JP2022029144A - Polyarylene sulfide resin composition - Google Patents

Abstract

To provide a polyarylene sulfide resin composition that is excellent in mechanical strength, heat resistance and reduced burrs while holding excellent properties of a polyarylene sulfide resin.SOLUTION: A resin composition contains (A) a polyarylene sulfide resin (A component) and (B) a polycarbonate resin (B component), and relative to the total of A and B components of 100 pts.wt., (C) 0.001-10 pts.wt. of a compound having a reactive functional group (C component) and (D) 10-350 pts.wt. of a glass fiber (D component). The resin composition forms a sea-island structure with the polyarylene sulfide resin as a continuous phase and the polycarbonate resin as a dispersed phase, and has the morphology with glass fibers dispersed only in the polyarylene sulfide resin continuous phase.SELECTED DRAWING: None

Description

The present invention is composed of a polyarylene sulfide resin, a polycarbonate resin, a compound having a reactive functional group and a glass fiber, and forms a sea-island structure in which the polyarylene sulfide resin has a continuous phase and the polycarbonate resin has a dispersed phase, and the polyarylene sulfide resin is formed. A resin composition having a morphology in which glass fibers are dispersed only in a continuous phase, and having excellent mechanical strength, heat resistance, and low variability while retaining the excellent properties of a polyarylene sulfide resin. It relates to a composition.

Polyarylene sulfide resin is an engineering plastic having excellent chemical resistance, heat resistance, mechanical properties and the like. For this reason, polyarylene sulfide resins are widely used as electrical and electronic parts, vehicle-related parts, aircraft parts, and housing equipment parts. However, the polyarylene sulfide resin has a problem that burrs are generated during the molding process. As a means for solving this problem, Patent Document 1 discloses a resin composition containing a polyphenylene sulfide resin and a polycarbonate resin. However, since the conventionally commercially available polyphenylene sulfide resin contains a certain amount of sodium as an impurity due to the limitation of the polymer polymerization method, the polycarbonate resin is significantly decomposed during the molding process to exhibit excellent properties. Not reached. Patent Documents 2 and 3 propose polyphenylene sulfide resins having a reduced chlorine content. However, the decomposition of the polycarbonate resin cannot be suppressed only by using the polyphenylene sulfide resin having a reduced chlorine content. Further, in order to reduce the chlorine content, the reaction process becomes complicated and the cost competitiveness is inferior. Patent Document 4 discloses a polyphenylene sulfide resin in which an alkali metal is reduced, but it is not intended to be modified with a polycarbonate resin and is inferior in cost competitiveness. Patent Document 5 discloses a resin composition containing a polyphenylene sulfide resin and a thermoplastic resin having a dispersity of 2.5 or less and an alkali metal content of 50 ppm or less. However, it was not intended for modification with a polycarbonate resin, particularly for suppressing burrs, and the characteristics were not satisfactory. Further, Patent Document 6 discloses a resin composition containing a polyphenylene sulfide resin and a polycarbonate resin in which decomposition of the polycarbonate resin is suppressed, but the mechanical strength and heat resistance of the resin composition are insufficient. ..

Japanese Unexamined Patent Publication No. 51-59952 Japanese Unexamined Patent Publication No. 2010-70656 Japanese Unexamined Patent Publication No. 2013-181044 Japanese Unexamined Patent Publication No. 2008-231250 Japanese Unexamined Patent Publication No. 2008-231249 Japanese Unexamined Patent Publication No. 2015-30779

An object of the present invention is to provide a polyarylene sulfide resin composition excellent in mechanical strength, heat resistance and low burr property while retaining the excellent properties of the polyarylene sulfide resin.

As a result of diligent studies, the present inventor has created a sea-island structure composed of a polyarylene sulfide resin, a polycarbonate resin, a compound having a reactive functional group and a glass fiber, in which the polyarylene sulfide resin has a continuous phase and the polycarbonate resin has a dispersed phase. The resin composition having a morphology formed and having glass fibers dispersed only in the continuous phase of the polyarylene sulfide resin has mechanical strength, heat resistance and low burrs while retaining the excellent properties of the polyarylene sulfide resin. We have found that it is excellent in properties and have reached the present invention.

Specifically, the above-mentioned problem is a compound (C) having a reactive functional group with respect to a total of 100 parts by weight of (A) polyarylene sulfide resin (A component) and (B) polycarbonate resin (B component). A resin composition containing 0.001 to 10 parts by weight of (component) and 10 to 350 parts by weight of (D) glass fiber (component D), in which a polyarylene sulfide resin has a continuous phase and a polycarbonate resin has a dispersed phase. It is achieved by a resin composition having a morphology in which a structure is formed and glass fibers are dispersed only in a continuous phase of a polyarylene sulfide resin.

Hereinafter, the details of the present invention will be described.

(Component A: Polyarylene sulfide resin)
As the polyarylene sulfide resin used as the component A of the present invention, any polyarylene sulfide resin may be used as long as it belongs to the category called polyarylene sulfide resin.

The polyarylene sulfide resin has, as its constituent units, for example, p-phenylene sulfide unit, m-phenylene sulfide unit, o-phenylene sulfide unit, phenylene sulfide sulfone unit, phenylene sulfide ketone unit, phenylene sulfide ether unit, diphenylene sulfide unit. , Phenylene sulfide unit containing substituent, phenylene sulfide unit containing branched structure, etc. Among them, those containing 70 mol% or more, particularly 90 mol% or more of p-phenylene sulfide unit. Preferred, more preferably poly (p-phenylene sulfide).

The total chlorine content of the polyarylene sulfide resin used as the component A of 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 may increase, the mold deposit may increase, and the peelability may deteriorate.

The total sodium content of the polyarylene sulfide resin used as the component A 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 it exceeds 39 ppm, not only the deterioration of physical properties due to the promotion of decomposition of the resin but also the increase in water absorption of the resin due to the coordination bond between the sodium metal and the water molecule in a high temperature and high humidity environment may reduce the moisture resistance. be. The total sodium content was measured by ICP emission spectrometry (ICP-AES method).

The dispersity (Mw / Mn) represented by the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polyarylene sulfide resin used as the component A of the present invention is preferably 2.7 or more, more preferably 2. It is 8.8 or more, more preferably 2.9 or more. If the degree of dispersion is less than 2.7, burrs may be generated during molding. The upper limit of the degree of dispersion (Mw / Mn) is not particularly specified, but is preferably 10 or less. Here, the weight average molecular weight (Mw) and the 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 polymerization is carried out by a known method, but particularly suitable polymerization methods are US Registered Patents No. 4,746,758 and 4,786. , 713, Japanese Patent Application Laid-Open No. 2013-522385, Japanese Patent Application Laid-Open No. 2012-233210, Japanese Patent No. 5167276, and the like. These production methods are methods in which a diiodoaryl compound and solid sulfur are directly heated and polymerized without a polar solvent.

The production method includes an iodination step and a polymerization step. In the iodination step, the aryl compound is reacted with iodine to obtain a diiodoaryl compound. In the subsequent polymerization step, a polyarylene sulfide resin is produced by polymerizing a diiodoaryl compound with solid sulfur using a polymerization inhibitor. Iodine is generated in the form of a gas in this step, and it is recovered and used again in the iodide step. Iodine is essentially a catalyst.

As a typical solid sulfur used in the above-mentioned production method, a cycloocta-sulfur form ( _S8 ) in which eight atoms are linked at room temperature can be mentioned. However, the sulfur compound used in the polymerization reaction is not limited, and any form can be used as long as it is solid or liquid at room temperature.

Representative examples of the diiodoaryl compound used in the above-mentioned 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 groups or sulfon groups are bonded or oxygen or nitrogen is introduced are also used. Iodoaryl compounds are classified into different isomers depending on the bond position of their iodine atom, and preferred examples of these isomers are p-diiodobenzene, 2,6-diiodonaphthalene, and p, p'-diiodine. Iodine is a compound such as biphenyl that is symmetrically located at both ends of the molecule of the aryl compound. The content of the iodine aryl 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 terminators used in the above-mentioned production method include monoiodoaryl compounds, benzothiazoles, benzothiazolesulfenamides, thiurams, dithiocarbamates, aromatic sulfide compounds and the like. Preferred examples of the monoiodoaryl compound include at least one selected from the group consisting of iodobiphenyl, iodophenol, iodoaniline and iodobenzophenone. Preferred examples of the benzothiazoles include at least one selected from the group consisting of 2-mercaptobenzothiazole and 2,2'-dithiobisbenzothiazole. Preferred examples of the benzothiazole sulfenamides are N-cyclohexylbenzothiazole2-sulfenamide, N, N-dicyclohexyl-2-benzothiazolesulfenamide, 2-morpholinothiobenzothiazole, benzothiazolesulfenamide. , Dibenzothiazole disulfide, N-dicyclohexylbenzothiazole 2-sulfenamide, at least one selected from the group. Preferred examples of thiurams include at least one selected from the group consisting of tetramethylthiuram monosulfide and tetramethylthiuram disulfide. Preferred examples of the dithiocarbamates include at least one selected from the group consisting of zinc dimethyldithiocarbamate and zinc diethyldithiocarbamate. Preferred examples of the aromatic sulfide compound include at least one selected from the group consisting of diphenyl sulfide, diphenyl disulfide, diphenyl ether, biphenyl and benzophenone. Further, in any of the polymerization inhibitors, 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 and the like, preferred examples thereof include a carboxyl group and an amino group, and further preferred examples thereof include a carboxyl group and an amino group. Examples include a carboxyl group and an amino group showing a peak of 1600 to 1800 cm ^-1 or 3300 to 3500 cm ^-1 on the FT-IR spectrum. The content of the polymerization inhibitor 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 A component of the present invention, a carboxyl group, a carboxyl group derivative group, a thiol group, a sulfone group, a hydroxy group, an amino group, an epoxy group, and the like, for the purpose of obtaining higher compatibility. A polyarylene sulfide resin having a reactive functional group such as a mercapto group, a cyano group or a nitro group at the end can also be used. By using a polyarylene sulfide resin having the reactive functional group at the end, a resin showing excellent compatibility with other polymer materials, carbon fibers, etc., excellent in peelability, and having higher mechanical strength. The composition can be obtained. A more preferable example of the polyarylene sulfide resin having the reactive functional group at the terminal is a polyarylene sulfide resin having at least one terminal group structure selected from a carboxyl group and an amino group. The polyarylene sulfide resin having at least one terminal group structure selected from the carboxyl group and the amino group is about 1600 to 1800 cm ^-1 or amino derived from the carboxyl group in the FT-IR spectrum of FT-IR spectroscopy. When the height intensity of the aromatic ring expansion / contraction peak showing a peak of about 3300 to 3500 cm ^-1 derived from the group and appearing at 1400 to 1600 cm ^-1 is 100%, the above-mentioned about 1600 to 1800 cm ^-1 or about 3300 ^to 3500 cm-. It is a polyarylene sulfide resin having a relative height intensity of ¹ peak of 0.001 to 10%.

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

（式中、Ａｒ基はアリーレン基であり、ｎは繰り返し単位数である。）

(In the formula, the Ar group is an arylene group and n is the number of repeating units.)

Here, as the arylene group, a p-phenylene group, an m-phenylene group, an o-phenylene group, a substituted phenylene group and the like can be used. Specifically, the substituted phenylene group is one or more F, Cl, Br, C1-C3 alkyl, trifluoromethyl, C1-C3 alkoxy, trifluoromethoxy, trifluoromethylthio, dimethylamino, cyano, It is a phenylene group arbitrarily 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 the polymerization is carried out by a known method, but the general formula (2) may be one or more on the conjugated aromatic ring skeleton. Examples thereof include a method using a polymerization terminator having a represented group. Examples of the conjugated aromatic ring skeleton used in the polymerization terminator include diphenyldisulfide, monoiodobenzene, thiophenol, 2,2'-dibenzothiazolyl disulfide, 2-mercaptobenzothiazole, and N-cyclohexyl-2-benzo. Examples thereof include thiazolyl sulfenamide, 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）

(In the formula, R is a hydrogen atom or an alkali metal atom)

As a suitable polymerization method of the method for producing a polyarylene sulfide resin having a terminal group structure of a carboxyl group, a step of polymerizing a reactant containing a diiode aromatic compound and an element of sulfur, and a step of carrying out the polymerization reaction step, the carboxyl Examples thereof include a production method in which a compound having a group is added to replace the terminal group of the polyarylene sulfide main chain with a carboxyl group. A representative example used in the above-mentioned compound having a carboxyl group is at least one selected from the group consisting of 2-iodobenzoic acid, 3-iodobenzoic acid, 4-iodobenzoic acid, and 2,2'-dithiobenzoic acid. Seeds are mentioned. The compound having a carboxyl group can be added in an amount of about 0.0001 to 5 parts by weight based on 100 parts by weight of the diiodot aromatic compound.

A polymerization reaction catalyst may be used in the above-mentioned production method, and a nitrobenzene-based catalyst can be mentioned as a typical polymerization reaction catalyst. Preferred examples of nitrobenzene catalysts are 1,3-diiodo-4-nitrobenzene, 1-iodo-4-nitrobenzene, 2,6-diiodo-4-nitrophenol, iodonitrobenzene, and 2,6-diiodo-4-. At least one selected from the group consisting of nitroamines may 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.

Typical examples of the reaction conditions of the production method are from the initial reaction conditions of a temperature of 180 to 250 ° C. and a pressure of 50 to 450 Torr (6.7 to 60 kPa), a temperature of 270 to 350 ° C. and a pressure of 0.001 to 20 Torr (0). The process is allowed to proceed for 1 to 30 hours while raising the temperature and lowering the pressure until the final reaction conditions of .00013 to 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 less 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) The following can be mentioned.

However, the conditions of 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. The reaction conditions can be appropriately set by those skilled in the art in consideration of the process conditions.

By using this polymerization method, it is not necessary to substantially reduce the sodium content, and a polyphenylene sulfide resin having excellent cost performance can be obtained.

Further, the polyphenylene sulfide resin of the present invention may contain a polyphenylene sulfide resin obtained by another polymerization method.

(B component: polycarbonate resin)
The polycarbonate resin used in the present invention is obtained by reacting a divalent 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, a ring-opening polymerization method of a cyclic carbonate compound, and the like, but the melt transesterification method is preferable. The polycarbonate resin may also be a branched polycarbonate resin obtained by polymerizing a trifunctional phenol, and further copolymerized 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 was obtained by inserting the specific viscosity (η _sp ) obtained at 20 ° C. from a solution of 0.7 g of the polycarbonate resin 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 (however, [η] is the ultimate viscosity)
[Η] = 1.23 × 10 ^-4 M ^0.83
c = 0.7

The polycarbonate resin used in the present invention may be various polycarbonate resins having high heat resistance or low water absorption, which are 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 polymerized using other divalent phenols are preferably as follows.

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

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

(3) The BPM component is 20 to 80 mol% (more preferably 40 to 75 mol%, further preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and The 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%). Copolymerized polycarbonate. These special polycarbonates may be used alone or in combination of two or more. Further, these can also be used by mixing them with the 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, JP-A-2002-117580 and the like. ing. Further, a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing a polyorganosiloxane unit can also be used.

As the polycarbonate resin, not only the virgin raw material but also the polycarbonate resin regenerated from the used product can be used. Examples of the used products include containers typified by water bottles, optical discs, and automobile headlamps.

The content of the B component is preferably 1 to 50 parts by weight, more preferably 5 to 45 parts by weight, still more preferably 5 to 40 parts by weight, out of 100 parts by weight of the total of the A component and the B component. If the content is less than 1 part by weight, the characteristics of the polycarbonate resin may not be exhibited and the generation of burrs may not be suppressed, and the polyarylene sulfide resin does not form a sea-island structure having a continuous phase and the polycarbonate resin has a dispersed phase. There is. On the other hand, if the amount is more than 50 parts by weight, the characteristics of the polyphenylene sulfide resin may not be exhibited, the mechanical strength may be lowered, and the heat resistance may be deteriorated. Further, the polyarylene sulfide resin has a continuous phase and the polycarbonate resin has a dispersed phase. It may not form a sea-island structure.

(C component: compound having a reactive functional group)
The resin composition of the present invention contains a compound having a reactive functional group as the C component. The compound having a reactive functional group used in the present invention is preferably a compound represented by the following general formula (3).

In formula (3), R ¹ contains up to 20 carbon atoms, has at least one sulfur atom in the molecule, and consists of a thiol group, a carboxyl group, a hydroxy group, an epoxy group and an amino group. A hydrocarbon group or an organic silicon group having a reactive functional group containing at least one group selected from the group. R ² contains a hydrogen atom or up to 20 carbon atoms and at least one in the molecule. A hydrocarbon having a sulfur atom, containing a thiol group or a disulfide group, and having a reactive functional group containing at least one group selected from the group consisting of a carboxyl group, a hydroxy group, an epoxy group and an amino group. Group or organic silicon group.)

Examples of compounds having reactive functional groups include 2-mercaptobenzoic acid, 3-mercaptobenzoic acid, 4-mercaptobenzoic acid, thioglycolic acid, thiolactic acid, 2-mercaptoaniline, 3-mercaptoaniline, 4-mercapto. Aniline, 2-mercaptopyridine, 4-mercaptopyridine, 2-mercaptobenzothiazole, 3-mercaptopropyltrimethoxysilane, 2,2'-dithiodibenzoic acid, dithioglycolic acid, α, α'-dithiodilactic acid, β, β'-dithiodilactic acid, 2,2'-dithiodianiline, 3,3'-dithiodianiline, 4,4'-dithiodianiline, 3,3'-dithiodipyridine, 2,2'-dithiobis (benzo Thiazol), 2,2'-dithiobis (benzimidazole), 2,2'-dithiobis (benzoxazole), 2- (4'-morpholinodithio) benzothiazole and the like can be mentioned. When a compound containing a sulfur atom having no reactive functional group is used, the viscosity of the resin is lowered and the burr is deteriorated.

The content of the C component is 0.001 to 10 parts by weight, preferably 0.005 to 5 parts by weight, and more preferably 0.05 to 1 part by weight with respect to 100 parts by weight of the total of the A component and the B component. It is a department. If the content of the C component is less than 0.001 part by weight, the glass fiber does not have a morphology in which the glass fiber is dispersed only in the continuous phase of the polyarylene sulfide resin, and the mechanical strength and heat resistance are inferior, exceeding 10 parts by weight. As a result, the mechanical strength decreases, plasticization of the resin occurs, and burrs also worsen.

(D component: glass fiber)
The glass fiber used in the present invention is not particularly limited in the glass composition of A glass, C glass, E glass and the like, and may contain components such as TiO ₂ , SO ₃ and P ₂ O ₅ in some cases. It may be. However, it is more preferable when E glass (non-alkali glass) is blended with the thermoplastic resin. Furthermore, it is also possible to use two or more of these glass fibers in combination. The glass fiber is made by stretching molten glass by various methods and quenching it to form a predetermined fibrous or milled form. The quenching and stretching conditions in such a case are not particularly limited. Further, the cross-sectional shape may be a shape other than a perfect circle, such as an ellipse, an eyebrows, or a trefoil, in addition to the perfect circle. Further, a perfect circular glass fiber and a glass fiber having a shape other than the perfect circle may be mixed. Of these, the more preferable one is a perfect circular glass fiber. In addition, these glass fibers are pretreated 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, and an epoxy compound, and an organic onium ion for a swellable layered silicate. It is preferable to use it in the sense of obtaining better mechanical strength. The glass fiber used in the present invention preferably has a diameter (D) of 6 to 13 μm, a cut length (L) of 30 μm to 9 mm, and an L / D of 2.3 to 1500.

The content of the D component is 10 to 350 parts by weight, preferably 20 to 300 parts by weight, and more preferably 60 to 200 parts by weight with respect to 100 parts by weight of the total of the A component and the B component. If the content of the D component is less than 10 parts by weight, the mechanical strength and heat resistance are inferior, and the burr also deteriorates. If it exceeds 350 parts by weight, the moldability is lowered.

(Other ingredients)
The resin composition in the present invention may contain a filler component other than the D component as long as the effect of the present invention is not impaired. The suitable filler component is not particularly limited, but a reinforcing material such as fibrous, plate-like, powder-like, or granular can be used. Specifically, inorganic fibers such as wallastnite, carbon fiber, potassium titanate, zinc oxide whisker, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, stone fiber, metal fiber, and total aromatic polyamide fiber, etc. Organic fibers and the like, and wallastnite, carbon fibers, and all aromatic polyamide fibers are preferably used. In addition, silicates such as sericite, kaolin, mica, clay, bentonite, asbestos, talc, and alumina silicate, swellable layered silicates such as montmorillonite and synthetic mica, alumina, silicon oxide, magnesium oxide, zirconium oxide, and titanium oxide. , Metal compounds such as iron oxide, carbonates such as magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, glass flakes, glass beads, ceramic beads, boron nitride, silicon carbide, calcium phosphate and silica, etc. However, glass flakes, mica, talc, and glass beads are preferably used. These may be hollow, and it is also possible to use two or more kinds of these reinforcing materials in combination.

In addition, these reinforcing materials are pretreated 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, and an epoxy compound, and with an organic onium ion for a swellable layered silicate. It is preferable to use it in the sense of obtaining better mechanical strength.

Examples of the reinforcing material for imparting conductivity to the resin composition of the present invention include a conductive filler. The conductive filler is not particularly limited as long as it is a conductive filler usually used for making a resin conductive, and specific examples thereof include metal powder, metal flakes, metal ribbons, metal fibers, metal oxides, and conductive substances. Examples include coated inorganic fillers, carbon powders, graphite, carbon fibers, carbon flakes, scaly carbon and the like. Specific examples of metal powders, metal flakes, and metal species of 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. The metal powder, metal flakes, metal ribbons, and metal fibers may be surface-treated with a surface treatment agent such as titanate-based, aluminum-based, or silane-based.

Specific examples of the metal oxide include SnO ₂ (anti-mondoping), In ₂ O ₃ (anti-mondoping), ZnO (aluminum doping), and the like, and these are surfaces of titanate-based, aluminum-based, silane-based coupling agents, and the like. The surface may be treated with a treatment agent.

Specific examples of the conductive substance in the inorganic filler coated with the conductive substance include aluminum, nickel, silver, carbon, SnO ₂ (antimony dope), In ₂ O ₃ (antimony dope) and the like. The 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, titanium acid whiskers, and carbonized products. A silicon whiskers and the like can be exemplified. Examples of the coating method include a vacuum vapor deposition method, a sputtering method, an electroless plating method, and a baking method. Further, 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, naphthalin black, thermal black, furnace black, lamp black, channel black, roll black, disc black, etc. according to its raw material and manufacturing method. The carbon powder that can be used in the present invention is not particularly limited in its raw material and production method, but acetylene black and furnace black are particularly preferably used.

The resin composition in the present invention may contain an elastomer component as long as the effects of the present invention are not impaired. Suitable elastomer components include core-shells such as acrylonitrile-butadiene-styrene copolymer (ABS resin), methylmethacrylate / butadiene-styrene copolymer (MBS resin) and silicone-acrylic composite rubber graft copolymer. Examples thereof include graft copolymer resins, and thermoplastic elastomers such as silicone-based thermoplastic elastomers, olefin-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, polyester-based thermoplastic elastomers, and polyurethane-based thermoplastic elastomers.

The resin composition in the present invention may contain other thermoplastic resins as long as the effects of the present invention are not impaired. Examples of other thermoplastic resins include general-purpose plastics typified by polyethylene resin, polypropylene resin, polyalkyl methacrylate resin, polyphenylene ether resin, polyacetal resin, aromatic polyester resin, liquid crystal polyester resin, polyamide resin, and annular resin. Engineering plastics typified by polyolefin resins, polyarylate resins (acrystalline polyarylate, liquid crystal polyarylate), polytetrafluoroethylene, polyether ether ketone, polyetherimide, polysulfone, polyether sulfone, etc. The so-called super engineering plastics can be mentioned.

In the resin composition of the present invention, an antioxidant, a heat-resistant stabilizer (hindered phenol-based, hydroquinone-based, phosphite-based and their substitutes, etc.) and a weather-resistant agent (resorcinol-based) are used as long as the effects of the present invention are not impaired. , Salicylate type, benzotriazole type, benzophenone type, hindered amine type, etc.), antistatic agent and lubricant (montanoic acid and its metal salt, its ester, its half ester, stearyl alcohol, stearamide, various bisamides, bisurea and polyethylene wax, etc. ), Pigments (cadmium sulfide, phthalocyanine, carbon black, etc.), dyes (niglosin, etc.), crystal nucleating agents (talc, silica, kaolin, clay, etc.), plasticizing agents (octyl oxybenzoate, N-butylbenzene sulfonamide, etc.) Etc.), Antistatic agents (alkylsulfate-type anionic antistatic agents, quaternary ammonium salt-type cationic antistatic agents, nonionic antistatic agents such as polyoxyethylene sorbitan monostearate, betaine-based amphoteric antistatic agents Etc.), flame retardant (red phosphorus, phosphate ester, 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 bromine-based flame retardants and antimon trioxide, etc.) and other polymers can be added.

(Manufacturing of resin composition)
The resin composition of the present invention can be produced by mixing the above components simultaneously or in any order with a mixer such as a tumbler, a V-type blender, a Nauter mixer, a Banbury mixer, a kneading roll, or an extruder. It is preferable to melt-knead by a twin-screw extruder, and if necessary, it is preferable to supply an arbitrary component to other melt-mixed components from a second supply port using a side feeder or the like. As the extruder, one having a vent capable of degassing the moisture in the raw material and the volatile gas generated from the melt-kneaded resin can be preferably used. A vacuum pump is preferably installed from the vent to efficiently discharge the generated water and volatile gas to the outside of the extruder. It is also possible to install a screen for removing foreign substances and the like mixed in the extruded raw material in the zone in front of the die portion of the extruder to remove the foreign substances from the resin composition. Examples of such a screen include a wire mesh, a screen changer, a sintered metal plate (disc filter, etc.) and the like.

The screws used in the twin-screw extruder are made by inserting screw pieces of various shapes between the forward flight pieces for transportation, combining them in a complicated manner, and integrating them into one screw. A screw piece such as a forward kneading piece, a reverse kneading piece, a reverse flight piece, a forward flight piece having a notch, and a reverse flight piece are arranged and combined in an appropriate order and position in consideration of the characteristics of the raw material to be processed. Can be mentioned. 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 shafts, in addition to the twin-screw extruder.

The resin extruded as described above is either directly cut and pelletized, or the strands are cut and pelletized with a pelletizer after forming the strands. When it is necessary to reduce the influence of external dust and the like during pelletization, it is preferable to clean the atmosphere around the extruder. The shape of the obtained pellet can take a general shape such as a cylinder, a prism, and a sphere, but is more preferably a cylinder. The diameter of the cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, still more preferably 2 to 3.5 mm. On the other hand, the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, still more preferably 2.5 to 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. When the total amount of sodium exceeds 39 ppm, the decomposition of the polycarbonate resin cannot be suppressed, so that the effect of suppressing burrs by the polycarbonate resin is not exhibited, and in the worse case, pelletization may be difficult.

The resin composition of the present invention has a morphology in which a polyarylene sulfide resin forms a continuous phase and a polycarbonate resin forms a sea-island structure, and glass fibers are dispersed only in the polyarylene sulfide resin continuous phase. When the polyarylene sulfide resin does not form a sea-island structure having a continuous phase and the polycarbonate resin has a dispersed phase, the characteristics of the polyphenylene sulfide resin are not exhibited, the mechanical strength is lowered, and the heat resistance is also deteriorated. Further, even when the glass fiber is not dispersed only in the continuous phase of the polyarylene sulfide resin, the characteristics of the polyphenylene sulfide resin are not exhibited, the mechanical strength is lowered, and the heat resistance is also deteriorated.

(About molded products)
A molded product using the resin composition of the present invention can be obtained by molding pellets produced as described above. Preferably, it is 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, and heat insulating metal. Examples thereof include mold molding, rapid heating / cooling mold molding, two-color molding, multicolor molding, sandwich molding, and ultra-high-speed injection molding. In addition, either a cold runner method or a hot runner method can be selected for molding. Further, in extrusion molding, various deformed extruded products, sheets, films and the like can be obtained. Inflation method, calendar method, casting method, etc. can also be used for forming sheets and films. Further, it can be molded as a heat-shrinkable tube by applying a specific stretching operation. Further, the resin composition of the present invention can be made into a molded product by rotary molding, blow molding or the like.

The resin composition of the present invention is a resin composition composed of a polyarylene sulfide resin, a polycarbonate resin, a compound having a reactive functional group, and a glass fiber, and is a machine while retaining the excellent properties of the polyarylene sulfide resin. Since it is a polyarylene sulfide resin composition having excellent strength, heat resistance and low variability, it is a personal computer, a tablet, a housing for a mobile phone, a display, an OA device, a mobile phone, a mobile information terminal, a facsimile, a compact disk, and a portable. MD, portable radio cassette, PDA (portable information terminal such as electronic notebook), video camera, digital still camera, optical equipment, audio, air conditioner, lighting equipment, entertainment equipment, toy equipment, other electric and electronic equipment such as home appliances Housing and internal parts such as trays and chassis, their cases, mechanical parts, building materials such as panels, motor parts, alternator terminals, alternator connectors, IC regulators, light deer potential meter bases, suspension parts, exhaust gas valves, etc. Various valves, fuel related, exhaust system or intake system various pipes, air intake nozzle snorkel, intake manifold, various arms, various frames, various hinges, various bearings, fuel pumps, gasoline tanks, CNG tanks, engine cooling water joints, carburetor main Body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crank shaft 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 boards, fuel related electromagnetic valves Coil, fuse connector, battery tray, AT bracket, headlamp support, pedal housing, handle, door beam, protector, chassis, frame, armrest, horn terminal, step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, Neu Zshield, radiator support, spare tire cover, seat shell, solenoid bobbin, engine oil filter, ignition device case, undercover, scuff plate, pillar trim, propeller shaft, wheel, fender, facer, bumper, bumper beam, bonnet, aero parts, Aircraft such as platforms, cowl louvers, roofs, instrument panels, spoilers and various modules for automobiles, motorcycle-related parts, parts and skins and landing gear pods, winglets, spoilers, edges, rudder, elevators, failing, ribs, etc. Widely useful in related parts, parts and skins, windmill blades, etc., especially electronic equipment housings such as computers, notebooks, ultrabooks, tablets, housings for mobile phones, inverter housings for hybrid and electric vehicles, etc. It is widely useful in Japan, and its industrial effect is exceptional.

6 is an SEM image of a cross section of a test piece of Example 6. 6 is an SEM image of a cross section of a test piece of Comparative Example 3.

The embodiment of the present invention, which the present inventor considers to be the best at present, is a collection of preferable ranges of the above-mentioned requirements. For example, a representative example thereof will be described in the following examples. Of course, the present invention is not limited to these forms.

[Evaluation of resin composition]
(1) Mechanical strength evaluation The tensile strength at break was measured in accordance with ISO527-1 and ISO527-2 (measurement conditions 23 ° C.). The test piece was dried at 130 ° C. for 6 hours in a hot air circulation type dryer, and then used in an injection molding machine (SG-150U manufactured by Sumitomo Heavy Industries, Ltd.) to have a cylinder temperature of 300 ° C. and a mold temperature. Molded under the condition of 150 ° C. The larger this value is, the better the mechanical strength of the resin composition is.

(2) Heat resistance evaluation Using a test piece having a thickness of 4 mm prepared in accordance with ISO 75-1 and 2 of the ISO standard, the deflection temperature under load was measured with a load of 1.80 MPa.

(3) Evaluation of burrs The evaluation of burrs was carried out by measuring the length of burrs at the portion of the test piece in contact with the gas vent in accordance with ISO527-1 and ISO527-2 described above. The thickness of the gas vent was 10 μm and the width was 5 mm.

(4) Morphology observation In morphology observation, the central part of the test piece conforming to the above ISO527-1 and ISO527-2 is cut and polished, gold vapor deposition is performed, and the reflection is performed with a scanning electron microscope (SEM) at a measurement magnification of 3000 times. An electron image was observed. In the SEM image, the gray part is the polyarylene sulfide resin (PPS resin) phase, the black part is the polycarbonate resin (PC resin) phase, and the white part is the glass fiber (GF).

[Examples 1 to 17, Comparative Examples 1 to 8]
Polyarylene sulfide resin, polycarbonate resin, compounds having reactive functional groups and glass fibers were melt-kneaded at the respective blending amounts shown in Tables 1 and 2 using a bent twin-screw extruder to obtain pellets. The vent type twin-screw extruder was manufactured by Japan Steel Works, Ltd .: TEX-30XSST (complete meshing, rotating in the same direction). The extrusion conditions were a discharge rate of 12 kg / h, a screw rotation speed of 150 rpm, a vacuum degree of vent of 3 kPa, and an extrusion temperature of 300 ° C. from the first supply port to the die portion. The glass fiber was supplied from the second supply port using the side feeder of the extruder, and the polyarylene sulfide resin, the polycarbonate resin and the compound having a reactive functional group were supplied to the extruder from the first supply port. The first supply port referred to here is the supply port farthest from the die, and the second supply port is a supply port located between the die of the extruder and the first supply port. The obtained pellets were dried at 130 ° C. for 6 hours in a hot air circulation type dryer, and then used by an injection molding machine (SG-150U manufactured by Sumitomo Heavy Industries, Ltd.) to have a cylinder temperature of 300 ° C. and a mold temperature of 150 ° C. Under the conditions, a test piece for evaluation was molded.

<Component A>
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 (content of 0.65% by weight based on the weight of finally polymerized PPS) as a polymerization inhibitor was added 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 obtained mixture was polymerized for 8 hours while gradually changing the temperature and pressure so that the final temperature and pressure were 320 ° C. and 1 Torr, respectively, to produce a polyphenylene sulfide resin. The total sodium content was 7 ppm. The dispersity (Mw / Mn) represented by the weight average molecular weight (Mw) and the number average molecular weight (Mn) was 4.7.

A-2: Polyphenylene sulfide resin obtained in Production Method 2 [Production Method 2]
A reaction product containing 5130 g of paradiiodobenzene and 450 g of sulfur and 4 g of mercaptobenzothiazole as a reaction initiator is heated to 180 ° C. to completely melt and mix, then the temperature is raised to 220 ° C. and the pressure is 350 Torr. The pressure was lowered. The polymerization reaction of the obtained mixture proceeded while gradually changing the temperature and pressure so that the final temperature and pressure were 300 ° C. and 1 Torr or less, respectively. When the polymerization reaction proceeded by 80% (the degree of progress of the polymerization reaction was confirmed by a method of relative ratio by 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 in a nitrogen atmosphere for 10 minutes. Was produced at the end of the main chain. In the FT-IR spectrum of the obtained polyarylene sulfide, the presence of a carboxyl group peak of 1600 to 1800 cm ^-1 was confirmed. Further, when the height intensity of the aromatic ring expansion / contraction peak appearing at 1400 to 1600 cm ^-1 was 100%, the relative height intensity of the peak at 1600 to 1800 cm ^-1 was 3.4%. The total sodium content was 7 ppm. The dispersity (Mw / Mn) represented by the weight average molecular weight (Mw) and the number average molecular weight (Mn) was 4.11.
A-3: Polyphenylene sulfide resin (DIC-PPS MA-510 manufactured by DIC)

<B component>
B-1: Polycarbonate resin obtained in Production Method 3 (viscosity average molecular weight 12500)
[Manufacturing method 3]
219.4 parts of ion-exchanged water and 40.2 parts of a 48% sodium hydroxide aqueous solution were charged in a reactor with a thermometer, a stirrer and a reflux condenser, and 2,2-bis (4-hydroxyphenyl) propane 57. After adding 5 parts and 0.12 parts of hydroxide and dissolving in 25 minutes, add 181 parts of methylene chloride in 5 minutes, and blow in 27.8 parts of phosgen at 15 to 25 ° C with stirring for 40 minutes. is. After the injection of phosgen is completed, 2,2-bis (4-hydroxyphenyl) propane is added to 7.2 parts of 48% sodium hydroxide aqueous solution, 3.10 parts of p-tert-butylphenol and 1 part of 7.4% sodium hydroxide aqueous solution. 0.65 part of a solution in which 0.20 part was dissolved 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 completion of the reaction, 200 parts of methylene chloride was added to the product and mixed, 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 conductivity of the aqueous phase became almost the same as that of the ion-exchanged water. The obtained purified polycarbonate resin solution was filtered through a SUS304 filter having a filtration accuracy of 1 μm. Next, 100 L of ion-exchanged water was poured into a 1000 L kneader made of SUS316 L as the material of the inner wall provided with an isolation chamber having a foreign matter outlet in the bearing portion of the organic solvent solution, and methylene chloride was evaporated at a water temperature of 42 ° C. The powder and granules were prepared, and the mixture of the powder and granules and water was put into a hot water treatment tank in a hot water treatment step having a hot water treatment tank with a stirrer whose water temperature was controlled to 95 ° C., and 25 parts of the powder and granules, water. The mixture was mixed with a stirrer for 30 minutes at a mixing ratio of 75 parts. The mixture of the powder or granular material and water was separated by a centrifuge to obtain a powder or granular material containing 0.5% by weight of methylene chloride and 45% by weight of water. Next, the powder or granular material was continuously supplied at 50 kg / Hr (polycarbonate resin equivalent) to a SUS316L conduction heat receiving groove type twin-screw continuous dryer controlled at 140 ° C., and the condition was that the average drying time was 6 hours. To obtain a powder or granular material having a viscosity average molecular weight of 11800. The obtained powder or granular material was put into acetone, stirred for 30 minutes, the powder or granular material slurry solution was taken out, and after solid-liquid separation, the powder or granular material was dried at 140 ° C. for 4 hours in a nitrogen atmosphere. A powder having an amount of 13 eq / ton was obtained.

<C component>
C-1: 1,3,5-Tris (2- (3-sulfanylbutanoyloxy) ethyl) -1,3,5-triazinan-2,4,6-trion (Calens MT / NR1 (Showa Denko KK) ) Made))
C-2: 1,4-Benzenedithiol (manufactured by Tokyo Chemical Industry Co., Ltd.)
C-3: 4-Mercaptobenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
C-4: 2,2'-dithionibenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
C-5: 4,4'-dithiodianiline (manufactured by Tokyo Chemical Industry Co., Ltd.)
C-6: 4,4'-dithiodiphenol (manufactured by Tokyo Chemical Industry Co., Ltd.)
C-7: 4-Mercaptophenol (manufactured by Tokyo Chemical Industry Co., Ltd.)
C-8: 3-Mercaptopropyltrimethoxysilane (KBM-803 (manufactured by Shin-Etsu Chemical Co., Ltd.))
C-9: Diphenyl disulfide (manufactured by Tokyo Chemical Industry Co., Ltd.)
C-10: p-toluenethiol (manufactured by Tokyo Chemical Industry Co., Ltd.)

<D component>
D-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-based focusing agent)
D-2: Circular cross-section chopped glass fiber (T-756H manufactured by Nippon Electric Glass Co., Ltd., diameter: 10.5 μm, cut length: 3 mm, urethane-based sizing agent)

Claims (3)

0.001 to 10 parts by weight of (C) a compound having a reactive functional group (C component) with respect to a total of 100 parts by weight of (A) polyarylene sulfide resin (A component) and (B) polycarbonate resin (B component). And (D) a resin composition containing 10 to 350 parts by weight of glass fiber (component D), which forms a sea-island structure in which a polyarylene sulfide resin has a continuous phase and a polycarbonate resin has a dispersed phase, and the polyarylene sulfide resin is formed. A resin composition having a morphology in which glass fibers are dispersed only in a continuous phase. The resin composition according to claim 1, wherein the ratio (weight ratio) of the component A to the component B (component A / component B) is 99/1 to 50/50. The C component is a compound having at least one sulfur atom and having at least one reactive functional group selected from the group consisting of a thiol group, a carboxyl group, a hydroxy group, an epoxy group and an amino group. The resin composition according to claim 1 or 2.

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