) is usually 30,000 to 60,000, preferably 40,000 to 40,000, more preferably 40,000 to 40,000. It is 300,000.

 The molecular weight distribution (MwZMn) is usually 5.0 or less, preferably 4.5 or less, and more preferably 4.0 or less. Mn indicates a number average molecular weight.

 The production of the above-mentioned polyolefin can be carried out by any conventionally known method. For example, the polymerization can be carried out using a titanium-based catalyst, a vanadium-based catalyst, a meta-open catalyst, or the like.

The ethylenically unsaturated carboxylic acid or a derivative thereof used in the present invention is a compound having an ethylenic double bond and at least one carboxylic acid or a derivative thereof in the molecule. Specifically, acrylic acid, methacrylic acid, maleic acid, Fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norpolonenedicarboxylic acid, bicyclo [2,2,1] hept-1-ene-5,6-dicarboxylic acid And the like, or their anhydrides or their derivatives (eg, acid halides, amides, imides, esters, etc.). Examples of specific compounds include maleenyl chloride, malenylimide, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-1-ene. 1,5,6-dicarboxylic anhydride, dimethyl maleate, monomethyl maleate, getyl maleate, getyl fumarate, dimethyl itaconate, getyl citrate, dimethyl tetrahydrophthalate, bicyclo [2,2,1] heptoh 2-ene-5,6-dimethyl carboxylate, hydroxyshethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, methacrylic acid Examples thereof include aminoethyl and aminopropyl methacrylate. Among them, (meth) acrylic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene_5 , 6-dicarboxylic anhydride, hydroxyxethyl (meth) acrylate, glycidylmethacrylate, and aminopropyl methacrylate are preferred.

 Furthermore, dicarboxylic anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydro anhydrous phthalic acid, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic anhydride Is particularly preferred.

 The acid-modified polyolefin (c1) in the present invention is obtained by radical-initiating the above-mentioned polyolefin with an ethylenically unsaturated carboxylic acid or a derivative thereof and, if necessary, other ethylenically unsaturated monomers. It can be produced by heating and reacting in the presence or absence of an agent.

 When the graft polymerization is carried out in the presence of a radical initiator, the efficiency of the graft reaction is increased.Therefore, in producing the modified ethylene polymer of the present invention, the graft reaction can be carried out using a radical initiator. preferable.

Examples of the radical initiator used here include organic peroxides and azo compounds. Specific examples of organic peroxides include dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylpyroxy) hexane, 2,5 —Dimethyl-1,2,5-bis (t-butylperoxy) hexine — 3,1,3-bis (t-butylperoxyisopropyl) benzene, 1,1-bis (t-butylperoxy) balalate, benzoylperoxa Ide, t-butylperoxybenzoate, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3, 5, 5 — Trimethylhexanoyl peroxide, 2,4-dichrolic benzoyl peroxide and m-tolyl peroxide Can. In addition, examples of the azo compound include azoisobutyronitrile and dimethylazosopyronitrile.

 The above-mentioned graft polymerization may be carried out in any state where at least a part of the polyolefin is in a solid state, in a molten state, or at least partly in an organic solvent.

 When the graft polymerization is carried out in a state where at least a part of the thermoplastic polymer is dissolved in an organic solvent, it is usually 50 to 200 ° C, preferably 60 to 190 ° C, more preferably. The reaction is carried out at a temperature of 70 to 180 ° C.

 Examples of the organic solvent used at that time include aromatic hydrocarbon solvents such as benzene, tonolene, and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, and heptane.

 When the graft polymerization is carried out in a state where the polyolefin is melted, the reaction is usually carried out at a temperature higher than the melting point of the polyolefin. That is, the graft polymerization reaction is carried out at a temperature equal to or higher than the melting point of the polyolefin, specifically at a temperature of usually 80 to 300 ° C., preferably 80 to 260 ° C.

 The graft amount of the carboxylic acid or its derivative in the acid-modified polyolefin thus prepared is usually 0.01 to 20% by weight, preferably 0.05%.

-15% by weight, more preferably 0.1-10% by weight.

The polyfunctional epoxy compound used in the present invention may be any compound, polymer or prepolymer containing two or more oxysilane ring structures in the molecule. Although an epoxy resin can be used, it is preferable to use an epoxy resin containing two or more epoxy groups in the molecule. The polyfunctional epoxy compound may be aromatic or aliphatic.

 The epoxy resins used here include bisphenol A type epoxy resin, bisphenol F type epoxy resin, resorcinol type epoxy resin, tetrahydroxyphenylmethane type epoxy resin, tetrahydroxyphenylethane type epoxy resin, and phenol novolak. Epoxy resin, cresol nopolak epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, epoxidized polybutadiene, epoxidized styrene / butadiene rubber, and the like.

 Among them, phenol nopolak-type epoxy resin, cresol novolak-type epoxy resin, tetrahydroxyphenylmethane-type epoxy resin, and tetrahydroxyloxy-xylethane-type epoxy resin are resin compositions having a high polar group content. It is preferable in that it can obtain.

 Among these epoxy resins, the polar resin usually has an epoxy equivalent of 50 to 500, preferably 100 to 300, and more preferably 100 to 250. This is preferable in that a resin composition having good compatibility with the above can be obtained.

 The epoxy-modified polyolefin (c) in the present invention can be obtained by melt-kneading the acid-modified polyolefin (c1) and the polyfunctional epoxy compound (c2).

 There is no particular limitation on the kneading method when the above components are melt-kneaded, but the above-mentioned components are simultaneously or sequentially added to, for example, a hensile mixer, a V-type blender, a tumbler blender, a ribbon blender, and the like. After being charged and kneaded, it can be obtained by melt-kneading with a single-screw extruder, multi-screw extruder, kneader, Banbury mixer, or the like. Among these, it is preferable to use a kneading machine having excellent kneading performance such as a multi-screw extruder, a kneader, a Banbury mixer, etc., since it is possible to obtain a resin composition in which each component is more uniformly dispersed and reacted. .

In the present invention, the reaction conditions for melt-mixing the polyolefin, the ethylenically unsaturated carboxylic acid or its derivative, the organic peroxide, and the polyfunctional epoxy compound are the same as the conditions for the above-described graft reaction. It can be performed under conditions. The content of the epoxy-modified polyolefin (C) obtained by the reaction of the epoxy compound with the polyolefin is determined by the polyolefin other than polyphenylene sulfide, polyester, epoxy group-containing polyolefin, and epoxy group-containing polyolefin. Is 0.5 to 20 parts by weight based on 100 parts by weight of the resin composition comprising Preferably it is 0.5 to 15 parts by weight, more preferably 1 to 10 parts by weight. In the molded product obtained by processing the resin composition of the present invention, as shown in FIG. 1, the modified PPS resin 1 forms a continuous phase, and the polyester (bl) 2 of the modified polyester resin (b) Is a dispersed phase, and the poly-olefin (b 3) 3 other than the epoxy group-containing polyolefin (b 2) and the epoxy group-containing polyolefin is dispersed in the polyester. Here, the resin phase separation structure of the present invention is not limited to the embodiment shown in FIG. 1, but includes a modified polyester resin (b), an epoxy group-containing polyolefin (b 2), and a polyolefin (b) other than the epoxy group-containing polyolefin (b). The shape of 3) may be non-circular such as polygonal or substantially elliptical.

 By using an epoxy-modified polyolefin (c) obtained by the reaction of an epoxy compound and polyolefin, the above sea-island-lake structure can be formed stably irrespective of the shape of the molded article and molding conditions. You. Furthermore, the dispersed particle size of the dispersed phase can be reduced, and the dispersed phase of the modified polyester resin (b) is dispersed and dispersed at an average dispersed particle size of 5 m or less, and the dispersed phase of the modified polyester resin (b) is dispersed. The epoxy group-containing polyolefin (b 2) and the polyolefin (b 3) other than the epoxy group-containing polyolefin form a dispersed phase with an average dispersed particle size of 1 or less. With this resin phase separation structure, the specific impact resistance and permeation resistance, which are the objects of the present invention, can be significantly improved.

The dispersed particle size of the modified polyester resin (b) is more preferably 3 m or less. The dispersed particle size of the epoxy group-containing polyolefin (t イ ン 2) and the polyolefin (b 3) other than the epoxy group-containing polyolefin is preferably 0.8 μm or less. The lower limit of the dispersion particle size is not particularly limited, but the dispersion particle size of the modified polyester resin (b) achievable by ordinary melt-kneading is about 0.03 m, and the epoxy group-containing polyolefin (b 2) Less than polyolefin containing epoxy group The dispersed particle size of the outer polyolefin (b 3) is about 0.01 μm.

 The molded product obtained by molding the resin composition of the present invention has a part or the whole of a phase structure in which the modified PPS resin (a) is a continuous phase and the modified polyester resin (b) is a dispersed phase. Here, for example, the modified PPS resin (a) is a small component, such as 100 to 250 parts by weight of the modified PPS resin (b), relative to 100 parts by weight of the modified PPS resin. By appropriately controlling the melt viscosity ratio (here, the melt viscosity ratio is defined as the melt viscosity of the modified PPS resin and the melt viscosity of the modified polyester resin), the phase in which the modified PPS resin takes a continuous phase is controlled. A molded article forming the structure can be obtained.

The resin composition of the present invention is generally formed by melt molding. However, in the melt molding, a temperature difference and a stress difference easily occur between the resin surface layer and the inside of the resin during flow. In the present invention, this can be used to obtain the above-mentioned phase structure. In other words, the modified PPS resin (a) and the modified polyester resin (b) use resins with different melt viscosities depending on the shear rate for the modified polyester resin (b). In this method, the modified PPS resin (a) partially or entirely forms a continuous phase. For example, taking injection molding as an example, when molding at a certain molding temperature, the shear rate increases at the surface layer of the molded product due to friction with the mold as compared with the central portion of the molded product. Shearing speed 100 seconds-If the combination is such that the melt viscosity ratio at any shearing speed of about ¹ or more is 0.7 or more, the molded product surface is modified PPS resin (a) and modified polyester resin (b) May form a co-continuous phase, both of which are continuous phases. However, if the melt viscosity ratio at any shear rate of 200 seconds to about ¹ or less at that temperature is 0.5 or less, the molded article The modified PPS resin (a), which is a requirement of the present invention, can form a portion where the modified PPS resin (a) becomes a continuous phase and the modified polyester resin (b) becomes a disperse phase at the center. Can be preferably used as a method for forming a phase structure in which the modified polyester resin (b) becomes a dispersed phase. There is no particular limitation on the shape of the molded article. There is also an embodiment in which a plurality of the phase structures are formed in the molded article. This phase structure can be observed and confirmed using scanning and transmission electron microscopes. The resin composition of the present invention has an inorganic filler for imparting mechanical strength, rigidity and barrier properties. 塡 material can be contained. The material is not particularly limited, but fibrous, plate-like, powder-like, and granular fillers can be used. Specifically, for example, fibers such as glass fiber, carbon fiber, titanic acid-reducing force, zinc oxide whisker, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, stone fiber, and metal fiber Swelling properties such as silicates such as fillers, wallastite, sericite, kaolin, myriki, cres, bentonites, asbestos, talc, alumina silicates, monmorillonite, synthetic mica Metal compounds such as layered silicate, alumina, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide and iron oxide; carbonates such as calcium carbonate, magnesium carbonate and dolomite; sulfates such as calcium sulfate and barium sulfate; Glass' beads, ceramic beads, boron nitride, silicon carbide, calcium phosphate and silica Include non-fibrous charged 塡剤 of, these may be hollow, it is also possible that further a combination of these charging 塡剤 two or more.

In addition, these inorganic fillers are pre-treated with a coupling agent such as an isocyanate-based compound, an organic silane-based compound, an organic titanate-based compound, an organic borane-based compound, or an epoxy compound, and an organic ion for a swellable layered silicate. It is preferable to use more excellent mechanical strength and barrier property. _C The content of the inorganic filler is the total amount of the modified PPS resin (a) and the modified polyester resin (b). It is preferable that the amount be 0.1 to 200 parts by weight based on 100 parts by weight. It is more preferably 0.5 to 200 parts by weight, particularly preferably 1 to 150 parts by weight.

The resin composition of the present invention may contain a conductive filler and / or a conductive polymer for imparting conductivity. The material is not particularly limited, but the conductive filler is not particularly limited as long as it is a conductive filler that is generally used for making a resin conductive. Specific examples thereof include metal powder, metal flake, and metal. Examples of the filler include carbon, inorganic filler coated with a conductive material, carbon powder, graphite, carbon fiber, carbon flake, and flaky carbon. Specific examples of metal types of metal powder, metal flakes, and metal ribbons include silver, nickel, copper, zinc, aluminum, stainless steel, iron, brass, chromium, and tin. Specific examples of the metal type of the metal fiber include iron, copper, stainless steel, aluminum, brass and the like.

 Such metal powder, metal flakes, metal repons, and metal fibers may be subjected to a surface treatment with a surface treating agent such as a titanate, aluminum, or silane.

S n 0 ₂ Specific examples of the metal oxides (antimony de one-flop), I n ₂ 0 ₃ (antimony de one-flop), Z n O (aluminum-doped) and the like can be exemplified, they titanate system, Surface treatment may be performed with a surface treatment agent such as an aluminum-based or silane-based coupling agent.

Conductive material coated with an inorganic FILLER § Specific examples of the conductive material in one Noreminiumu, nickel, silver, carbon, S n 0 ₂ (doped with antimony), I n ₂ 0 such as (antimony-doped) can be exemplified. Inorganic fillers to be coated include: My power, glass beads, glass fiber, carbon fiber, potassium titanate whisker, barium sulfate, zinc oxide, titanium oxide, aluminum borate whiskers, zinc oxide whiskers, Examples include titanic acid whiskers and silicon carbide whiskers. Examples of the coating method include a vacuum deposition method, a sputtering method, an electroless plating method, and a baking method. These may be surface-treated with a surface treating agent such as a titanate-based, aluminum-based, or silane-based coupling agent.

Carbon powder is classified into acetylene black, gas black, oil black, naphthalene black, thermal black, furnace black, lamp black, channel black, roll black, disk black, etc. according to its raw material and production method. The raw material and production method of the carbon powder that can be used in the present invention are not particularly limited, but acetylene black and furnace black are particularly preferably used. Various carbon powders with different properties such as particle diameter, surface area, DBP oil absorption, and ash are manufactured. The carbon powder that can be used in the present invention is not particularly limited in these characteristics, but from the viewpoint of balance between strength and electric conductivity, the average particle size is preferably 500 nm or less, and more preferably 5 to 10 nm. 0 nm, particularly preferably 10 to 70 nm. The specific surface area (BET method) 1 0 m ² Roh g or more, more 3 0 m ² or more. The DBP refueling amount is preferably at least 500 m1 / 100 g, particularly preferably at least 100 m1 / 100 g. The ash content is 0. It is preferably at most 5% by weight, particularly preferably at most 0.3% by weight.

 Such a carbon powder may be subjected to a surface treatment with a surface treating agent such as a titanate, aluminum, or silane. It is also possible to use a granulated material to improve the workability of melt-kneading.

 Molded articles obtained by processing the resin composition of the present invention often require surface smoothness. From such a viewpoint, the conductive filler used in the present invention, like the inorganic filler used in the present invention, is more powdery, granular, and plate-like than the fibrous filler having a high aspect ratio. It is preferably in any of a scaly shape or a fibrous shape having a length-to-diameter ratio of 200 or less in the resin composition.

 Specific examples of the conductive polymer include poly (arylene), polypyrrole, polyacetylene, poly (paraphenylene), polythiophene, and polyphenylenevinylene. ^

 The conductive filler and the conductive polymer or the conductive polymer may be used in combination of two or more. Among such conductive fillers and conductive polymers, particularly strong black is preferably used in view of strength and economy.

 Since the content of the conductive filler and Z or the conductive polymer used in the present invention varies depending on the type of the conductive filler and / or the conductive polymer used, it cannot be specified unconditionally. From the viewpoint of balance with mechanical strength, etc., 1 to 250 parts by weight, preferably 3 to 100 parts by weight, of the total of 100 parts by weight of the components (a) and (b) is used. A range is preferably selected. More preferably, the range of 3 to 100 parts by weight is preferably selected for imparting a conductive function to the total of 100 parts by weight of the components (a) and (b).

When conductivity is imparted, the volume resistivity is preferably 10 '° Ω · cm or less from the viewpoint of obtaining sufficient antistatic performance. However, the compounding of the conductive filler and the conductive polymer generally tends to cause deterioration in strength and fluidity. Therefore, if the target conductivity level can be obtained, it is desirable that the blending amounts of the conductive filler and the conductive polymer be as small as possible. The target conductivity level depends on the application, but usually the volume resistivity is in the range of more than 100 Ω · cm and less than 100 ′ ° Ω · cm. Other components in the resin composition of the present invention within a range that does not impair the effects of the present invention, For example, antioxidants, heat stabilizers (hindered phenols, hydroquinones, phosphites and their substitutes), weathering agents (resorcinols, salicylates, benzotriazoles, benzophenones, hinders) Release agents and lubricants (montanic acid and its metal salts, esters, half esters, stearyl alcohol, stearamide, various bisamides, bisurea, polyethylene wax, etc.), pigments (sulfided Power dough, phthalocyanine, carbon black, etc.), dyes (Nig mouth, etc.), crystal nucleating agents (talc, silica, power ol, crepe, etc.), plasticizers (p-oxybenzoyl octyl, N-butylbenzene sulfo) Amide, etc.), antistatic agent (alkyl sulfate type anio) Antistatic agents, quaternary ammonium salt type cationic antistatic agents, nonionic antistatic agents such as polyoxyethylene sorbitan monostearate, betaine amphoteric antistatic agents, etc., flame retardants (for example, red phosphorus, Hydroxides such as melamine cyanurate, magnesium hydroxide, and aluminum hydroxide, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, brominated epoxy resin, and brominated flame retardants of these And antimony trioxide, etc.) and other polymers can be added.

The method for obtaining the resin composition of the present invention is not particularly limited as long as the present invention satisfies the requirements.In order to achieve a preferable phase structure in melt-kneading, for example, a twin-screw extruder is used. A method in which, when kneading, a modified PPS resin (a) and a modified polyester resin (b) previously melt-kneaded and an epoxy-modified polyolefin (c) obtained by reacting an epoxy compound with a polyolefin are supplied from a main feeder; The PPS (a1) and the epoxy group-containing polyolefin (a2) are supplied from the main feeder, melt-kneaded, and the modified polyester resin (b) and the epoxy-modified polyolefin obtained by reacting the epoxy compound with the polyolefin ( c) from the side feeder at the extruder tip, polyester from the main feeder b 1), epoxy group-containing polyolefin (b 2), and polyolefin (b 3) other than epoxy group-containing polyolefin are supplied, melt-kneaded, and modified PPS resin (a) and the mixture of epoxy compound and polyolefin. The epoxy-modified polyolefin (c) obtained by the reaction is transferred to the side fin of the extruder. For example, there is a method of supplying from a feeder. After melt-kneading, the mixture was formed into strands, cooled with a cooling bath, and pelletized with a strand force.

 As a method for molding the resin composition of the present invention, conventionally known methods (such as injection molding, extrusion molding, blow molding, and press molding) can be employed. Among them, it is preferable to adopt a method selected from injection molding, injection compression molding and compression molding from the viewpoints of low water absorption and improvement of permeation resistance of the molded article. The molding temperature is usually selected from a temperature range 5 to 50 ° C higher than the melting point of PPS.

 The structure of the molded product is generally a single layer, but may be a multilayer structure by a method such as a two-color injection molding method or a co-extrusion molding method. Here, the multilayer structure refers to a structure having at least one layer made of the resin composition of the present invention. The arrangement of each layer is not particularly limited, and all the layers may be composed of the resin composition of the present invention, or the other layers may be composed of another thermoplastic resin.

 Such a multilayer structure can also be manufactured by a two-color injection molding method or the like. In the case of obtaining a film or sheet, the composition forming each layer is melted by a separate extruder, and then fed to a multi-layered die, co-extrusion molding, another layer is formed in advance Thereafter, it can be produced by a so-called lamination molding method in which a layer comprising the resin composition of the present invention is melt-extruded. When the shape of the laminated structure is a hollow container such as a bottle, a barrel, or a tank, or a tubular body such as a pipe or a tube, an ordinary co-extrusion molding method can be employed. For example, the inner layer is formed of the resin composition of the present invention. In the case of a two-layer hollow molded body in which the outer layer and the outer layer are formed of other resin layers, the resin composition and the other resin are separately supplied to two extruders, and these two types of molten resins are supplied. After pressure is supplied into the common die to form an annular flow, the resin composition layer is joined to the inner layer side and the other resin layer is joined to the outer layer side, and then the resin composition is shared outside the die. The two-layer hollow molded body can be obtained by extruding and performing a generally known tube molding method, blow molding method, or the like. In the case of a three-layer hollow molded body, a three-layer structure is formed by the same method as described above using three extruders, or a two-layer three-layer hollow structure is formed using two extruders. It is also possible to obtain molded objects. Among these methods, it is preferable to form using a co-extrusion molding method from the viewpoint of the eyebrow adhesive strength.

The thermoplastic resin used as another layer includes saturated polyester, polysulfur Hong, polyethylene tetrafluoride, polyether imide, polyamide imid, polyamide, polyketone copolymer, polyphenylene ether, polyimide, polyester sulfone, polyether ketone, polythioether ketone, polyether a Examples thereof include terketone, thermoplastic polyurethane, polyolefin, ABS, polyamide elastomer, polyester elastomer, and the like. These may be used as a mixture thereof or with various additives added thereto.

 Molded articles obtained by molding the resin composition of the present invention include, for example, chlorofluorocarbon 11, fluorocarbon 12, fluorocarbon 21, fluorocarbon 22, fluorocarbon 11, fluorocarbon 11 4 , CFC 1 1 5, CFC 1 3 4a, CFC 1 3 2, CFC 1 2 3, CFC 1 2 4, CFC 1 2 5, CFC 1 4 3a, CFC 1 4 1b , Chlorofluorocarbon _ 14 2 b, fluorocarbon 225, fluorocarbon C 3 18, R—502, 1, 1, 1 — trichloroethane, methyl chloride, methylene chloride, chlorinated methyl, methylchloroform, Propane, isobutane, n-butane, dimethyl ether, castor oil based brake fluid, glycol ether based brake fluid, borate ester based brake fluid, brake fluid for extreme cold regions, silicone oil based brake fluid, mineral oil based brake fluid, power sariline G oil, window washer fluid, Gases such as gasoline, methanol, ethanol, isobutanol, butanol, nitrogen, oxygen, hydrogen, carbon dioxide, methane, propane, natural gas, argon, helium, xenon, pharmaceutical agents, and Z or liquid or vaporized gas Due to its low permeability and excellent properties, reservoir tanks for oils and other chemical storage containers such as shampoos, rinses, liquid stones, etc. Parts, brake hose connection parts, window washer liquid nozzles, cooling water, refrigerant hose connection parts, air conditioner refrigerant tube connection parts, fire extinguishers and fire extinguishing equipment hoses, medical cooling equipment tube connections Parts and valves, other chemicals and gas transport tubes Applications, such as chemicals and gas storage resistance, such as containers for chemicals, containers for storing chemicals, automotive parts, internal combustion engines, and mechanical parts such as power tool housings, electrical and electronic parts, medical care, food, and households. · Effective for various uses such as office supplies, building materials-related parts, and furniture parts.

Example Hereinafter, the present invention will be described in detail with reference to examples, but the gist of the present invention is not limited to the following examples. First, characteristics used for evaluation of the resin composition according to the present invention will be described.

 (1) Alcohol permeability

 20 g of methanol was precisely weighed in an aluminum container having a diameter of 6 O mm and a depth of 5 cm, sealed with a 1 mm thick square test piece adjusted by injection molding, and fixed with bolts so as not to leak. Thereafter, the entire weight was measured, and the test container was placed in an explosion-proof oven at 60 ° C., every 500 hours, and then the reduced weight was measured.

 (2) Alcohol permeability when absorbing moisture

 The test container filled with methanol was treated in a thermo-hygrostat at a temperature of 60 ° C. and a relative humidity of 65% for 500 hours in the same manner as in the above (1), and the reduced weight was measured.

 (3) Absorbency of alcohol

 ASTM No. 1 tensile test specimen (thickness: 1/8 inch) prepared by injection molding was immersed in methanol in an autoclave, and placed in an explosion-proof oven at 60 ° C. for 24 hours. The liquid absorbency was determined as the weight increase during liquid absorption from the ratio of the weight measured at the time of absolute drying (at the time of absolute drying) immediately after molding and the weight measured after the alcohol liquid absorption treatment. Liquid absorption rate (%) = {(weight after liquid absorption-weight when absolutely dry) / weight when absolutely dry) X100

(4) Absorbency of alcohol gasoline

 ASTM No. 1 tensile test specimen (thickness: 1/8 inch) prepared by injection molding was mixed in a autoclave with model gasoline (toluene / isooctane = 50 // 50% by volume) and ethanol at 90: 1. After being immersed in alcohol gasoline mixed at 0 weight ratio, it was placed in an explosion-proof oven at 60 ° C and treated for 24 hours. The liquid absorbency was determined as the weight increase rate during liquid absorption from the ratio of the weight measured immediately after molding to the absolute dry state (at the absolute dry time) and the weight measured after the alcohol gasoline liquid absorption treatment.

Liquid absorption rate (%) = {(weight after liquid absorption—weight when absolutely dry) Z Weight when absolutely dry) X 100

(5) Material strength

 It was measured according to the following standard method.

Tensile strength: Measured according to the method described in ASTM D638.

Izod (Iz0d) Impact strength: ASTM D256 (temperature 23 ° C) Measured according to the method described.

Low temperature impact strength: Izod impact strength measured according to ASTM D256 except that the temperature atmosphere was 140 ° C.

 (6) Observation of phase separation structure and dispersion morphology-0.1 to 0.3 mm part (surface layer) and 1.4 to 1.8 mm part (center) from the surface in the thickness direction of A STM No. 1 test piece Were observed using a TEM (H-7100 transmission electron microscope manufactured by Hitachi, Ltd.) or SEM (S210A OA scanning electron microscope manufactured by Hitachi, Ltd.).

 (7) Melt viscosity ratio

Using a plunger-type capillary rheometer (capillary graph type 1C, manufactured by Toyo Seiki Seisaku-Sho, Ltd.), the melt viscosities at the kneading temperature of 100 seconds- ¹ and 500 seconds- ¹ (P a's) was measured and determined by the following equation (1). (Equation 1)

[Melt viscosity of modified polyphenylene sulfide resin] Melt viscosity ratio = · (1)

 [Melt viscosity of modified polyester resin]

(8) Dispersion phase dispersion particle size

 The 1.4-1.8 mm portion (center) from the thickness direction of the ASTM No. 1 test piece was observed using TEM (magnification: 10,000 times), and 100 arbitrary disperse phases were selected. The average value of the maximum diameter and the minimum diameter was calculated as a number average value.

 The modified PPS resin and modified polyester resin used in Examples and Comparative Examples are as follows. In addition, unless otherwise noted, polymerization was carried out in accordance with a conventional method.

 [Reference Example 1] Production of p-phenylene sulfide Zm-phenylene sulfide copolymer

In an autoclave with a stirrer, add 47% aqueous sodium hydrosulfide solution (Sankyo Kasei) 2.98 kg (25 mol), 96% sodium hydroxide 1.06 kg (25.44 mol) N-methyl-1-pyrrolidone (NMP) 4.0 kg (4.12 ), 0.69 kg (8.41 mol) of sodium acetate, and 3.75 kg of ion-exchanged water, and gradually increase the temperature to 225 ° C over about 3 hours while passing nitrogen at normal pressure. After heating and distilling 5.25 kg of water and 0.1 kg of NMP, the reaction vessel was cooled to 150 ° C. The amount of hydrogen sulfide scattered was 1.8 mol%.

 Next, p-dichlorobenzene (Sigma Aldrich) 3.36 k (2.86 mol), m-dichlorobenzene (Tokyo Kasei) 0.36 kg (2.45 mol), NMP 3. 28 k (33.1 mol) was added, the reaction vessel was sealed under nitrogen gas,

227 ° while stirring at 400 rpm. The temperature was raised at a rate of 0.8 ° C "min. Until then, and then the temperature was raised at a rate of 0.6 ° CZ up to 270 ° C and held at 270 for 170 min. Cooled to 80 ° C at a rate of 0.4 min, then quenched to near room temperature Remove the contents, dilute with 12.5 liters of NMP, sieve solvent and solids (8 O The resulting particles were washed several times with 25 liters of warm water and filtered to obtain PPS polymer particles, which were dried with hot air at 80 ° C and dried at 120 ° C. It was dried under reduced pressure at ° C to obtain about 2.2 kg of p-phenylene sulfide m-phenylene sulfide copolymer.

 The obtained P-phenylene sulfide Zm-phenylene sulfide copolymer has a melting point of 248 ° C and a melt flow rate of 350 g / 10 minutes (hereinafter abbreviated as MFR). : 3 1

5 ° C, load 5 kg).

 [Reference Example 2] Production of modified PP S resin (a)

(A-1): Melting point 280 ° C, MFR 200 g / 10 min (3 15 ° C, 5 kg load), melt viscosity 1550 P a 's (320 ° C, MFR 310 minutes (190.C, 2.16 kg load) ethylene / glycidyl methacrylate based on 100 parts by weight of polyphenylene sulfide resin with a shear rate of 100 000 sec- ¹ ) 288/12 (wt%) copolymer was mixed in 25 parts by weight and melt-extruded at a cylinder temperature of 300 ° C using a twin-screw extruder to give an Izod impact strength of 350. JZm modified PPS resin.

(A-2): melting point 280. C, MFR 200 g / 10 min (31.5 C, 5 kg load), melt viscosity 150 Pas (320 ° C, shear rate 10000 sec- ¹ ) For 100 parts by weight of polyphenylene sulfide resin, ethylene Z glycidyl methacrylate = 88/12 (weight%) for MFR 310 minutes (190.C, 2.16 kg load) When 100 parts by weight of the modified PPS resin obtained by mixing 12.5 parts by weight of the polymer is used, MFR = 0.5 (190 ° C, 2.16 kg load), density 0. The ethylene-butene copolymer of 860 was mixed at a ratio of 12 parts by weight, and melt-extruded at a cylinder temperature of 300 ° C using a twin-screw extruder. 0 0 JZm modified PPS resin.

 (A- 2 '): Melting point 280 ° C, MFR 200 10 minutes (315 ° C, 5 kg load), melt viscosity 150 Pas (320 ° C, Glycidyl ethylenenomethacrylate with MFR S gZ l Oj ^ C ig O ° C and a load of 2.16 kg) was added to 100 parts by weight of polyphenylene sulfide resin with a shear rate of 100 sec— When the modified PPS resin obtained by mixing 12.5 parts by weight of the 8 8 Z 12 (weight%) copolymer was 100 parts by weight, the MFR was 0.5 (190 ° C, 2 ° C). Unmelted mixture of ethylene Z 1 -butene copolymer with a density of 0.860 at a ratio of 12 parts by weight. (A-3): p-phenylene sulfide m obtained at the melting point of 2 48 ° C and MFR 350 0 min (3 15 ° C, 5 kg load) obtained in Reference Example 1 above. —Ethylene / glycidyl methacrylate with MFR of 3 g / 10 min (190 ° C, 2.16 kg load) = 100 wt parts of phenylene sulfide copolymer = 88 / 1 2 (% by weight) When the modified PPS resin obtained by mixing 12.5 parts by weight of the copolymer is 100 parts by weight, MF R = 0.5 (190 ° C, 2.1 6 kg load) Ethylene / 1-butene copolymer with a density of 0.860 is mixed at a ratio of 12 parts by weight, and melt-extruded at a temperature of 270 ° C in a cylinder using a twin-screw extruder. The resulting modified PPS resin with an Izod impact strength of 450 JZm.

(A-4): melting point 280. (: MFR 200 g / 10 min (3 15 ° C, 5 kg load), melt viscosity 1 500 Pa · s (320 ° C, shear rate 10000 sec— Ethylene / glycidyl methacrylate with MFR of 3 gZl 0 min (190 ° C, 2.16 kg load) per 100 parts by weight of styrene sulfide resin = 88/12 (% by weight) When the modified PPS resin obtained by mixing 15 parts by weight of the copolymer is 100 parts by weight, MFR = 0.5 (190 ° C, 2.16 kg load), density 0.8 The ethylene 1-butene copolymer of 60 was mixed at a ratio of 25 parts by weight, and melt-extruded at a cylinder temperature of 300 ° C. using a twin-screw extruder to obtain an Izod impact strength of 650. JZm denaturation PPS resin.

 (A-5): Melting point 280 ° C, MFR 200 g / 10 min (3 15 ° C, 5 kg load), melt viscosity 150 Pas (320 ° C, MFR 3 gZl 0 min (190 ° C, 2.16 kg load) ethylene glycidyl methacrylate per 100 parts by weight of polyphenylene sulfide resin with a shear rate of 1000 sec ') = 8 8 1 2 (% by weight) When 100 parts by weight of a modified PPS resin obtained by mixing 5 parts by weight of a copolymer, MFR = 0.5 (190.C, 2.16 kg load), ethylene / 1-butene copolymer with a density of 0.860 was mixed at a ratio of 5 parts by weight and melt-extruded at a cylinder temperature of 300 ° C. using a twin-screw extruder. Modified PPS resin with Izod impact strength of 380 JZm.

 (A-6): Melting point 280 ° C, MFR 200 gZ 10 minutes (3 15 ° C, 5 kg load), melt viscosity 150 Pas (32 ° C, shearing) Polyphenylene sulfide resin with a speed of 100 000 sec ').

 [Reference Example 3] Production of modified polyester resin (b)

 (B-1): Ethylene / methacrylic acid of MFR 310 minutes (190 ° C, 2.16 kg load) with respect to 100 parts by weight of polyethylene terephthalate resin having an intrinsic viscosity of 0.65 Daricidil = 88/12 (wt%) 33 parts by weight of copolymer, MFR = 0.5 (190 ° C, 2.16 Kg load), ethylene / density 0.860 1—Modified polyester resin with an Izod impact strength of 950 J Zm obtained by mixing 33 parts by weight of a butene copolymer and melt-extruding the mixture at a cylinder temperature of 280 ° C using a twin-screw extruder .

 (B-II): Ethylene with MFR of 3 g ”for 10 minutes (at 190 ° C, 2.16 kg load) with respect to 100 parts by weight of polyethylene terephthalate resin having an intrinsic viscosity of 0.65 / Glycidyl methacrylate = 88/12 (wt%) 33 parts by weight of copolymer, MFR = 0.5 (190 ° C, 2.16 kg load), density 0.86 0 An unmelted mixture obtained by mixing ethylene monobutene copolymer in a ratio of 33 parts by weight.

(B-2): Ethylene of MFR 310 minutes (190 ° C, 2.16 kg load) with respect to 100 parts by weight of polyethylene terephthalate resin having an intrinsic viscosity of 0.65 Glycidyl methacrylate = 88/12 (% by weight) 25 parts by weight of copolymer, M FR = 0.5 (190 ° C, 2.16 kg load), 30 parts by weight of ethylenebutene copolymer having a density of 0.860 are mixed, and the cylinder temperature is adjusted using a twin-screw extruder. Modified polyester resin with an Izod impact strength of 900 JZm obtained by melt extrusion at 280 ° C.

 (B-3): Ethylene Z with MFR of 3 g / 10 minutes (190 ° C, 2.16 kg load) with respect to 100 parts by weight of polyethylene terephthalate resin having an intrinsic viscosity of 0.65 Glycidyl methacrylate = 9 4/6 (33 parts by weight of copolymer, MFR = 0.5 (190 ° C, 2.16 kg load), Ethylene Z 1 with density of 0.860 — A modified polyester with an Izod impact strength of 150 J "m, obtained by mixing 33 parts by weight of a butene copolymer and melt-extruding the mixture at a cylinder temperature of 280 ° C using a twin-screw extruder. Resin.

 (B-4): a polyethylene terephthalate resin having an intrinsic viscosity of 1.40.

 [Reference Example 4] Production of epoxy-modified polyolefin (c)

 (C-1): Ethylene / butene copolymer (density 0.861, MFR: 0.5 g / 10 minutes) 100 parts by weight, 0.5 part by weight of maleic anhydride, 2 parts by weight 30.0 parts by weight of 3,5-dimethyl-2,5-bis (tert-butylperoxy) hexine were mixed with a helical mixer, and the cylinder temperature was set to 30 mm2 with a cylinder temperature of 240 ° C. The graft modification was performed using an extruder.

 Next, based on 100 parts by weight of the obtained acid-modified ethylene / butene copolymer, a cresol novolak-type epoxy resin (epoxy equivalent: 220, molecular weight: 180

0) 4.6 parts by weight were melt-kneaded with a 3 O mm0 twin screw extruder set at a cylinder temperature of 250 ° C, and the polar group content was 20.0 mmo 1/100 g of epoxy grease. Polyolefin was obtained.

The polar group content is a value obtained by calculation using the following equation (2). (Equation 2)

We 100

 Polar group content (mmol / 100g) = x Ne x 1000

 MWe Wt

We: amount of epoxy resin added (g)

 MWe: molecular weight of epoxy resin

 Ne: Number of epoxy groups per molecule of epoxy resin

 Wt: Total amount of polymer composition (g)

(C-2): ethylene / butene copolymer (density 0.870, MFR: 0.5 g / 10 minutes) 100 parts by weight, 0.5 part by weight of maleic anhydride, 2 parts by weight , 5—Dimethyl-1,2,5-bis (tert-butylperoxy) hexine — 30.0 parts by weight were mixed with a hensil mixer, and the cylinder temperature was set at 240 ° C. Graft modification was performed using a screw extruder.

 Then, 4.6 parts by weight of a cresol nopolak-type epoxy resin (epoxy equivalent: 220, molecular weight: 180,000) was added to 100 parts by weight of the obtained acid-modified ethylene-butene copolymer. The mixture was melted and kneaded with a 3 O mm0 twin screw extruder set to a binder temperature of 250 ° C. to obtain an epoxy-modified polyolefin having a polar group content of 20.0 mmo 1/1000 g.

 (C-3): ethylene / butene copolymer (density 0.870, MFR: 0.5 g / 10 minutes) 100 parts by weight, 1.0 part by weight of maleic anhydride, 30.06 parts by weight of 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexine was mixed with a Hensile mixer, and the mixture was set at a cylinder temperature of 240 ° C. Graft modification was performed using a screw extruder.

Then, with respect to 100 parts by weight of the obtained acid-modified ethylene / butene copolymer, 9.2 parts by weight of a cresol novolak type epoxy resin (epoxy equivalent: 220, molecular weight: 180,000) was added to a cylinder. The mixture was melted and kneaded with a 3 O mm0 twin screw extruder set at a temperature of 250 ° C. to obtain an epoxy-modified polyolefin having a polar group content of 38.3 mmo 1/1000 g. (C-4): Ethylene butene copolymer (density 0.861, MFR: 0.5% / 10 minutes) 100 parts by weight, 0.5 parts by weight of maleic anhydride, 2, 5-dimethyl-1,2,5-bis (tert-butylperoxy) hexine-30.0 parts by weight, and cresol nopolak epoxy resin (epoxy equivalent: 220, molecular weight: 180,000) ) 4.6 parts by weight were mixed with a Hensile mixer, melt-kneaded using a 30 mm ø twin screw extruder set at a cylinder temperature of 240 ° C, and the polar group content was 20.0 mmo 1 / 100 g of an epoxy-modified polyolefin was obtained.

Examples 1 to 8

 As shown in Table 1, the above-mentioned modified PPS resin (a), modified polyester resin (b), and epoxy-modified polyolefin (c) obtained by the reaction of an epoxy compound with polyolefin were used as TEX 30 products manufactured by Nippon Steel Corporation. The melt was kneaded at a cylinder temperature of 280 to 300 ° C and a screw rotation speed of 200 rpm, supplied from the main figure of a twin-screw extruder. After drying the obtained pellet, a test piece was prepared by injection molding (IS100FA manufactured by Toshiba Machine Co., cylinder temperature 280-300 ° C, mold temperature 130 ° C). Table 1 shows the results of measuring the barrier properties and material strength of each sample.

Example 9

Melting point: 280 ° C, MFR: 200 minutes (3,15 ° C, 5 kg load), melt viscosity: 1,500 Pa · s (320 ° C, shear rate: 100,000 sec— ¹ ) 100 parts by weight of the polyphenylene sulfide resin, ethylene glycol glycidyl methacrylate with MFR of 3 g / 10 minutes (190 ° C, 2.16 kg load) = 88/12 (% By weight) When the modified PPS resin obtained by mixing 12.5 parts by weight of the copolymer is 100 parts by weight, MF R = 0.5 (190 ° C, 2.16 kg load) ) The unmelted mixture (A-2 ′) obtained by mixing ethylene-butene copolymer having a density of 0.860 at a ratio of 12 parts by weight was mixed with a TEX30 type twin-screw extruder manufactured by Japan Steel Works, Ltd. Supplied from the main feeder, the modified polyester resin (B-1) and the epoxy-modified polyolefin (C-1) obtained by the reaction of the epoxy compound with the polyolefin are mixed, and then mixed through the side feeder at the tip of the extruder. Supply and syring Over temperature 3 0 0 ° C, Sukuriyu rpm was melt-kneaded as 2 0 0 r P m. The main feeder and side feeder at this time The supply amount from the beginning was adjusted and supplied so that the obtained resin composition had the composition shown in Table 2. After the obtained pellet was dried, a test piece was prepared by injection molding (IS 100 FA manufactured by Toshiba Machine Co., cylinder temperature 300 ° C., mold temperature 130 ° C.). Table 2 shows the results of measuring the barrier properties and material strength of the obtained samples.

Example 10

 For 100 parts by weight of polyethylene terephthalate resin with an intrinsic viscosity of 0.65, ethylene glycol glycidyl methacrylate with an MFR of 3 g / 10 minutes (190 ° C, 2.16 kg load) was used. = 8 8/1 2 (% by weight) 33 parts by weight of copolymer, MFR = 0.5 (190 ° C, 2.16 kg load), density of 0.860 Ethyrenno 1-butene An unmelted mixture (B-Γ) obtained by mixing the copolymer at a ratio of 33 parts by weight was supplied from the main feeder of a TEX 30 type twin screw extruder manufactured by Nippon Steel Works, Ltd., and the modified PPS resin (A-2) and The epoxy-modified polyolefin (C-1) obtained by the reaction between the epoxy compound and polyolefin is mixed and supplied from the side feeder at the tip of the extruder. The cylinder temperature of 300 ° C from the side feeder to the die at the end of the extruder, screw rotation speed 200 r Melt kneading was performed at pm. At this time, the supply amounts from the main feeder and the side feeder were adjusted and supplied so that the obtained resin composition had the composition shown in Table 2. After drying the obtained pellet, a test piece was prepared by injection molding (IS100FA manufactured by Toshiba Machine Co., cylinder temperature 300 ° C, mold temperature 130 ° C). Table 2 shows the results of measuring the barrier properties and material strength of the obtained samples.

Example 11

Melting point 280 ° C, MFR 200 gZl 0 min (3 15 ° C, 5 kg load), melt viscosity 150 Pas (320.C, shear rate 10000 sec— ¹ ) 100 parts by weight of the polyphenylene sulfide resin, MFR 3 g / 10 minutes (190 ° C, 2.16 kg load) Ethylene glycidyl methacrylate = 88/12 (% By weight) When the modified PPS resin obtained by mixing 12.5 parts by weight of the copolymer is 100 parts by weight, MF R = 0.5 (190 ° C, 2.16 kg load) ) The density of 0.86 ethylene An unmelted mixture (A-2 ′) obtained by mixing a butene copolymer at a ratio of 12 parts by weight was supplied from the main feeder of a TEX 30 type twin screw extruder manufactured by Nippon Steel Works, Ltd., and the intrinsic viscosity was 0.65. For each 100 parts by weight of the polyethylene terephthalate resin, ethylene glycol glycidyl methacrylate of MFR 310 minutes (190 ° C, 2.16 kg load) = 88/12 (% by weight) ) 33 parts by weight of copolymer, MFR = 0.5 (190 ° C, 2.16 kg load), 33 weight of ethylene / 1-butene copolymer with density of 0.860 Parts of the unmelted mixture (B-1 ') and the epoxy-modified polyolefin (C-1) obtained by the reaction of the epoxy compound with the polyolefin, and the mixture is supplied from the side feeder at the tip of the extruder. The melt kneading was carried out at a cylinder temperature of 300 ° C. and a screw rotation speed of 200 rpm. At this time, the supply amounts from the main feeder 1 and the side feeder 1 were adjusted and supplied so that the obtained resin composition had the composition shown in Table 2. After the obtained pellet was dried, a test piece was prepared by injection molding (IS 100 FA manufactured by Toshiba Machine Co., Ltd., cylinder temperature: 300 ° C., mold temperature: 130 ° C.). Table 2 shows the results of measurement of the barrier properties and material strength of the obtained samples.

Comparative Examples 1 to 7

 As shown in Table 3, the above-mentioned modified PPS resin (a), modified polyester resin (b), or the following polyamide resin, epoxy-modified polyolefin (c) obtained by reacting an epoxy compound with polyolefin, and the following epoxy Group-containing polyolefins and polyolefins other than the following epoxy group-containing polyolefins were supplied from the main feeder of a TEX30 type twin screw extruder manufactured by Nippon Steel Works, Ltd., and the cylinder temperature was 280-300 ° C. Melt kneading was performed at a screw rotation speed of 200 rpm. After drying the obtained pellets, test specimens were prepared by injection molding (Toshiba Machine Co., IS 100 FA, cylinder temperature 280-300 ° C, mold temperature 130 ° C). did. Table 3 shows the results of measuring the barrier properties and material strength of each sample.

Epoxy group-containing polyolefin>

 Ethylene Z glycidyl methacrylate = 94/4 (weight copolymer) with a length of 33/10 minutes (190, 2.16 kg load)

Polyolefins other than epoxy group-containing polyolefins> MFR = 0.5 (190.C, 2.16 kg load), ethylene / 1-butene copolymer with density 0.860

Polyamide resin>

(MXD 6): Nylon MXD 6 resin with a relative viscosity of 2.20.

 a) Melt viscosity of modified PPS resin Melt viscosity of Z-modified polyester resin

 b) Dispersed particle size of modified polyester resin

c) The dispersed particle size of the epoxy group-containing polyolefin and the polyolefin other than the epoxy group-containing polyolefin in the modified polyester resin d) The parts by weight when the total of the modified PPS resin and the modified polyester resin is 100 parts by weight

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Modified PPS resin type A-2 A-2 ' ^a A-2' ^a)

 Arrangement

 Main quantity ώ | 7 丄 uu 丄 uu

 Feeder Modified Po] ester resin type B- l Β— l

f bone:, ^b )

 d n

 Formulation Epoxy-modified polyolefin type c-i

 FF

 Modified PPS resin type A—2 ο

 Side compounding amount by weight 100

Feeder Modified positive ester resin type ^: Β— 丄 B— 1

 Formulation 鼋 parts by weight 100 100

 Epoxy-modified polyolefin type 1 C-c-1 C-1

Compounding amount by weight ^e ) 5 5 5

 Kneading processing temperature. c 300 300 280-300 300

 Continuous phase of surface layer

 Denatured PPS Denatured PPS Denatured PPS Denatured PPS

 Phase separation

 Central continuous phase

 Denatured PPS Denatured PPS Denatured PPS Denatured PPS

 m.

 Dispersed phase denaturation denaturation denaturation denaturation

 Woester E. Riester Ho. Riester Wolester

 Dispersion particle size (C) 11 m 2 1.5 1.8 2.5

 Dispersion particle size (d) 11 m 0.5 0.5 0.8 0.8

 Barrier properties Permeable permeability 'g 0.45 0.50 0.40 0.55

 G when absorbing moisture 0.85 0.90 0.80 0.90

 Alcohol absorption rate% 1.80 1.75 1.70 1.90

 Alcohol gasoline absorption% 1.35 1.40 1.30 1.45

Material properties Tensile strength MPa 33 31 32 31

 Izod impact strength J / m 900 900 850 850

Low temperature properties Low temperature impact strength J / m 860 850 800 780

a) Unmelted mixture of A_2 components

b) Unmelted mixture of B-1 components

c) Dispersion particle size of modified polyester resin

d) Epoxy group-containing polyolefin in modified polyester resin and dispersed particle size of polyolefin other than epoxy group-containing polyolefine) Part by weight when the total of modified PPS resin and modified polyester resin is 100 parts by weight

As is clear from Examples 1 to 11 and Comparative Examples 1 to 11, a resin composition comprising a modified PPS resin, a modified polyester resin, and an epoxy-modified polyolefin obtained by reacting an epoxy compound with polyolefin was molded. The molded article obtained by this method has excellent barrier properties, particularly excellent impact resistance at low temperatures, and also has excellent barrier properties under moisture absorption and has high practical value.

 Industrial availability

 The molded article obtained by molding the resin composition according to the present invention has good barrier properties and impact resistance, and can be developed for various uses.For example, electric, gas and electronic related equipment, precision machinery related equipment, Suitable for office equipment, automobile and vehicle-related parts, building materials, packaging materials, furniture, and daily necessities.

Claims

Scope of demand

 1. 100 parts by weight of a modified polyphenylene sulfide resin (a) containing a polyphenylene sulfide (a 1) and an epoxy group-containing polyolefin (a 2), and a polyester (b 1) Modified polyester resin containing polyolefin (b 2) containing group and polyolefin (b 3) other than polyolefin containing epoxy group

(b) an epoxy-modified polyolefin obtained by reacting an epoxy compound with polyolefin with respect to 100 parts by weight of a resin composition containing 40 to 250 parts by weight;

a resin composition containing 0.5 to 20 parts by weight of (c), wherein a molded article of the resin composition has a modified resin phase separation structure observed by an electron microscope, and is a modified polyolefin X diene sulfide. A resin composition characterized in that a resin (a) forms a continuous phase and a modified polyester resin (b) forms a dispersed phase in at least a part thereof.

 2. The dispersed phase of the modified polyester resin (b) has an average dispersed particle size of 5 / zm or less, and the epoxy group-containing polyolefin (b 2) and the epoxy group-containing polyolefin (b 2) are dispersed in the dispersed phase of the modified polyester resin (b). The polyolefin (b3) other than the epoxy group-containing polyolefin forms a dispersed phase, and the dispersed phase has a dispersed structure dispersed with an average dispersed particle size of 1 m or less. Resin composition.

 3. The resin composition according to claim 1, wherein the epoxy group-containing polyolefins (a 2) and (b 2) are a copolymer containing a one-year-old olefin and an epoxy group-containing monomer. object.

4. The epoxy-modified polyolefin according to claim 1, wherein the epoxy-modified polyolefin (c) is an epoxy-modified polyolefin obtained by reacting an epoxy compound with a polyolefin having a density of 0.940 g / cm ³ or less. The resin composition according to any one of the above.

 5. The above-mentioned epoxy-modified polyolefin (c) is an ethylene / one-year-old olefin copolymer, and modified ethylene // α- is obtained by grafting at least one kind selected from ethylenically unsaturated carboxylic acids and derivatives thereof. The resin composition according to any one of claims 1 to 4, wherein the resin composition is an epoxy-modified polyolefin obtained by a reaction between a refining copolymer and an epoxy compound.

6. The epoxy-modified polyolefin (c) is strongly mixed with at least one selected from ethylenically unsaturated carboxylic acids and derivatives thereof in the ethylene / α-olefin copolymer. The resin composition according to any one of claims 1 to 4, wherein the resin composition is an epoxy-modified polyolefin obtained by heating a seed together with an epoxy compound in the presence of a radical generator.

 7. The epoxy group-containing polyolefin (a2) is used in an amount of 1 to 50 parts by weight based on 100 parts by weight of the modified polyphenylene sulfide resin (a) and polyphenylene sulfide (a1). The resin composition according to any one of claims 1 to 6, wherein the resin composition is contained.

 8. The modified polyphenylene sulfide resin (a) is used in an amount of 100 parts by weight of a composition comprising a polyphenylene sulfide (a1) and an epoxy group-containing polyolefin (a2). The resin composition according to any one of claims 1 to 7, further comprising 1 to 50 parts by weight of a polyolefin (a3) other than the epoxy group-containing polyolefin.

 9. The resin composition according to any one of claims 1 to 8, wherein the modified polyphenylene sulfide resin (a) has an Izod impact strength of at least 300 J / m.

 100. 100 parts by weight of the modified polyester resin (b), 100 to 100 parts by weight of the polyester (b1), and 100 to 80 parts by weight of an epoxy group-containing polyolefin (b2) and an epoxy group-containing polyolefin. The resin composition according to any one of claims 1 to 9, comprising 10 to 80 parts by weight of a polyolefin other than the above (b3).

11. The resin composition according to any one of claims 1 to 10, wherein the modified polyester resin (b) has an Izod impact strength of 500 JZm or more.