JP7233962B2 - Polyarylene sulfide resin composition - Google Patents

Description

The present invention relates to a resin composition comprising a polyarylene sulfide resin and a polycarbonate resin having a specific amount of hydroxyl end groups, which retains the excellent properties of the polyarylene sulfide resin, as well as peelability during molding and chemical resistance. The present invention relates to a polyarylene sulfide resin composition excellent in toughness and low burr properties.

Polyarylene sulfide resins are engineering plastics that are excellent in chemical resistance, heat resistance, mechanical properties, and the like. Therefore, polyarylene sulfide resins are widely used as electrical and electronic parts, vehicle-related parts, aircraft parts, and housing equipment parts. However, polyarylene sulfide resins are inferior in toughness and impact strength, and there is a problem that burrs are generated during molding. As means for solving this problem, Patent Document 1 discloses a resin composition containing a polyphenylene sulfide resin and a polycarbonate resin. However, conventional commercially available polyphenylene sulfide resins contain a certain amount of sodium as an impurity due to limitations in the polymer polymerization method. Not yet. Patent Document 2 proposes a polyphenylene sulfide resin with a reduced chlorine content. However, decomposition of the polycarbonate resin cannot be suppressed only by using polyphenylene sulfide with a reduced chlorine content. In addition, since the chlorine content is reduced, the reaction process becomes complicated, resulting in poor cost competitiveness. Although Patent Document 3 discloses polyphenylene sulfide with reduced alkali metal content, it is not aimed at modification with polycarbonate resin and is inferior in cost competitiveness. Patent Document 4 discloses a resin composition containing a polyphenylene sulfide resin having a degree of dispersion of 2.5 or less and an alkali metal content of 50 ppm or less and a thermoplastic resin. However, it was not aimed at modification with a polycarbonate resin, particularly for suppressing burrs, and the properties were not satisfactory.

Furthermore, Patent Document 5 discloses a resin composition comprising a polyphenylene sulfide resin and a polycarbonate resin having a branched structure, and Patent Document 6 discloses a resin composition containing a polyphenylene sulfide resin and a polycarbonate resin that suppress decomposition of the polycarbonate resin. Although disclosed, there is no reference to the releasability of the resin composition during molding, and the resin does not stand up to practical use in terms of productivity, such as sticking of the resin to the mold.

JP-A-51-59952 JP 2010-70656 A Japanese Patent Application Laid-Open No. 2008-231250 JP 2008-231249 A JP 2014-231583 A JP 2015-30779 A

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyarylene sulfide resin composition which is excellent in peelability during molding, chemical resistance and low burr property while maintaining the excellent properties of polyarylene sulfide resins.

As a result of extensive studies, the inventors of the present invention have found that a resin composition comprising a polyarylene sulfide resin and a polycarbonate resin having a specific amount of hydroxyl end groups retains the excellent properties of the polyarylene sulfide resin, and at the time of molding, The present inventors have found that they are excellent in releasability, chemical resistance and burr resistance, and have completed the present invention.

Specifically, the above problems are (A) 99 to 1 part by weight of a polyarylene sulfide resin (component A) and (B) a polycarbonate resin (component B) having a hydroxyl group end group content of 20 to 80 eq/t (1 to 99 parts by weight). It is achieved by a polyarylene sulfide resin composition containing parts by weight.

The details of the present invention will be described below.
(A component: polyarylene sulfide resin)
As the polyarylene sulfide resin used as component A in the present invention, any resin may be used as long as it belongs to the category called polyarylene sulfide resin.

Examples of polyarylene sulfide resins include p-phenylene sulfide units, m-phenylene sulfide units, o-phenylene sulfide units, phenylene sulfide sulfone units, phenylene sulfide ketone units, phenylene sulfide ether units, and diphenylene sulfide units. , substituent-containing phenylene sulfide units, branched structure-containing phenylene sulfide units, etc. Among them, those containing 70 mol% or more, particularly 90 mol% or more of p-phenylene sulfide units Preferred, and more preferred is poly(p-phenylene sulfide).

The total chlorine content of the polyarylene sulfide resin used as component A in the present invention is preferably 500 ppm or less, more preferably 450 ppm or less, still more preferably 300 ppm or less, and particularly preferably 50 ppm or less. If the total chlorine content exceeds 500 ppm, the amount of generated gas increases, mold deposits increase, and peelability may deteriorate.

The total sodium content of the polyarylene sulfide resin used as component A in the present invention is preferably 39 ppm or less, more preferably 30 ppm or less, even more preferably 10 ppm or less, and particularly preferably 8 ppm or less. If it exceeds 39 ppm, not only physical properties are lowered by promoting decomposition of the resin, but also in a high temperature and high humidity environment, the water absorption amount of the resin is increased due to the coordination bond between sodium metal and water molecules, which may reduce the heat and humidity resistance. be. The total sodium content was measured by ICP emission spectrometry (ICP-AES method).

The polyarylene sulfide resin used as the A component of the present invention preferably has a dispersity (Mw/Mn) represented by a weight average molecular weight (Mw) and a number average molecular weight (Mn) of 2.7 or more, more preferably 2. 0.8 or more, more preferably 2.9 or more. If the degree of dispersion is less than 2.7, burrs may occur more frequently during molding. Although the upper limit of the degree of dispersion (Mw/Mn) is not particularly defined, it is preferably 10 or less. Here, the weight average molecular weight (Mw) and number average molecular weight (Mn) are values calculated in terms of polystyrene by gel permeation chromatography (GPC). 1-Chloronaphthalene was used as a solvent, and the column temperature was 210°C.

The method for producing the polyarylene sulfide resin is not particularly limited, and it is polymerized by a known method. , 713, JP-A-2013-522385, JP-A-2012-233210, and the production methods described in Japanese Patent No. 5167276. These production methods are methods in which a diiodoaryl compound and solid sulfur are directly heated and polymerized without a polar solvent.

The manufacturing method includes an iodination step and a polymerization step. In the iodination step, an aryl compound is reacted with iodine to give a diiodoaryl compound. In the subsequent polymerization step, the diiodoaryl compound is polymerized with solid sulfur using a polymerization terminator to prepare a polyarylene sulfide resin. Iodine is generated in gaseous form in this process, and this is recovered and used again in the iodination process. Iodine is essentially a catalyst.

A representative solid sulfur used in the method of preparation includes the cyclooctasulphur form (S ₈ ) with 8 atoms linked at room temperature. However, the sulfur compound used in the polymerization reaction is not limited and may be used in any form as long as it is solid or liquid at room temperature.

Typical diiodoaryl compounds used in the production method include at least one selected from the group consisting of diiodobenzene, diiodonaphthalene, diiodobiphenyl, diiodobisphenol and diiodobenzophenone, and alkyl Derivatives of iodoaryl compounds to which a group or sulfone group is attached, or to which oxygen or nitrogen is introduced are also used. Iodoaryl compounds are classified into different isomers depending on the bonding position of the iodine atom, and preferred examples of these isomers are p-diiodobenzene, 2,6-diiodonaphthalene, and p,p'-diiodine. It is a compound in which iodine is symmetrically positioned at both ends of an aryl compound, such as biphenyl. The content of the iodoaryl compound is preferably 500 to 10,000 parts by weight with respect to 100 parts by weight of the solid sulfur. This amount is determined in consideration of the formation of disulfide bonds.

Typical polymerization terminator used in the production method include monoiodoaryl compounds, benzothiazoles, benzothiazolesulfenamides, thiurams, dithiocarbamates, aromatic sulfide compounds and the like. Preferred examples of monoiodoaryl compounds include at least one selected from the group consisting of iodobiphenyl, iodophenol, iodoaniline, and iodobenzophenone. Preferred examples of benzothiazoles include at least one selected from the group consisting of 2-mercaptobenzothiazole and 2,2'-dithiobisbenzothiazole. Preferred examples of benzothiazolesulfenamides include N-cyclohexylbenzothiazole 2-sulfenamide, N,N-dicyclohexyl-2-benzothiazolesulfenamide, 2-morpholinothiobenzothiazole, and benzothiazolesulfenamide. , dibenzothiazole disulfide, and N-dicyclohexylbenzothiazole 2-sulfenamide. Preferred examples of thiurams include at least one selected from the group consisting of tetramethylthiuram monosulfide and tetramethylthiuram disulfide. Preferred examples of dithiocarbamates include at least one selected from the group consisting of zinc dimethyldithiocarbamate and zinc diethyldithiocarbamate. Preferred examples of aromatic sulfide compounds include at least one selected from the group consisting of diphenyl sulfide, diphenyl disulfide, diphenyl ether, biphenyl, and benzophenone. In any polymerization terminator, one or more functional groups may be substituted on the conjugated aromatic ring skeleton. Examples of the functional group include a hydroxy group, a carboxyl group, a mercapto group, an amino group, a cyano group, a sulfo group, a nitro group, etc. Preferred examples include a carboxyl group and an amino group, and more preferred examples include includes a carboxyl group and an amino group showing a peak at 1600 to 1800 cm ^-1 or 3300 to 3500 cm ^-1 on the FT-IR spectrum. The content of the polymerization terminator is preferably 1 to 30 parts by weight with respect to 100 parts by weight of the solid sulfur. This amount is determined in consideration of the formation of disulfide bonds.

Further, as the polyarylene sulfide resin used as the component A of the present invention, for the purpose of obtaining higher compatibility, a carboxyl group, a carboxyl group derivative group, a thiol group, a sulfone group, a hydroxy group, an amino group, an epoxy group, A polyarylene sulfide resin having a terminal reactive functional group such as a mercapto group, a cyano group, or a nitro group can also be used. By using a polyarylene sulfide resin having the reactive functional group at the end, it exhibits excellent compatibility with other polymer materials and carbon fibers, etc., is excellent in peelability, and has higher mechanical strength. A composition can be obtained. A more preferred example of the polyarylene sulfide resin having the reactive functional group at its terminal is a polyarylene sulfide resin having at least one terminal group structure selected from carboxyl groups and amino groups. The polyarylene sulfide resin having at least one terminal group structure selected from carboxyl groups and amino groups is an FT-IR spectrum derived from a carboxyl group at about 1600 to 1800 cm ^-1 or amino When the peak of about 3300 to 3500 cm ^-1 derived from the group and the height intensity of the aromatic ring stretching peak appearing at 1400 to 1600 cm ^-1 is taken as 100%, the above about 1600 to 1800 cm ^-1 or about 3300 to 3500 cm ^{-1 1} is a polyarylene sulfide resin having a peak relative height intensity of 0.001 to 10%.

A particularly preferred example of the polyarylene sulfide resin having at least one terminal group structure selected from the carboxyl group and amino group is a polyarylene sulfide resin having a terminal group structure of a carboxyl group, which has the following general formula (1 ) in structural units.

（式中、Ａｒ基はアリーレン基である。）

(In the formula, the Ar group is an arylene group.)

Here, the arylene group may be p-phenylene group, m-phenylene group, o-phenylene group, substituted phenylene group, and the like. Specifically, the substituted phenylene group is one or more of F, Cl, Br, C1-C3 alkyl, trifluoromethyl, C1-C3 alkoxy, trifluoromethoxy, trifluoromethylthio, dimethylamino, cyano, A phenylene group optionally substituted with (C1-C3 alkyl)SO ₂ —, (C1-C3 alkyl)NHSO ₂ —, (C1-C3 alkyl)2NSO ₂ —, NH ₂ SO ₂ —.

The method for introducing the reactive functional group into the polyarylene sulfide resin is not particularly limited, and polymerization is performed by a known method. A method using a polymerization terminator having the represented group is included. Examples of the conjugated aromatic ring skeleton used in the polymerization terminator include diphenyl disulfide, monoiodobenzene, thiophenol, 2,2′-dibenzothiazolyl disulfide, 2-mercaptobenzothiazole, N-cyclohexyl-2-benzo thiazolylsulfenamide, 2-(morpholinothio)benzothiazole, N,N'-dicyclohexyl-1,3-benzothiazole-2-sulfenamide and the like.

（式中、Ｒは水素原子またはアルカリ金属原子である。）

(Wherein, R is a hydrogen atom or an alkali metal atom.)

As a suitable polymerization method for producing a polyarylene sulfide resin having a carboxyl terminal group structure, a step of polymerizing a reactant containing a diiodo aromatic compound and a sulfur element, and during the polymerization reaction step, carboxyl A manufacturing method of adding a compound having a group to substitute a terminal group of a polyarylene sulfide main chain with a carboxyl group. Typical examples used in the compound having a carboxyl group include at least one selected from the group consisting of 2-iodobenzoic acid, 3-iodobenzoic acid, 4-iodobenzoic acid, and 2,2'-dithiobenzoic acid. seeds. The compound having a carboxyl group may be added in an amount of about 0.0001-5 parts by weight based on 100 parts by weight of the diiodo aromatic compound.

A polymerization reaction catalyst may be used in the production method, and a typical polymerization reaction catalyst is a nitrobenzene-based catalyst. Preferred examples of nitrobenzene-based catalysts include 1,3-diiodo-4-nitrobenzene, 1-iodo-4-nitrobenzene, 2,6-diiodo-4-nitrophenol, iodonitrobenzene, 2,6-diiodo-4- At least one selected from the group consisting of nitroamines can be mentioned. The content of the polymerization reaction catalyst is preferably 0.01 to 20 parts by weight with respect to 100 parts by weight of the solid sulfur. This amount is determined in consideration of the formation of disulfide bonds.

A representative example of the reaction conditions for the production process ranges from initial reaction conditions of temperature 180-250° C. and pressure 50-450 Torr (6.7-60 kPa) to temperature 270-350° C. and pressure 0.001-20 Torr (0.001-20 Torr). The temperature is increased and the pressure is decreased for 1-30 hours to a final reaction condition of .00013-2.7 kPa). Preferably, the initial reaction conditions are a temperature of 180° C. or higher and a pressure of 450 Torr (60 kPa) or lower in consideration of the reaction rate, and the final reaction conditions are a temperature of 350° C. or lower and a pressure of 20 Torr (2. 7 kPa) or less.

However, the conditions for the polymerization reaction are not particularly limited because they depend on the structural design and production rate of the reactor and are known to those skilled in the art. Reaction conditions can be appropriately set by those skilled in the art in consideration of process conditions.
By using this polymerization method, it is possible to obtain a polyphenylene sulfide resin excellent in cost performance without substantially reducing the sodium content.
The polyphenylene sulfide resin of the present invention may also contain polyphenylene sulfide resins obtained by other polymerization methods.

(B component: polycarbonate resin)
The polycarbonate resin used in the present invention is obtained by reacting a dihydric phenol with a carbonate precursor. Examples of the reaction method include an interfacial polymerization method, a melt transesterification method, a solid-phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound, but the melt transesterification method is preferred. The polycarbonate resin may also be a branched polycarbonate resin obtained by polymerizing trifunctional phenols, and a copolymer obtained by copolymerizing an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, or a divalent aliphatic or alicyclic alcohol. It may be polycarbonate.

The viscosity average molecular weight of the polycarbonate resin is preferably 1.3×10 ⁴ to 4.0×10 ⁴ , more preferably 1.5×10 ⁴ to 3.8×10 ⁴ . The viscosity average molecular weight (M) of the aromatic polycarbonate resin is obtained by inserting the specific viscosity (η _sp ) obtained at 20° C. from a solution of 0.7 g of the polycarbonate resin dissolved in 100 ml of methylene chloride into the following equation. Details of such a polycarbonate resin are described in JP-A-2002-129003.
η _sp /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[η]=1.23×10 ⁻⁴ M ^0.83
c=0.7

The hydroxyl end group content of the polycarbonate resin is 20 to 80 eq/t, preferably 30 to 75 eq/t, more preferably 35 to 65 eq/t. If the amount of hydroxyl terminal groups is less than 20 eq/t, the compatibility with polyarylene sulfide is lowered and the releasability is deteriorated. On the other hand, if it is more than 80 eq/t, the degree of crystallinity of polyarylene sulfide will be lowered and the peelability will be deteriorated. The hydroxyl end group content of the polycarbonate resin can be adjusted by the following method. In the case of the interfacial polycondensation method, the amount of hydroxyl terminal groups is adjusted by the use of the catalyst and the amount and time of addition of the terminal terminator. It is also effective to carry out the polymerization reaction in a stationary state. In the melt transesterification method, it is possible to reduce the amount of hydroxyl terminal groups by making the abundance ratio of the dihydric phenol and the carbonate ester closer to the carbonate ester.

In addition, the amount of hydroxyl group terminal groups of polycarbonate resin is measured by the following NMR method. That is, the amount of hydroxyl group end groups is obtained by performing 1H-NMR non-decoupling measurement from a solution in which 40 mg of polycarbonate resin pellets or powder is dissolved in 1 ml of heavy chloroform, and chemical shifts of 6.66 to 6.73 ppm and 6.66 to 6.73 ppm from the 1H-NMR spectrum chart. It is obtained by inserting the integrated value of the peak at 6.93 to 7.00 ppm into the following equation.
OH terminal group amount (eq/ton) = [(A/2)/(B/(C×2/100))]×(1000000/D)
A: 6.66 to 6.73 ppm peak integral value B: 6.93 to 7.00 ppm peak integral value C: Abundance of carbon isotope 13C (1.108%)
D: mass number per unit of PC (bisphenol A polycarbonate: 254)

Polycarbonate resins used in the present invention may be various polycarbonate resins having high heat resistance or low water absorption, polymerized using other dihydric phenols, in addition to the commonly used bisphenol A type polycarbonate. good. Specific examples of various polycarbonate resins having high heat resistance or low water absorption that are polymerized using other dihydric phenols include the following.

(1) 4,4'-(m-phenylenediisopropylidene)diphenol (hereinafter abbreviated as "BPM") component in 100 mol% of the dihydric phenol component constituting the polycarbonate is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%), and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (hereinafter abbreviated as “BCF”) component is 20 to 80 mol % (more preferably 25 to 60 mol %, still more preferably 35 to 55 mol %) copolymerized polycarbonate.

(2) Bisphenol A component is 10 to 95 mol% (more preferably 50 to 90 mol%, still more preferably 60 to 85 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and a copolymer polycarbonate having a BCF component of 5 to 90 mol% (more preferably 10 to 50 mol%, still more preferably 15 to 40 mol%).

(3) BPM component is 20 to 80 mol% (more preferably 40 to 75 mol%, still more preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane component is 20 to 80 mol% (more preferably 25 to 60 mol%, still more preferably 35 to 55 mol%) Copolycarbonate. These special polycarbonates may be used alone or in combination of two or more. Moreover, these can also be used by mixing with a widely used bisphenol A type polycarbonate. The manufacturing method and characteristics of these special polycarbonates are described in detail in, for example, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435 and JP-A-2002-117580. ing. It is also possible to use a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing polyorganosiloxane units.

As polycarbonate resins, not only virgin raw materials but also polycarbonate resins recycled from used products can be used. Examples of used products include containers typified by water bottles, optical discs, and automobile headlamps.

The content of component B is 1 to 99 parts by weight, preferably 5 to 95 parts by weight, more preferably 5 to 30 parts by weight and 70 to 95 parts by weight, based on a total of 100 parts by weight of components A and B. . When the content is 5 to 30 parts by weight, it may be possible to design a resin that takes advantage of the excellent properties of the polyphenylene sulfide resin, while when the content is 70 to 95 parts by weight, the polycarbonate resin is more excellent. It may be possible to design a resin that takes advantage of its characteristics. If the content is less than 1 part by weight, the characteristics of the polycarbonate resin cannot be exhibited and the occurrence of burrs cannot be suppressed. On the other hand, if the amount is more than 99 parts by weight, the characteristics of the polyphenylene sulfide resin are not exhibited and the chemical resistance is deteriorated.

(C component: filler)
The resin composition of the present invention may further contain fillers. Although the material is not particularly limited, fillers such as fibrous, plate-like, powdery and granular fillers can be used. Specific examples include glass fiber, milled glass fiber, wollastonite, carbon fiber, wholly aromatic polyamide fiber, potash titanate whisker, zinc oxide whisker, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, gypsum fiber. , metal fibers and the like, and glass fibers, glass milled fibers, wollastonite, carbon fibers and wholly aromatic polyamide fibers are preferably used. In addition, sericite, kaolin, mica, clay, bentonite, asbestos, talc, silicates such as alumina silicate, swelling layered silicates such as montmorillonite and synthetic mica, alumina, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide , iron oxide and other metal compounds, calcium carbonate, magnesium carbonate, dolomite and other carbonates, calcium sulfate, barium sulfate and other sulfates, glass flakes, glass beads, ceramic beads, boron nitride, silicon carbide, calcium phosphate and silica, and glass flakes, mica, talc, calcium carbonate, and glass beads are preferably used. These may be hollow, and two or more of these fillers may be used in combination.

These fillers are pretreated with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, and an epoxy compound, or with an organic onium ion in the case of a swelling layered silicate. Its use is preferable in terms of obtaining better mechanical strength.

A conductive filler can be used as a filler for imparting conductivity to the resin composition of the present invention. The conductive filler is not particularly limited as long as it is a conductive filler that is commonly used to make resin conductive, and specific examples thereof include metal powder, metal flakes, metal ribbons, metal fibers, metal oxides, and conductive substances. Coated inorganic fillers, carbon powder, graphite, carbon fibers, carbon flakes, scaly carbon and the like can be used. Specific examples of metal powders, metal flakes, and metal ribbons include silver, nickel, copper, zinc, aluminum, stainless steel, iron, brass, chromium, and tin. Specific examples of metal species of metal fibers include iron, copper, stainless steel, aluminum, and brass. Such metal powders, metal flakes, metal ribbons, and metal fibers may be surface-treated with a titanate-based, aluminum-based, or silane-based surface treatment agent.

Specific examples of metal oxides include SnO ₂ (antimony-doped), In ₂ O ₃ (antimony-doped), and ZnO (aluminum-doped). It may be surface-treated with a treating agent.

Specific examples of conductive substances in inorganic fillers coated with conductive substances include aluminum, nickel, silver, carbon, SnO ₂ (antimony-doped), and In ₂ O ₃ (antimony-doped). Inorganic fillers to be coated include mica, glass beads, glass fibers, carbon fibers, potassium titanate whiskers, barium sulfate, zinc oxide, titanium oxide, aluminum borate whiskers, zinc oxide whiskers, titanate whiskers, carbonized A silicon whisker etc. can be illustrated. Examples of coating methods include a vacuum deposition method, a sputtering method, an electroless plating method, and a baking method. Moreover, these may be surface-treated with a surface treatment 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 manufacturing method. The raw material and manufacturing 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.

The content of component C is preferably 5 to 400 parts by weight, more preferably 10 to 200 parts by weight, and particularly preferably 20 to 150 parts by weight, based on 100 parts by weight of components A and B combined. be. If the content of the C component is less than 5 parts by weight, the rigidity and heat resistance may be deteriorated, and if it exceeds 400 parts by weight, the moldability may be deteriorated.

By the way, as the C component in the present invention, carbon fibers having a tensile elastic modulus of 250 GPa or more as measured by JIS R7608 are preferable from the viewpoint of the effect of the present invention. Specific carbon fibers include carbon fibers, carbon milled fibers, carbon nanotubes, and the like. Carbon nanotubes preferably have a fiber diameter of 0.003 to 0.1 μm. They may also be monolayer, bilayer and multilayer, with multilayers (so-called MWCNTs) being preferred. Carbon milled fibers preferably have an average fiber length of 0.05 to 0.2 mm. Among these, carbon fiber is preferable in terms of excellent mechanical strength. Any of cellulose-based, polyacrylonitrile-based, and pitch-based carbon fibers can be used as the carbon fiber. Alternatively, it can be obtained by spinning or molding a raw material composition consisting of a solvent and a polymer of aromatic sulfonic acids or their salts with a methylene type bond, followed by carbonization, and spinning without an infusibilization step. It is also possible to use the Among these, a polyacrylonitrile-based high elastic modulus type is particularly preferable. However, if the tensile modulus of the carbon fiber exceeds 600 GPa, the carbon fiber becomes very expensive and the versatility of the raw material decreases, so the preferable range of the tensile modulus of the carbon fiber to be used is 250 to 600 GPa. , more preferably 260 to 500 GPa. Moreover, the tensile strength of the carbon fiber measured according to JIS R7608 is preferably 3,000 MPa or more. However, if the tensile strength of the carbon fiber exceeds 7,000 MPa, the carbon fiber becomes very expensive as well as the tensile modulus, and the versatility decreases from the viewpoint of raw material supply. 3,000 to 7,000 MPa, more preferably 5,000 to 6,500 MPa. Although the average fiber diameter of the carbon fiber is not particularly limited, it is preferably 3 to 15 μm, more preferably 4 to 13 μm. Carbon fibers having an average fiber diameter within this range can exhibit good mechanical strength and fatigue properties without impairing the appearance of molded products. The number average fiber length of carbon fibers in the resin composition is preferably 60 to 500 μm, more preferably 80 to 400 μm, particularly preferably 100 to 300 μm. The number-average fiber length is a value calculated by an image analysis device from optical microscopic observation of the carbon fiber residue collected by processing such as high-temperature incineration, solvent dissolution, and chemical decomposition of the molded product. be. In addition, when calculating such a value, the value is obtained by a method that does not count fibers having a length equal to or less than the fiber length.

The above carbon fiber may be coated with a metal layer on the surface of the carbon fiber. Examples of metals include silver, copper, nickel, and aluminum, and nickel is preferred from the viewpoint of corrosion resistance of the metal layer. As the method of metal coating, various methods described above in the surface coating of the glass filler with a different material can be employed. Among them, the plating method is preferably used. Also in the case of such a metal-coated carbon fiber, the carbon fiber mentioned above can be used as the original carbon fiber. The thickness of the metal coating layer is preferably 0.1-1 μm, more preferably 0.15-0.5 μm. More preferably, it is 0.2 to 0.35 μm. Such metal-uncoated carbon fibers and metal-coated carbon fibers are preferably bundled with olefin-based resins, styrene-based resins, acrylic-based resins, polyester-based resins, epoxy-based resins, and urethane-based resins. In particular, carbon fibers treated with urethane-based resins and epoxy-based resins are suitable in the present invention because of their excellent mechanical strength. The amount of the sizing agent in the metal-uncoated carbon fiber and the metal-coated carbon fiber is not particularly limited, but the smaller the amount of the sizing agent, the better, in order to improve the weld strength. A preferred amount of sizing agent is 0-4%, more preferably 0.1-3%.

When carbon fiber or wholly aromatic polyamide fiber is used as the C component, the content is preferably 15 to 180 parts by weight, more preferably 18 to 150 parts by weight, with respect to the total 100 parts by weight of the A component and the B component. More preferably 20 to 140 parts by weight.

(other ingredients)
The resin composition of the present invention may contain an elastomer component within a range that does not impair the effects of the present invention. Suitable elastomer components include acrylonitrile-butadiene-styrene copolymer (ABS resin), methyl methacrylate-butadiene-styrene copolymer (MBS resin), and core-shell such as silicone-acrylic composite rubber graft copolymer. Examples thereof include graft copolymer resins, thermoplastic elastomers such as silicone thermoplastic elastomers, olefin thermoplastic elastomers, polyamide thermoplastic elastomers, polyester thermoplastic elastomers, and polyurethane thermoplastic elastomers.

The resin composition of the present invention may contain other thermoplastic resins as long as the effects of the present invention are not impaired. Other thermoplastic resins include, for example, polyethylene resins, polypropylene resins, general-purpose plastics represented by polyalkyl methacrylate resins, polyphenylene ether resins, polyacetal resins, aromatic polyester resins, liquid crystalline polyester resins, polyamide resins, cyclic Engineering plastics represented by polyolefin resin, polyarylate resin (amorphous polyarylate, liquid crystalline polyarylate), polytetrafluoroethylene, polyetheretherketone, polyetherimide, polysulfone, polyethersulfone, etc. So-called super engineering plastics can be mentioned.

Antioxidants, heat stabilizers (hindered phenols, hydroquinones, phosphites and substituted compounds thereof), weathering agents (resorcinol , salicylates, benzotriazoles, benzophenones, hindered amines, etc.), release agents and lubricants (montanic acid and its metal salts, its esters, its half esters, stearyl alcohol, stearamide, various bisamides, bisurea and polyethylene waxes, etc.) ), pigments (cadmium sulfide, phthalocyanine, carbon black, etc.), dyes (nigrosine, etc.), crystal nucleating agents (talc, silica, kaolin, clay, etc.), plasticizers (octyl p-oxybenzoate, N-butylbenzenesulfonamide etc.), antistatic agents (alkyl sulfate type anionic antistatic agents, quaternary ammonium salt type cationic antistatic agents, nonionic antistatic agents such as polyoxyethylene sorbitan monostearate, betaine amphoteric antistatic agents etc.), flame retardants (red phosphorus, phosphates, melamine cyanurate, magnesium hydroxide, hydroxides such as aluminum hydroxide, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, brominated epoxy resins or combinations of these brominated flame retardants with antimony trioxide) and other polymers can be added.

(Manufacture of resin composition)
The resin composition of the present invention can be produced by mixing the above components at the same time or in any order using a mixer such as a tumbler, V-type blender, Nauta mixer, Banbury mixer, kneading rolls, and extruder. Melt-kneading by a twin-screw extruder is preferable, and if necessary, it is preferable to feed optional components into other melt-mixed components from a second feed port using a side feeder or the like. As the extruder, it is preferable to use an extruder having a vent capable of degassing moisture in the raw material and volatile gas generated from the melt-kneaded resin. A vacuum pump is preferably installed from the vent for efficiently discharging generated moisture and volatile gas to the outside of the extruder. It is also possible to install a screen in front of the die portion of the extruder to remove foreign matters and the like mixed in the extruded raw material to remove the foreign matters from the resin composition. Such screens include wire meshes, screen changers, sintered metal plates (such as disk filters), and the like.

Screws used in twin-screw extruders are constructed by inserting screw pieces of various shapes between forward flight pieces for transportation, combining them in a complex manner, and integrating them into a single screw. Screw pieces such as forward kneading pieces, reverse kneading pieces, reverse flight pieces, forward flight pieces with notches, reverse flight pieces, etc. are arranged and combined in an appropriate order and position in consideration of the characteristics of the raw material to be processed. and so on. Examples of the melt-kneader include a Banbury mixer, a kneading roll, a single-screw extruder, and a multi-screw extruder having three or more screws, in addition to the twin-screw extruder.

The resin extruded as described above is either directly cut and pelletized, or is pelletized by forming strands and then cutting the strands with a pelletizer. It is preferable to clean the atmosphere around the extruder when it is necessary to reduce the influence of external dust during pelletization. The shape of the obtained pellets can take general shapes such as cylinders, prisms, and spheres, but cylinders are more preferable. The diameter of such a cylinder is preferably 1-5 mm, more preferably 1.5-4 mm, still more preferably 2-3.5 mm. On the other hand, the length of the cylinder is preferably 1-30 mm, more preferably 2-5 mm, and even more preferably 2.5-4 mm.

The total sodium content of the resin composition of the present invention is preferably 39 ppm or less, more preferably 30 ppm or less, still more preferably 10 ppm or less, and particularly preferably 8 ppm or less. If the total sodium content exceeds 39 ppm, the decomposition of the polycarbonate resin cannot be suppressed, so that the burr suppressing effect of the polycarbonate resin is not exhibited, and in the worse case, pelletization may become difficult.

(About molded products)
A molded article using the resin composition of the present invention can be obtained by molding the pellets produced as described above. It is preferably obtained by injection molding or extrusion molding. In injection molding, not only ordinary molding methods, but also injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including the method of injecting supercritical fluid), insert molding, in-mold coating molding, heat insulation metal Mold molding, rapid heating and cooling mold molding, two-color molding, multi-color molding, sandwich molding, ultra-high speed injection molding and the like can be mentioned. For molding, either cold runner method or hot runner method can be selected. Extrusion molding can also provide various shaped extruded products, sheets, films, and the like. Inflation method, calendering method, casting method and the like can be used for forming sheets and films. Further, it can be molded as a heat-shrinkable tube by subjecting it to a specific stretching operation. The resin composition of the present invention can also be molded by rotational molding, blow molding, or the like.

The resin composition of the present invention is a resin composition comprising a polyarylene sulfide resin and a polycarbonate resin having a specific amount of hydroxyl end groups, which maintains the excellent properties of the polyarylene sulfide resin and exhibits peeling during molding. Because it is a polyarylene sulfide resin composition with excellent chemical resistance and low burr properties, it is widely used in PCs, tablets, mobile phone housings, displays, OA equipment, mobile phones, personal digital assistants, facsimiles, compact discs, and portable devices. Electric and electronic equipment such as MDs, portable radio cassettes, PDAs (personal digital assistants such as electronic notebooks), video cameras, digital still cameras, optical equipment, audio equipment, air conditioners, lighting equipment, entertainment goods, toys, and other home appliances housings and internal members such as trays and chassis, their cases, mechanical parts, construction materials such as panels, motor parts, alternator terminals, alternator connectors, IC regulators, potentiometer bases for light gear, suspension parts, exhaust gas valves, etc. Various valves, fuel related pipes, exhaust or intake system pipes, air intake nozzle snorkels, intake manifolds, various arms, various frames, various hinges, various bearings, fuel pumps, gasoline tanks, CNG tanks, engine coolant joints, carburetor mains Body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake butt wear sensor, thermostat base for air conditioner, heating hot air flow control Valves, brush holders for radiator motors, water pump impellers, turbine vanes, wiper motor related parts, distributors, starter switches, starter relays, wire harnesses for transmissions, window washer nozzles, air conditioner panel switch substrates, fuel-related electromagnetic valves Coils, fuse connectors, battery trays, AT brackets, headlamp supports, pedal housings, steering wheels, door beams, protectors, chassis, frames, armrests, horn terminals, step motor rotors, lamp sockets, lamp reflectors, lamp housings, brake pistons, noise sea Ludo, radiator support, spare tire cover, seat shell, solenoid bobbin, engine oil filter, ignition device case, under cover, scuff plate, pillar trim, propeller shaft, wheel, fender, fascia, bumper, bumper beam, bonnet, aero parts, Automobiles such as platforms, cowl louvers, roofs, instrument panels, spoilers and various modules, motorcycle-related parts, members and aircraft such as outer panels, landing gear pods, winglets, spoilers, edges, ladders, elevators, failings and ribs Widely useful in related parts, members and outer panels, windmill blades, etc., especially electronics housings such as housings for computers, notebooks, ultrabooks, tablets, mobile phones, and inverter housings for hybrid and electric vehicles. It is widely useful in the field, and its industrial effect is exceptional.

The best mode of the present invention, which the present inventors consider to be the best, summarizes the preferable range of each of the requirements described above, and representative examples thereof are described in the following examples, for example. Of course, the present invention is not limited to these forms.

[Evaluation of Resin Composition]
(1) Peelability Evaluation The degree of peeling during molding of test pieces was evaluated according to ISO527-1. The test piece was obtained by drying the pellets obtained below at 130 ° C. for 6 hours in a hot air circulation dryer, and then using an injection molding machine (SG-150U manufactured by Sumitomo Heavy Industries, Ltd.) at a cylinder temperature of 300 ° C. Molding was performed at a mold temperature of 150°C. When sticking to the mold was observed, it was assumed that peeling failure occurred, and the occurrence rate was calculated from the number of peeling failures observed during continuous 10 shots. When the rate of poor peeling was 0 to 10%, ◯ was given. When the rate of poor peeling was 20 to 30%, Δ was given.
(2) Fluidity Evaluation Using the resin pellets obtained below, the melt volume rate (MVR value) was measured at 300° C. under a load of 2.16 kg according to ISO1133 standards. The thermoplastic material was preliminarily dried at 130° C. for 4 hours with a hot air dryer for the measurement. Melt Indexer 2A manufactured by Toyo Seiki Co., Ltd. was used for the measurement.
(3) Evaluation of burrs Evaluation of burrs was carried out by measuring the length of the burrs on the portion of the test piece that comes into contact with the gas vent in accordance with ISO527-1. The gas vent had a thickness of 10 μm and a width of 5 mm.
(4) Evaluation of chemical resistance A test piece conforming to ISO527-1 was immersed in gasoline, and the appearance was observed after 24 hours. The case where there was no change in appearance was rated as ◯, and the case where cracks or the like occurred was rated as x.

[Examples 1 to 16, Comparative Examples 1 to 4]
A polyarylene sulfide resin, a polycarbonate resin and a filler were melt-kneaded in the amounts shown in Tables 1 and 2 using a vented twin-screw extruder to obtain pellets. The vented twin-screw extruder used was TEX-30XSST (completely meshed, co-rotating) manufactured by The Japan Steel Works, Ltd. The extrusion conditions were a discharge rate of 12 kg/h, a screw rotation speed of 150 rpm, and a vent vacuum degree of 3 kPa. The fillers other than the particulate fillers (calcium carbonate) are supplied from the second supply port using the side feeder of the extruder, and the polyarylene sulfide resin, polycarbonate resin and particulate fillers (calcium carbonate ) was supplied to the extruder through the first supply port. The first supply port here is the supply port farthest from the die, and the second supply port is the supply port located between the die and the first supply port of the extruder. After drying the obtained pellets at 130 ° C. for 6 hours in a hot air circulating dryer, an injection molding machine (SG-150U manufactured by Sumitomo Heavy Industries, Ltd.) was used at a cylinder temperature of 300 ° C. and a mold temperature of 130 ° C. Under these conditions, a test piece for evaluation was molded.

The total sodium content of the polyphenylene sulfide resin is determined by adding sulfuric acid to the pellets, incinerating them, melting them with potassium hydrogen sulfate, dissolving them in dilute nitric acid, adding pure water to a constant volume, and then analyzing them by ICP emission spectrometry (ICP-AES method). ) was used for quantitative analysis. As a measurement device, ICP-AES VISTA-MPX manufactured by Varian was used.

The specific viscosity of the polycarbonate resin oligomer or polymer was measured by dissolving 0.7 g of the oligomer or polymer in 100 ml of methylene chloride and using an Ostwald viscometer at a temperature of 20°C.

The hydroxyl group terminal amount of the polycarbonate resin was calculated by obtaining an integral value from the NMR spectrum chart. 40 mg of polycarbonate resin pellets or powder was dissolved in 1 ml of deuterated chloroform, charged into an NMR sample tube with an inner diameter of 5 mm so that the liquid level was 40 mm, and capped to prepare a sample for NMR measurement. This was subjected to 1H-NMR measurement using FT-NMR AL-400 manufactured by JEOL Ltd. without decoupling, with 512 integration times. From the obtained NMR spectrum chart, the integrated values of the peaks at chemical shifts of 6.66 to 6.73 ppm and 6.93 to 7.00 ppm were obtained, and the amount of hydroxyl terminal groups (eq/ton) was calculated from the following formula.
Amount of hydroxyl group end groups (eq/ton) = [(A/2)/(B/(C×2/100))]×(1000000/D)
A: 6.66 to 6.73 ppm peak integral value B: 6.93 to 7.00 ppm peak integral value C: Abundance of carbon isotope 13C (1.108%)
D: mass number per unit of PC (bisphenol A polycarbonate: 254)

Each component represented by symbols in Tables 1 and 2 is as follows.
<A component>
A-1: Polyphenylene sulfide resin obtained in Production Method 1 [Production Method 1]
To 300.00 g of paradiiodobenzene and 27.00 g of sulfur, 0.60 g of diphenyl disulfide as a polymerization terminator (content of 0.65% by weight based on the weight of the final polymerized PPS) was added and heated to 180°C. After heating to completely melt and mix them, the temperature was raised to 220°C and the pressure was lowered to 200 Torr. The resulting mixture was polymerized for 8 hours while changing the temperature and pressure stepwise so that the final temperature and pressure were 320° C. and 1 Torr, respectively, to prepare a polyphenylene sulfide resin. Total sodium content was 7 ppm. Further, the dispersity (Mw/Mn) represented by weight average molecular weight (Mw) and number average molecular weight (Mn) was 4.7.

A-2: Polyphenylene sulfide resin obtained in Production Method 2 [Production Method 2]
The reactants containing 5130 g of paradiiodobenzene and 450 g of sulfur and 4 g of mercaptobenzothiazole as a reaction initiator were heated to 180° C. for complete melting and mixing, then the temperature was raised to 220° C. and the pressure was raised to 350 Torr. dropped to. The polymerization reaction was allowed to proceed while gradually changing the temperature and pressure of the resulting mixture so that the final temperature and pressure were 300° C. and 1 Torr or less, respectively. When the polymerization reaction has progressed by 80% (the degree of progress of the polymerization reaction was confirmed by the relative ratio of viscosity ((current viscosity/target viscosity)×100%)), 25 g of mercaptobenzothiazole was added as a polymerization terminator. and reacted. After 1 hour, 51 g of 4-iodobenzoic acid was added and the reaction was carried out for 10 minutes under nitrogen atmosphere. at the main chain end of the polyarylene sulfide resin. The presence of a carboxyl group peak at 1600 to 1800 cm ⁻¹ was confirmed in the FT-IR spectrum of the obtained polyarylene sulfide. The relative height intensity of the peak at 1600 to 1800 cm ^-1 was 3.4% when the height intensity of the aromatic ring stretching peak appearing at 1400 to 1600 cm ^-1 was taken as 100%. Total sodium content was 7 ppm. Further, the dispersity (Mw/Mn) represented by weight average molecular weight (Mw) and number average molecular weight (Mn) was 4.11.
A-3: Polyphenylene sulfide resin (DIC-PPS MA-505 manufactured by DIC, total sodium content 160 ppm, degree of dispersion (Mw/Mn) 3.5)

<B component>
B-1: Polycarbonate resin obtained by production method 3 (viscosity average molecular weight 89000, hydroxyl terminal group weight 22 eq/t)
[Manufacturing method 3]
146.2 parts by weight of bisphenol A and 157.2 parts by weight of diphenyl carbonate were mixed in a reactor equipped with a stirrer, a thermometer and a reflux condenser, and melted at 140°C. A cesium carbonate aqueous solution was added to this molten mixture, and the mixture was heated at 230° C. under a reduced pressure of 13.3 kPa for 60 minutes. While distilling off phenol from the reactor, the high-temperature and reduced-pressure conditions were changed in three stages: after heating at 260° C. and 4 kPa for 60 minutes, and then at 340° C. and 20 Pa for 150 minutes. Furthermore, 15 ppm of butyl p-toluenesulfonate was added to the reactor as a catalyst deactivator, and the molten resin was poured into water and pelletized.

B-2: Polycarbonate resin obtained by production method 4 (viscosity average molecular weight 48000, hydroxyl terminal group amount 39 eq/t)
[Manufacturing method 4]
Polymerization was carried out in the same manner as in production method 3, except that the third-stage polymerization was carried out at 300° C. and 40 Pa for 120 minutes, and the amount of the catalyst deactivator was changed to 10 ppm.

B-3: Polycarbonate resin obtained by production method 5 (viscosity average molecular weight 25000, hydroxyl end group content 78 eq/t)
[Manufacturing method 5]
Polymerization was carried out in the same manner as in production method 3, except that the third-stage polymerization was carried out at 280° C. and 50 Pa for 90 minutes, and the amount of the agent catalyst deactivation added was 5 ppm.

B-4: Polycarbonate resin obtained by production method 6 (viscosity average molecular weight 22000, hydroxyl end group content 90 eq/t)
[Manufacturing method 6]
Polymerization was carried out in the same manner as in production method 3, except that the third-stage polymerization was carried out at 280° C. and 60 Pa for 90 minutes, and the amount of the catalyst deactivator was changed to 1 ppm.

B-5: Polycarbonate resin obtained by production method 7 (viscosity average molecular weight 12500, hydroxyl end group weight 13 eq/t)
[Manufacturing method 7]
A reactor equipped with a thermometer, a stirrer and a reflux condenser was charged with 219.4 parts of ion-exchanged water and 40.2 parts of a 48% sodium hydroxide aqueous solution. 5 parts of hydrosulfite and 0.12 parts of hydrosulfite were added and dissolved in 25 minutes, then 181 parts of methylene chloride was added in 5 minutes, and 27.8 parts of phosgene was blown in at 15 to 25°C with stirring over 40 minutes. is. After the completion of the phosgene blowing, 2,2-bis(4-hydroxyphenyl)propane was added to 7.2 parts of 48% aqueous sodium hydroxide solution, 3.10 parts of p-tert-butylphenol and 1 part of 7.4% aqueous sodium hydroxide solution. 0.65 parts of a solution containing 0.20 parts dissolved therein was added, emulsified with a homomixer, stirring was stopped, and the mixture was allowed to stand at 28 to 33° C. for 2.5 hours to complete the reaction. After the completion of the reaction, 200 parts of methylene chloride was added to the product and mixed, then the stirring was stopped and the aqueous phase and the organic phase were separated to obtain an organic solvent solution having a polycarbonate resin concentration of 15% by weight. After adding 200 parts of ion-exchanged water to this organic solvent solution and stirring and mixing, the stirring was stopped and the aqueous phase and the organic phase were separated. This operation was repeated (4 times) until the electrical conductivity of the aqueous phase became almost the same as that of ion-exchanged water. The resulting purified polycarbonate resin solution was filtered through a SUS304 filter with a filtration accuracy of 1 μm. Next, 100 L of ion-exchanged water is put into a 1000 L kneader whose inner wall is made of SUS316L and has an isolated chamber having a foreign matter outlet in the bearing portion of the organic solvent solution, and methylene chloride is evaporated at a water temperature of 42 ° C. A mixture of the powder and water is put into a hot water treatment tank in a hot water treatment step having a hot water treatment tank with a stirrer controlled at a water temperature of 95 ° C., and 25 parts of the powder and water are added. Stirrer mixed for 30 minutes at a mixing ratio of 75 parts. A mixture of this granule and water was separated by a centrifugal separator to obtain a granule containing 0.5% by weight of methylene chloride and 45% by weight of water. Next, the granules were continuously supplied at 50 kg/Hr (converted to polycarbonate resin) to a SUS316L conductive heat-receiving grooved twin-screw stirring continuous dryer controlled at 140° C., and the average drying time was 6 hours. to obtain a powder having a viscosity-average molecular weight of 11,800. The resulting powder was put into acetone, and after stirring for 30 minutes, the slurry solution of powder was taken out. After solid-liquid separation, it was dried at 140°C for 4 hours under a nitrogen atmosphere, and extracted with acetone. A granule (powder) having a terminal group amount of 13 eq/ton was obtained.

<C component>
C-1: Circular cross-section chopped glass fiber (T-732H manufactured by Nippon Electric Glass Co., Ltd. diameter: 10.5 μm, cut length: 3 mm, epoxy sizing agent)
C-2: Calcium carbonate (KSS-1000 manufactured by Calfine Co., Ltd.)
C-3: Carbon fiber (manufactured by Teijin Ltd. IM702 6 mm major diameter: 6 μm, cut length: 6 mm, tensile modulus: 282 GPa, tensile strength: 5,490 MPa, urethane-based sizing agent))
C-4: Wholly aromatic polyamide fiber (manufactured by Teijin Limited, para-based wholly aromatic polyamide fiber T322EH 3-12 length: 12 μm, cut length: 3 mm)

Claims (4)

(A) 99 to 1 part by weight of a polyarylene sulfide resin (component A) and (B) 1 to 99 parts by weight of a polycarbonate resin (component B) having a hydroxyl terminal group content of 20 to 80 eq/t. is a polyphenylene sulfide resin having a total sodium content of 39 ppm or less . 2. The resin composition according to claim 1 , wherein at least part of component A is a polyphenylene sulfide resin containing a reactive functional group. 3. The resin composition according to claim 2 , which is a polyphenylene sulfide resin in which the reactive functional group is a carboxyl group. A molded article made of the resin composition according to any one of claims 1 to 3 .