JP2012158747A - Molding material, and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a molding material for easily producing a molded article having excellent dispersion of reinforced fiber into a molded article in injection molding and excellent heat resistance and mechanical characteristics without environmental pollution.SOLUTION: The molding material is obtained by adhering 35-98.9 wt.% of a thermoplastic resin (C) to a composite composed of 1-50 wt.% of a continuous reinforced fiber bundle (A) and 0.1-15 wt.% of a polyarylene sulfide (B) and the composite contains 0.001-20 mol%, based on sulfur atom in the component (B), a 0-valent transition metal compound (D) or a low valence iron compound (E). The method for producing the molding material is provided.

Description

  The present invention relates to a molding material and a method for producing the same. More specifically, when injection molding is performed, the reinforcing fiber is well dispersed in the molded product, has high fluidity and handleability, and has excellent heat resistance and mechanical properties. The present invention relates to a molding material that can be produced with reduced generation of gas.

  As a molding material having a continuous reinforcing fiber bundle and a thermoplastic resin as a matrix, a wide variety of forms such as thermoplastic prepreg, yarn, and glass mat (GMT) are known. Such molding materials are easy to mold by taking advantage of the properties of thermoplastic resins, and do not require storage load like thermosetting resins, and the resulting molded products have high toughness and are recyclable. It has the feature of being excellent. In particular, a molding material processed into a pellet can be applied to a molding method having excellent economic efficiency and productivity such as injection molding and stamping molding, and is useful as an industrial material.

  However, in the process of producing a molding material, impregnating a continuous reinforcing fiber bundle with a thermoplastic resin has a problem in terms of economy and productivity and is not widely used at present. For example, it is well known that the higher the melt viscosity of the resin, the more difficult the impregnation of the reinforcing fiber bundle is. Thermoplastic resins with excellent mechanical properties such as toughness and elongation are high molecular weight polymers, have higher viscosity than thermosetting resins, and require higher processing temperatures, making molding materials easier. In addition, it is unsuitable for manufacturing with good productivity.

  On the other hand, when a low molecular weight, that is, a low viscosity thermoplastic resin is used for the matrix resin due to the ease of impregnation, there is a problem that the mechanical properties of the obtained molded product are significantly lowered.

  Patent Document 1 discloses a molding material in which a high molecular weight thermoplastic resin is placed in contact with a composite composed of a low molecular weight thermoplastic polymer and continuous reinforcing fibers.

  In this molding material, a low molecular weight material is used separately for impregnation into a continuous reinforcing fiber bundle, and a high molecular weight material is used for the matrix resin, thereby achieving both economic efficiency, productivity and mechanical properties. Also, when this molding material is molded by injection molding, it is easily mixed with matrix resin while minimizing breakage of reinforcing fibers at the stage of material plasticization during molding, and molding with excellent fiber dispersibility Product can be manufactured. Therefore, the obtained molded product can increase the fiber length of the reinforcing fiber as compared with the conventional one, and can have both good mechanical properties and excellent appearance quality.

  In recent years, however, fiber-reinforced composite materials have gained a lot of attention, and their applications have been subdivided into various fields, requiring molding materials with excellent moldability, handleability, and mechanical properties of the resulting molded products. In addition, industrially higher economic efficiency and productivity have become necessary. For example, fiber reinforced composite materials have been used in harsher environments, and higher heat resistance has been required for matrix resins.

  Under such circumstances, the low molecular weight thermoplastic resin undergoes a thermal decomposition reaction at the process temperature of the molding process and generates a decomposition gas. Therefore, special equipment is required so as not to contaminate equipment around the molding equipment. Problems such as voids in the molded product and deterioration of mechanical properties occur. Accordingly, there has been a demand for molding materials that are excellent in heat resistance and that do not easily generate decomposition gas.

  Patent Document 2 discloses a molding material in which a high molecular weight thermoplastic resin is placed in contact with a composite made of high molecular weight polyarylene sulfide and continuous reinforcing fibers. This material is a molding material that is excellent in heat resistance and hardly generates decomposition gas because it uses a high molecular weight polyarylene sulfide having a small loss on heating. However, this molding material has a problem that a high temperature heating process is required for the polymerization of the high molecular weight polyarylene sulfide. Therefore, from the viewpoint of industrial economy and productivity, a molding material that can be easily manufactured at a lower temperature has been demanded.

Japanese Patent Laid-Open No. 10-138379 JP 2008-231292 A

  The present invention attempts to improve the problems of the prior art, and in a molding material composed of a continuous reinforcing fiber bundle and a thermoplastic resin, a thermoplastic resin capable of achieving both impregnation and low gasity can be easily obtained at a lower temperature. By making it possible to be polymerized, the injection of the reinforcing fiber in the molded product is good when performing injection molding, and the molded product having excellent heat resistance and mechanical properties can easily suppress the generation of decomposition gas. It is an object of the present invention to provide a molding material that can be manufactured by the method and a manufacturing method thereof.

The present invention for solving such problems has the following configuration. That is,
(1) A composite composed of a continuous reinforcing fiber bundle (A) 1 to 50% by weight and a polyarylene sulfide (B) 0.1 to 15% by weight is added to a thermoplastic resin (C) 35 to 98.9% by weight. Is a molding material formed by bonding, wherein the composite further contains 0.001 to 20 mol% of a zero-valent transition metal compound (D) with respect to sulfur atoms in the component (B).
(2) The molding material as described in (1) whose said component (D) is a compound containing the metal of 8th to 11th group of a periodic table, and 4th to 6th period.
(3) The molding material according to either (1) or (2), wherein the component (D) is a compound containing palladium or nickel.
(4) A composite comprising a continuous reinforcing fiber bundle (A) 1 to 50% by weight and a polyarylene sulfide (B) 0.1 to 15% by weight is added to a thermoplastic resin (C) 35 to 98.9% by weight. Is a molding material, wherein the composite further comprises 0.001 to 20 mol% of a low-valent iron compound (E) based on sulfur atoms in the component (B).
(5) The molding material according to (4), wherein the component (E) is a divalent iron compound.
(6) The component (B) is a polyarylene sulfide obtained by heat polymerization of the polyarylene sulfide prepolymer (B ′), and the component (B ′) further contains at least 50 cyclic polyarylene sulfide. The molding material according to any one of (1) to (5), which contains at least% by weight and has a weight average molecular weight of less than 10,000.
(7) The molding material in any one of (1)-(6) whose conversion rate to the said component (B) of the said component (B ') is 70% or more.
(8) The component (B) is a polyarylene sulfide having a weight average molecular weight of 10,000 or more and a dispersity represented by weight average molecular weight / number average molecular weight of 2.5 or less. ) To (7).
(9) The molding material according to any one of (1) to (8), wherein the weight loss of the component (B) when heated satisfies the following formula.
ΔWr = (W1-W2) /W1×100≦0.20 (%)
(Here, ΔWr is the weight loss rate (%), and thermogravimetric analysis was performed at a temperature rising rate of 20 ° C./min from 50 ° C. to an arbitrary temperature of 330 ° C. or higher in a non-oxidizing atmosphere at normal pressure. (It is a value obtained from the sample weight (W2) when reaching 330 ° C. with reference to the sample weight (W1) when reaching 100 ° C.)
(10) The molding material according to any one of (1) to (9), wherein the component (A) contains at least 10,000 single fibers of carbon fibers.
(11) Any of (1) to (10), wherein the component (C) is at least one selected from polyamide resins, polyetherimide resins, polyamideimide resins, polyetheretherketone resins, and polyphenylene sulfide resins. Molding material according to crab.
(12) The components (A) are arranged substantially parallel to the axial direction, and the length of the components (A) is substantially the same as the length of the molding material (1) to (11) The molding material in any one of.
(13) A complex composed of the component (A), the component (B), the component (D) or the component (E) has a core structure, and the component (C) covers the periphery of the complex. The molding material according to (12), which has a core-sheath structure.
(14) The molding material according to (13), wherein the form of the molding material is long fiber pellets.
(15) The molding material according to any one of (1) to (14), wherein the length is in the range of 1 to 50 mm.
(16) The component (C) is arranged and bonded in layers with a composite comprising the component (A), the component (B), the component (D) or the component (E), (1) The molding material in any one of-(11).
(17) Step (I) for obtaining a mixture comprising the component (B ′) and the component (D) or the component (E), and a step for obtaining a composite obtained by impregnating the component (A) with the mixture (II) ), A method of producing a molding material comprising the step (III) of adhering the composite to the component (C), wherein the component (B ′) is converted to the component (D) after the step (II). Or the manufacturing method of the molding material in any one of (1)-(16) which heat-polymerizes in the presence of the said component (E), and converts into the said component (B).
(18) The manufacturing method of the molding material as described in (17) which performs said process (I) under the temperature of 180-270 degreeC.
(19) The method for producing a molding material according to any one of (17) and (18), wherein the step (II) is performed at a temperature of 180 to 320 ° C.
(20) The method for producing a molding material according to any one of (17) to (19), wherein the heat treatment is further performed at a temperature of 180 to 320 ° C. after the steps (I) to (III).
It is.

  By using the molding material of the present invention, when the injection molding is carried out, the dispersion of the reinforcing fibers in the molded product is good, and a molded product having excellent heat resistance and mechanical properties can be easily produced without environmental pollution. Can do.

It is the schematic which shows an example of the form of the composite_body | complex which consists of a reinforced fiber bundle (A), a polyarylene sulfide (B), a zerovalent transition metal compound (D), or a low valence iron compound (E). It is the schematic which shows an example of the preferable aspect of the molding material of this invention. It is the schematic which shows an example of the shape of the axial direction cross section of the preferable aspect of the molding material of this invention. It is the schematic which shows an example of the shape of the axial direction cross section of the preferable aspect of the molding material of this invention. It is the schematic which shows an example of the shape of the axial direction cross section of the preferable aspect of the molding material of this invention. It is the schematic which shows an example of the shape of the axial direction cross section of the preferable aspect of the molding material of this invention. It is the schematic which shows an example of the shape of the orthogonal cross section of the preferable aspect of the molding material of this invention. It is the schematic which shows an example of the shape of the orthogonal cross section of the preferable aspect of the molding material of this invention. It is the schematic which shows an example of the shape of the orthogonal cross section of the preferable aspect of the molding material of this invention. It is the schematic which shows an example of the shape of the orthogonal cross section of the preferable aspect of the molding material of this invention. It is the schematic which shows an example of the shape of the orthogonal cross section of the preferable aspect of the molding material of this invention.

  The molding material of the present invention comprises a continuous reinforcing fiber bundle (A), a polyarylene sulfide (B), a thermoplastic resin (C), and a zero-valent transition metal compound (D) or a low-valent iron compound (E). Composed. First, each component will be described.

<Reinforcing fiber bundle (A)>
The reinforcing fiber used in the present invention is not particularly limited, but carbon fiber, glass fiber, aramid fiber, boron fiber, alumina fiber, mineral fiber, silicon carbide fiber and the like can be used, and two or more of these fibers are mixed. You can also.

  In particular, carbon fibers are preferable from the viewpoint of excellent specific strength and specific rigidity, and improving the mechanical properties of the molded product. Among these, from the viewpoint of obtaining a molded article having a light weight, high strength, and high elastic modulus, it is preferable to use carbon fibers, and it is particularly preferable to use carbon fibers having a tensile elastic modulus of 200 to 700 GPa. Furthermore, carbon fibers and reinforcing fibers coated with metal have high conductivity, and thus have the effect of improving the conductivity of the molded product. For example, for housing applications such as electronic devices that require electromagnetic shielding properties. Is particularly preferred.

  As a more preferred embodiment of the carbon fiber, the amount of surface functional groups (O / C), which is the ratio of the number of atoms of oxygen (O) and carbon (C) on the fiber surface measured by X-ray photoelectron spectroscopy, is 0. The range is from 0.05 to 0.4. The higher the O / C, the greater the functional group amount on the carbon fiber surface, and the higher the adhesiveness with the matrix resin. On the other hand, if O / C is too high, there is a concern about the destruction of the crystal structure on the surface of the carbon fiber. Within the preferable range of O / C, it is possible to obtain a molded product particularly excellent in the balance of mechanical properties.

The surface functional group amount (O / C) is determined by the following procedure by X-ray photoelectron spectroscopy. First, the carbon fibers from which the sizing agent and the like have been removed with a solvent are cut and spread and arranged on a copper sample support, and then the photoelectron escape angle is set to 90 °, MgK _α1,2 is used as the X-ray source, and the sample chamber Keep the inside at 1 × 10 ⁻⁸ Torr. As a correction of the peak accompanying charging during measurement, the kinetic energy value (KE) of the main peak of C1S is adjusted to 969 eV. The C1S peak area is the K.S. E. Is obtained by drawing a straight base line in the range of 958 to 972 eV. The O1S peak area E. It is obtained by drawing a straight base line in the range of 714 to 726 eV. Here, the surface functional group amount (O / C) is calculated as an atomic ratio from the ratio of the O1S peak area to the C1S peak area using a sensitivity correction value unique to the apparatus.

  The number of single fibers is preferably 10,000 or more because the number of single fibers in the reinforcing fiber bundle is more advantageous for economy. On the other hand, the larger the number of single fibers of the reinforcing fiber, the more likely it is that the impregnation property of the matrix resin tends to be disadvantageous. More preferably, 10000 or more and 100,000 or less, more preferably 20,000 or more and 50,000 or less can be used. In particular, it is an effect of the present invention that is excellent in the impregnation property of the thermoplastic resin in the process of producing the molding material, and that the reinforcing fiber is well dispersed in the molded product during the injection molding. Is suitable for a reinforcing fiber bundle having a larger number of fibers.

  Furthermore, a sizing agent may be used separately from the component (B) of the present invention for the purpose of bundling single fibers into a reinforcing fiber bundle. This is because the sizing agent is attached to the reinforcing fiber bundle, and the handling property at the time of transferring the reinforcing fiber and the processability in the process of producing the molding material are improved, and within the range not impairing the object of the present invention. Sizing agents such as resins, urethane resins, acrylic resins and various thermoplastic resins can be used alone or in combination of two or more.

  The continuous reinforcing fiber bundle (A) used in the molding material of the present invention means that a reinforcing fiber bundle in which single fibers are arranged in one direction is in a continuous state in the length direction. It is not necessary for all the single fibers of the fiber bundle to be continuous over the entire length, and some of the single fibers may be divided in the middle. Examples of such continuous reinforcing fiber bundles include unidirectional fiber bundles, bi-directional fiber bundles, and multidirectional fiber bundles, but from the viewpoint of productivity in the process of manufacturing a molding material, unidirectional The fiber bundle can be used more preferably.

<Polyarylene sulfide (B)>
The polyarylene sulfide used in the present invention (hereinafter sometimes abbreviated as PAS) has a repeating unit of the formula, — (Ar—S) —, as the main constituent unit, and preferably 80% by weight or more of the repeating unit. More preferably, it is a homopolymer or copolymer containing 90% by weight or more, more preferably 95% by weight or more. Ar includes units represented by the following formulas (a) to (k), among which the formula (a) is particularly preferable.

(R1 and R2 are substituents selected from hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an arylene group having 6 to 24 carbon atoms, and a halogen group, and R1 and R2 May be the same or different.)

  As long as this repeating unit is a main structural unit, it can contain a small amount of branching units or crosslinking units represented by the following formulas (l) to (n). The amount of copolymerization of these branched units or cross-linked units is preferably in the range of 0 to 1 mol% with respect to 1 mol of-(Ar-S)-units.

  Further, the PAS in the present invention may be any of a random copolymer, a block copolymer and a mixture thereof containing the above repeating unit.

  Typical examples of these include polyphenylene sulfide, polyphenylene sulfide sulfone, polyphenylene sulfide ketone, polyphenylene sulfide ether, random copolymers thereof, block copolymers and mixtures thereof. Particularly preferred PASs include p-phenylene sulfide units as the main structural unit of the polymer.

Of polyphenylene sulfide (hereinafter sometimes abbreviated as PPS).

  The molecular weight of PAS in the present invention is 10,000 or more, preferably 15,000 or more, more preferably 18,000 or more in terms of weight average molecular weight. When the weight average molecular weight is not less than the above-mentioned preferable lower limit, the low molecular weight component hardly causes a thermal decomposition reaction even at the time of molding at a higher temperature (for example, 360 ° C.), and the environmental pollution around the molding equipment is caused by the decomposition gas. It does not cause. The upper limit of the weight average molecular weight is not particularly limited, but 1,000,000 or less can be exemplified as a preferable range, more preferably 500,000 or less, and still more preferably 200,000 or less. Sex can be obtained.

  The molecular weight distribution of PAS in the present invention, that is, the degree of dispersion represented by the ratio of weight average molecular weight to number average molecular weight (weight average molecular weight / number average molecular weight) is 2.5 or less, preferably 2.3 or less, 2.1 or less is more preferable, and 2.0 or less is more preferable. When the degree of dispersion is within this preferred range, the amount of low molecular components contained in PAS is small, and environmental pollution around the molding equipment is not caused. In addition, the said weight average molecular weight and number average molecular weight can be calculated | required, for example using SEC (size exclusion chromatography) equipped with the differential refractive index detector.

  The melt viscosity of PAS in the present invention is not particularly limited, but a preferred range is usually a melt viscosity of 5 to 10,000 Pa · s (300 ° C., shear rate 1000 / sec).

  In the present invention, PAS preferably contains substantially no halogen other than chlorine, that is, fluorine, bromine, iodine, or astatine. When PAS contains chlorine as a halogen in the present invention, PAS is stable in the temperature range where PAS is normally used. Therefore, even if a small amount of chlorine is contained, the mechanical properties of PAS and the influence of generated gas on the human body are small. When halogens other than chlorine are contained, the cracked gas due to their unique properties may adversely affect the environment around the molding equipment, so excessive equipment is required to remove the cracked gas. Here, “substantially free of halogens other than chlorine” means, for example, that the polymer is burned and the combustion gas is absorbed, and the solution is subjected to quantitative analysis by ion chromatography or the like. Means below the detection limit. In the present invention, even when PAS contains chlorine as a halogen, from the same viewpoint, the preferable amount is 1% by weight or less, more preferably 0.5% by weight or less, and further preferably 0.2% by weight or less. is there.

The PAS used in the present invention preferably has a weight reduction upon heating satisfying the following formula (1) from the viewpoint of keeping the decomposition gas during molding low.
ΔWr = (W1-W2) /W1×100≦0.20 (%) (1).

  Here, ΔWr is a weight reduction rate (%), and when thermogravimetric analysis was performed at a temperature increase rate of 20 ° C./min from 50 ° C. to an arbitrary temperature of 330 ° C. or higher in a non-oxidizing atmosphere at normal pressure. The value obtained from the sample weight (W2) when reaching 330 ° C. with reference to the sample weight (W1) when reaching 100 ° C.

  In the PAS used in the present invention, ΔWr is 0.20% or less, preferably 0.16% or less, more preferably 0.13% or less, and 0.10% or less. Even more preferable. When ΔWr is in the preferred range, for example, even when the fiber-reinforced resin member is heated by a fire or the like, the amount of generated gas is small. ΔWr can be obtained by a general thermogravimetric analysis, and the atmosphere in this analysis is a normal pressure non-oxidizing atmosphere. The non-oxidizing atmosphere indicates an atmosphere that substantially does not contain oxygen, that is, an inert gas atmosphere such as nitrogen, helium, or argon.

  In the measurement of ΔWr, thermogravimetric analysis is performed by increasing the temperature from 50 ° C. to an arbitrary temperature of 330 ° C. or higher at a temperature increase rate of 20 ° C./min. In the present invention, thermogravimetric analysis is performed by holding at 50 ° C. for 1 minute and then increasing the temperature at a rate of temperature increase of 20 ° C./min.

<Polyarylene sulfide prepolymer (B ')>
In the present invention, PAS heats a polyarylene sulfide prepolymer containing at least 50% by weight or more of a cyclic polyarylene sulfide represented by the following formula (o) and having a weight average molecular weight of less than 10,000, It can be produced by converting the polymer to a high degree of polymerization having a weight average molecular weight of 10,000 or more.

  As a more preferred embodiment of the polyarylene sulfide prepolymer, the cyclic polyarylene sulfide is contained in an amount of 70% by weight or more, more preferably 80% by weight or more, and particularly preferably 90% by weight or more. The upper limit value of the cyclic polyarylene sulfide contained in the polyarylene sulfide prepolymer is not particularly limited, but 98% by weight or less, preferably 95% by weight or less can be exemplified as a preferred range.

  Usually, the higher the weight ratio of cyclic polyarylene sulfide in the polyarylene sulfide prepolymer, the higher the degree of polymerization of PAS obtained after heating. That is, in the present invention, by adjusting the abundance ratio of the cyclic polyarylene sulfide in the polyarylene sulfide prepolymer, the degree of polymerization of the PAS obtained can be adjusted, and the amount of gas generated during heating can be further reduced. .

  Therefore, after the polyarylene sulfide prepolymer is impregnated into a continuous reinforcing fiber bundle in advance, it is heated to convert the polyarylene sulfide prepolymer into a high degree of polymerization of PAS (I), or the polyarylene sulfide prepolymer is heated. A method of impregnating a continuous reinforcing fiber bundle while polymerizing the polymer, and a method of impregnating a continuous reinforcing fiber bundle after the polyarylene sulfide prepolymer is heated to be converted to a high degree of polymerization of PAS. In (III) and the like, a composite composed of continuous reinforcing fiber bundle (A) and polyarylene sulfide (B) can be formed. From the viewpoint of economy and productivity in the process of producing a molding material, The method (I) is preferred.

  Although there is no restriction | limiting in particular in the repeating number m in the said (o) formula of cyclic polyarylene sulfide, 4-50 are preferable, 4-25 are more preferable, 4-15 can be illustrated as a more preferable range, 8 or more can be illustrated. The (o) cyclic compound as the main component is even more preferable. As will be described later, the conversion of the cyclic polyarylene sulfide to the polyarylene sulfide by heating is preferably performed at a temperature higher than the temperature at which the cyclic polyarylene sulfide is melted, but when m is increased, the melting temperature of the cyclic polyarylene sulfide is melted. Therefore, it is advantageous to set m in the above range from the viewpoint that the conversion of the cyclic polyarylene sulfide to the polyarylene sulfide can be performed at a lower temperature. Since cyclic compounds having m of 7 or less tend to have low reactivity, it is advantageous to set m to 8 or more from the viewpoint that polyarylene sulfide can be obtained in a short time.

  Further, the cyclic compound of the formula (o) contained in the cyclic polyarylene sulfide may be either a single compound having a single repeating number or a mixture of cyclic compounds having different repeating numbers, but different repeating numbers. A mixture of cyclic compounds having a tendency to have a lower melt solution temperature than a single compound having a single number of repetitions, and the use of a mixture of cyclic compounds having different numbers of repetitions may result in conversion to polyarylene sulfide. Since the temperature at the time of performing can be made lower, it is preferable.

  The upper limit value of the molecular weight of the cyclic polyarylene sulfide is preferably 10,000 or less in terms of weight average molecular weight, more preferably 5,000 or less, and further preferably 3,000 or less, while the lower limit value is 300 or more in terms of weight average molecular weight. Preferably, 400 or more is preferable, and 500 or more is more preferable.

  Here, examples of the method for obtaining the polyarylene sulfide prepolymer include the following methods (1) and (2).

  (1) Granules separated by 80 mesh sieve (aperture 0.125 mm) by polymerizing polyarylene sulfide resin by heating a mixture containing at least a polyhalogenated aromatic compound, a sulfidizing agent and an organic polar solvent A mixture containing a PAS resin, a PAS component produced by polymerization and other than the granular PAS resin (referred to as polyarylene sulfide oligomer), an organic polar solvent, water, and an alkali metal halide salt; A method of obtaining a polyarylene sulfide prepolymer by separating and recovering the polyarylene sulfide oligomer contained therein and subjecting it to a purification operation.

  (2) A polyarylene sulfide resin is polymerized by heating a mixture containing at least a polyhalogenated aromatic compound, a sulfidizing agent and an organic polar solvent, and the organic polar solvent is removed after the polymerization is completed. A polyarylene sulfide resin containing a polyarylene sulfide prepolymer obtained by preparing a mixture containing water, an alkali metal halide salt, and refining the mixture is obtained, and the polyarylene sulfide resin is substantially dissolved therein. However, the polyarylene sulfide prepolymer is extracted using a solvent that dissolves, and the polyarylene sulfide prepolymer is recovered.

  In the polyarylene sulfide prepolymer of the present invention, from the viewpoint of keeping the decomposition gas during the production of the molding material low, the weight loss when heated is ΔWr of 5% or less in the formula (1), and 3% or less. Preferably, it is preferably 2% or less, and more preferably 1% or less. Further, by selecting a polyarylene sulfide prepolymer having such requirements, it is possible to minimize the decrease in raw materials during heat polymerization to polyarylene sulfide.

  Furthermore, the polyarylene sulfide in the present invention can be obtained by heating the polyarylene sulfide prepolymer in the presence of a zero-valent transition metal compound or a low-valent iron compound. According to this method, the above-described characteristics can be easily obtained. A polyarylene sulfide having the same can be obtained.

  In the above-described production method, the conversion rate of cyclic polyarylene sulfide to polyarylene sulfide is preferably 70% or more, more preferably 80% or more, and further preferably 90% or more. If the conversion is 70% or more, a polyarylene sulfide having the above-described characteristics can be obtained. Here, the conversion ratio of cyclic polyarylene sulfide to polyarylene sulfide indicates the ratio of cyclic polyarylene sulfide converted to high molecular weight polyarylene sulfide in polyarylene sulfide prepolymer (B ′). It is a thing.

<Zerovalent transition metal compound (D)>
In the present invention, various zero-valent transition metal compounds are used as a polymerization catalyst. As the zero-valent transition metal, metals of Group 8 to Group 11 and Period 4 to Period 6 of the periodic table are preferably used. For example, nickel, palladium, platinum, iron, ruthenium, rhodium, copper, silver, and gold can be exemplified as the metal species. Various complexes are suitable as the zero-valent transition metal compound. For example, triphenylphosphine, tri-t-butylphosphine, tricyclohexylphosphine, 1,2-bis (diphenylphosphino) ethane, 1 , 1'-bis (diphenylphosphino) ferrocene, dibenzylideneacetone, dimethoxydibenzylideneacetone, cyclooctadiene, and carbonyl complexes. Specifically, bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium, tetrakis (triphenylphosphine) palladium, bis (tri-t-butylphosphine) palladium, bis [1,2-bis (diphenylphosphine) Fino) ethane] palladium, bis (tricyclohexylphosphine) palladium, [P, P′-1,3-bis (di-i-propylphosphino) propane] [P-1,3-bis (di-i-propyl) Phosphino) propane] palladium, 1,3-bis (2,6-di-i-propylphenyl) imidazol-2-ylidene (1,4-naphthoquinone) palladium dimer, 1,3-bis (2,4 , 6-Trimethylphenyl) imidazol-2-ylidene (1,4-naphthoquinone) palladium dimer, bi (3,5,3 ′, 5′-dimethoxydibenzylideneacetone) palladium, bis (tri-t-butylphosphine) platinum, tetrakis (triphenylphosphine) platinum, tetrakis (trifluorophosphine) platinum, ethylenebis (tri Phenylphosphine) platinum, platinum-2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane complex, tetrakis (triphenylphosphine) nickel, tetrakis (triphenylphosphite) nickel, Examples thereof include bis (1,5-cyclooctadiene) nickel, dodecacarbonyl triiron, pentacarbonyl iron, dodecacarbonyl tetrarhodium, hexadecacarbonyl hexarhodium, dodecacarbonyl triruthenium and the like. These polymerization catalysts may be used alone or in combination of two or more.

  These polymerization catalysts may be added with a zero-valent transition metal compound as described above, or may form a zero-valent transition metal compound in the system. Here, in order to form a zero-valent transition metal compound in the system as in the latter case, a transition metal compound such as a transition metal salt and a ligand compound are added to form a transition metal complex in the system. And a method of adding a complex formed of a transition metal compound such as a transition metal salt and a compound serving as a ligand. Examples of transition metal compounds and ligands used in the present invention and complexes formed of transition metal compounds and ligands are given below. Examples of the transition metal compound for forming a zero-valent transition metal compound in the system include acetates and halides of various transition metals. Examples of the transition metal species include nickel, palladium, platinum, iron, ruthenium, rhodium, copper, silver, gold acetate, halide and the like. Specifically, nickel acetate, nickel chloride, nickel bromide. , Nickel iodide, nickel sulfide, palladium acetate, palladium chloride, palladium bromide, palladium iodide, palladium sulfide, platinum chloride, platinum bromide, iron acetate, iron chloride, iron bromide, iron iodide, ruthenium acetate, chloride Examples include ruthenium, ruthenium bromide, rhodium acetate, rhodium chloride, rhodium bromide, copper acetate, copper chloride, copper bromide, silver acetate, silver chloride, silver bromide, gold acetate, gold chloride, and gold bromide. The ligand added simultaneously to form a zero-valent transition metal compound in the system is one that generates a zero-valent transition metal when the cyclic polyarylene sulfide and the transition metal compound are heated. Although not particularly limited, basic compounds are preferable, and examples thereof include triphenylphosphine, tri-t-butylphosphine, tricyclohexylphosphine, 1,2-bis (diphenylphosphino) ethane, 1,1′-bis (diphenylphosphine). Fino) ferrocene, dibenzylideneacetone, sodium carbonate, ethylenediamine and the like. Moreover, as a complex formed with the compound used as a transition metal compound and a ligand, the complex which consists of the above various transition metal salts and a ligand is mentioned. Specifically, bis (triphenylphosphine) palladium diacetate, bis (triphenylphosphine) palladium dichloride, [1,2-bis (diphenylphosphino) ethane] palladium dichloride, [1,1′-bis (diphenylphosphine) Fino) ferrocene] palladium dichloride, dichloro (1,5′-cyclooctadiene) palladium, bis (ethylenediamine) palladium dichloride, bis (triphenylphosphine) nickel dichloride, [1,2-bis (diphenylphosphino) ethane] nickel Examples include dichloride, [1,1′-bis (diphenylphosphino) ferrocene] nickel dichloride, dichloro (1,5′-cyclooctadiene) platinum and the like. These polymerization catalysts and ligands may be used alone or in combination of two or more.

  The valence state of the transition metal compound can be grasped by X-ray absorption fine structure (XAFS) analysis. Transition metal compound used as a catalyst in the present invention or cyclic polyarylene sulfide containing a transition metal compound or polyarylene sulfide containing a transition metal compound is irradiated with X-rays, and the absorption coefficient peak when the absorption spectrum is normalized This can be grasped by comparing the maximum values.

  For example, when evaluating the valence of a palladium compound, it is effective to compare the absorption spectrum of the L3 end X-ray absorption near edge structure (XANES), and the X-ray energy is 3173 eV as a reference, 3163 to 3168 eV. This can be determined by comparing the peak maximum value of the absorption coefficient when the average absorption coefficient in the range of 0 and 3191 to 3200 eV is normalized to 1. In the example of palladium, the peak value of the absorption coefficient when normalized with the zero-valent palladium compound tends to be small compared to the divalent palladium compound, and further promotes the conversion of the cyclic polyarylene sulfide. A transition metal compound having a larger effect tends to have a smaller peak maximum value. The reason for this is presumed that the absorption spectrum for XANES corresponds to the transition of core electrons to empty orbitals, and the absorption peak intensity is affected by the electron density of d orbitals.

  In order for the palladium compound to promote the conversion of cyclic polyarylene sulfide to polyarylene sulfide, the peak maximum value of the absorption coefficient when normalized is preferably 6 or less, more preferably 4 or less, still more preferably Is 3 or less, and within this range, the conversion of the cyclic polyarylene sulfide can be promoted.

  Specifically, the peak maximum is 6.32 for divalent palladium chloride that does not promote the conversion of cyclic polyarylene sulfide, and zero-valent tris (dibenzylideneacetone) divalent that promotes the conversion of cyclic polyarylene sulfide. For palladium and tetrakis (triphenylphosphine) palladium and bis [1,2-bis (diphenylphosphino) ethane] palladium it is 3.43 and 2.99 and 2.07, respectively.

<Low-valent iron compound (E)>
In the present invention, various low-valent iron compounds (E) are used as a polymerization catalyst. It is known that an iron atom can theoretically take a valence state of -II, -I, 0, I, II, III, IV, V, and VI. The iron compound having a valence of -II to II. Further, the low-valent iron compound (E) described here is a valence of the iron compound in the reaction system at the time of conversion of the cyclic polyarylene sulfide to the polyarylene sulfide by heating is -II to II. It points to something.

  Examples of the low-valent iron compound (E) include iron compounds having a valence of −II to II. From the viewpoint of stability of the iron compound, ease of handling, availability, and the like, As the low-valent iron compound (E), zero-valent, I-valent, and II-valent iron compounds are preferably used, and among these, II-valent iron compounds are particularly preferable.

  As the divalent iron compound, various iron compounds are suitable, and examples thereof include divalent iron halides, acetates, sulfates, phosphates, ferrocene compounds, and the like. Specific examples include iron chloride, iron bromide, iron iodide, iron fluoride, iron acetate, iron sulfate, iron phosphate, iron nitrate, iron sulfide, iron methoxide, phthalocyanine iron, and ferrocene. Among these, from the viewpoint of uniformly dispersing the iron compound in the cyclic polyarylene sulfide, an iron halide having good dispersibility in the cyclic polyarylene sulfide is preferable. From the viewpoint of economy and the polyarylene sulfide obtained. From the viewpoint of the characteristics, iron chloride is more preferable. Examples of the characteristics of the polyarylene sulfide described here include solubility in 1-chloronaphthalene. When the preferred low-valent iron compound (E) of the present invention is used, there is a tendency to obtain a polyarylene sulfide having a small insoluble portion in 1-chloronaphthalene, and preferably having no insoluble portion. This means that there are few branch units or cross-linking units, and this is a desirable property as polyarylene sulfide from the viewpoint of obtaining properties such as high moldability and high mechanical strength of a molded product.

  Various iron compounds are suitable as the I-valent iron compound. Specific examples include cyclopentadienyl iron dicarbonyl dimer and 1,10-phenanthroline iron sulfate complex.

  Various iron compounds are suitable as the zero-valent iron compound, and specific examples include dodecacarbonyl triiron and pentacarbonyl iron.

  These polymerization catalysts may be used alone or in combination of two or more.

  These polymerization catalysts may be added with the low-valent iron compound (E) as described above, or may form a low-valent iron compound (E) in the system from a high-valent iron compound having a valence of III or higher. May be. Here, in order to form a low-valent iron compound (E) in the system as in the latter, a method of forming a low-valent iron compound (E) from a high-valent iron compound by heating, a cyclic polyarylene sulfide Examples thereof include a method of forming a low-valent iron compound in the system by adding a high-valent iron compound and a compound having reducibility to the high-valent iron compound as a promoter. Examples of the method for forming the low-valent iron compound (E) from the high-valent iron compound by heating include a method of forming the low-valent iron compound (E) by heating the high-valent iron halide compound. . Here, when heating the high-valent iron halide compound, it is presumed that the low-valent iron compound (E) is formed by elimination of a part of the halogen constituting the high-valent iron halide compound.

  In the present invention, when the low-valent iron compound (E) is a substance that gradually deteriorates during storage, it is added in the state of a more stable high-valent iron compound, and the polyarylene sulfide prepolymer ( In the process of converting B ′) to polyarylene sulfide (B), a method of forming a low-valent iron compound (E) in the system is preferably used. By using such a process, the molding material obtained can be stored for a long period of time, and the addition rate when the polyarylene sulfide prepolymer (B ′) is converted to the polyarylene sulfide (B) can be increased. Therefore, it is preferable.

  Examples of the high-valent iron compound used in the present invention are given below. Various iron compounds are suitable as the high-valent iron compound for forming the low-valent iron compound (E) in the system. For example, as the III-valent iron compound, iron chloride, iron bromide, fluoride Examples thereof include iron, iron citrate, iron nitrate, iron sulfate, iron acetylacetonate, iron benzoylacetonate diethyldithiocarbamate, iron ethoxide, iron isopropoxide, and iron acrylate. Among these, from the viewpoint of uniformly dispersing the iron compound in the cyclic polyarylene sulfide, an iron halide having good dispersibility in the cyclic polyarylene sulfide is preferable. From the viewpoint of economy and the polyarylene sulfide obtained. From the viewpoint of the characteristics, iron chloride is more preferable. Examples of the characteristics of the polyarylene sulfide described here include solubility in 1-chloronaphthalene. When the preferred low-valent iron compound (E) of the present invention is used, there is a tendency to obtain a polyarylene sulfide having a small insoluble portion in 1-chloronaphthalene, and preferably having no insoluble portion. This means that there are few branch units or cross-linking units, and this is a desirable property as polyarylene sulfide from the viewpoint of obtaining properties such as high moldability and high mechanical strength of a molded product.

  Examples of the promoter used in the present invention will be given below. As a co-catalyst added to form the low-valent iron compound (E) in the system, when the cyclic polyarylene sulfide and the high-valent iron compound are heated, the low-valent atom reacts with the high-valent iron compound. Although it will not specifically limit if it produces | generates a ferric iron compound, The compound which has various organic and inorganic reducibility is preferable, for example, copper chloride (I), tin chloride (II), titanium chloride (III), ethylenediamine, Examples thereof include N, N′-dimethylethylenediamine, triphenylphosphine, tri-t-butylphosphine, tricyclohexylphosphine, 1,2-bis (diphenylphosphino) ethane and the like. Among these, copper (I) chloride, tin (II) chloride, and titanium (III) chloride are preferable, and copper (I) and tin (II) chloride that can be safely handled in a solid state are more preferable.

  These polymerization catalysts and cocatalysts may be used alone or in combination of two or more.

  The valence state of the iron compound in the reaction system and the structure near the iron atom can be grasped by X-ray absorption fine structure (XAFS) analysis. The iron compound used as a catalyst in the present invention, or a cyclic polyarylene sulfide containing an iron compound, or a polyarylene sulfide containing an iron compound is irradiated with X-rays, and the shape of the absorption spectrum thereof is compared to compare the iron compound The valence state and the structure near the iron atom can be grasped.

  When evaluating the valence of iron compounds, it is effective to compare the absorption spectra for the X-ray absorption near edge structure (XANES) at the K end, and it is possible to make a judgment by comparing the energy at which the spectrum rises and the spectrum shape. is there. The spectrum obtained by measuring the II-valent iron compound compared to the spectrum obtained by measuring the III-valent iron compound, and further the spectrum obtained by measuring the zero-valent iron compound, the rising of the main peak is on the lower energy side. Tend to be. Specifically, in the case of iron (III) chloride, which is a trivalent iron compound, iron oxide (III), etc., the rise of the main peak is around 7120 eV, and iron (II) chloride, iron chloride (II) which is a divalent iron compound. II) The rise of the main peak is observed in the vicinity of 7110 to 7115 eV in tetrahydrate and the like, and the shoulder structure is observed in the spectrum from around 7110 eV in iron metal (0) that is a zerovalent iron compound. Further, the spectrum obtained by measuring the II-valent iron compound has a tendency that the peak top position of the main peak is on the lower energy side as compared with the spectrum obtained by measuring the III-valent iron compound. Specifically, the peak top of the main peak is observed in the vicinity of 7128-7139 eV in the case of the III-valent iron compound, and in the vicinity of 7120-7128 eV in the case of the II-valent iron compound, and more specifically, it is a III-valent iron compound. It is around 7128-7134 eV for iron (III) chloride, about 7132 eV for iron (III) oxide, about 7120 eV for iron (II) chloride, which is a divalent iron compound, and 7123 eV for iron (II) chloride tetrahydrate. A peak top of the main peak is observed in the vicinity.

  Moreover, when evaluating the structure of the iron compound near the iron atom, it is effective to compare the radial distribution functions obtained from the K-edge broad X-ray absorption fine structure (EXAFS), and the distance at which the peak is observed is determined. Judgment is possible by comparison. In iron metal (0), peaks attributed to the Fe—Fe bond are observed around 0.22 nm and 0.44 nm. In iron (III) chloride, a peak attributed to Fe—Cl bond is around 0.16 to 0.17 nm, and in iron (II) chloride, a peak attributed to Fe—Cl bond is around 0.21 nm. ) In the tetrahydrate, a peak due to the Fe—Cl bond is observed in the vicinity of 0.16 to 0.17 nm, and a sub-peak considered to be another Fe—Cl bond is also observed in the vicinity of 0.21 nm. In iron (III) oxide, a peak attributed to the Fe—O bond is observed near 0.15 to 0.17 nm, and a peak attributed to the Fe—Fe bond or the like is observed near 0.26 to 0.33 nm.

  That is, by comparing the spectrum obtained during X-ray absorption fine structure (XAFS) analysis of the reaction product or the reaction product with the spectra of various iron compounds, the valence state of the iron compound and the structure near the iron atom can be grasped. Is possible.

  When adding the iron compound, it is preferable to add it under conditions that do not contain moisture. A preferable amount of water contained in the gas phase in contact with the cyclic polyarylene sulfide and the iron compound to be added is 1% by weight or less, more preferably 0.5% by weight or less, and further preferably 0.1% by weight or less. It is even more preferable that substantially no be contained. The molar ratio of the amount of water contained in the cyclic polyarylene sulfide, the amount of water contained in the polymerization catalyst, and the total amount of water contained as a hydrate in the polymerization catalyst to the added polymerization catalyst is 9 or less. Preferably, it is 6 or less, more preferably 3 or less, even more preferably 1 or less, and even more preferably 0.1 or less, and still more preferably contains substantially no water. If it is below this moisture content, side reactions, such as an oxidation reaction and a hydrolysis reaction of a low valent iron compound (E), can be prevented. For this reason, the form of the iron compound to be added is preferably an anhydride rather than a hydrate.

  Moreover, when adding an iron compound, in order to prevent a water | moisture content from being contained in cyclic polyarylene sulfide and an iron compound, you may add an iron compound and a desiccant together. Examples of the desiccant include metals, neutral desiccants, basic desiccants, and acidic desiccants. In order to prevent oxidation of the low-valent iron compound (E), an oxidizing substance may not be present in the system. Since it is important, a neutral desiccant and a basic desiccant are preferable. Specific examples of these desiccants include calcium chloride, aluminum oxide, calcium sulfate, magnesium sulfate, and sodium sulfate as neutral desiccants, and potassium carbonate, calcium oxide, barium oxide, and the like as basic desiccants. Of these, calcium chloride and aluminum oxide, which have a relatively large moisture absorption capacity and are easy to handle, are preferable. When adding an iron compound and a desiccant together, the amount of water contained in the cyclic polyarylene sulfide, the amount of water contained in the polymerization catalyst, and the total amount of water molecules contained as a hydrate in the polymerization catalyst. Does not include the amount of water dehydrated by the desiccant.

  The water content can be quantified by the Karl Fischer method. The amount of water contained in the gas phase in contact with the cyclic polyarylene sulfide and the iron compound to be added can also be calculated from the temperature and relative humidity of the gas phase. In addition, the amount of water contained in the cyclic polyarylene sulfide and the amount of water contained in the polymerization catalyst can be quantified using an infrared moisture meter or gas chromatography, and the cyclic polyarylene sulfide, It can also be determined from the weight change before and after heating when the polymerization catalyst is heated at a temperature of about 100 to 110 ° C.

  It is preferable to add the iron compound in a non-oxidizing atmosphere. Here, the non-oxidizing atmosphere is an atmosphere in which the oxygen concentration in the gas phase in contact with the cyclic polyarylene sulfide and the iron compound to be added is 5% by volume or less, preferably 2% by volume or less, more preferably substantially free of oxygen. That is, it means an inert gas atmosphere such as nitrogen, helium, argon, etc. Among them, a nitrogen atmosphere is particularly preferable from the viewpoint of economy and easy handling. Moreover, when adding the said iron compound, it is preferable to add on the conditions which do not contain an oxidizing substance. Here, the term “not containing an oxidizing substance” means that the molar ratio of the oxidizing substance contained in the cyclic polyarylene sulfide to the added polymerization catalyst is 1 or less, preferably 0.5 or less, more preferably 0.1 or less. More preferably, it means substantially free of oxidizing substances. The oxidizing substance refers to a substance that oxidizes the polymerization catalyst and changes it to a compound having no catalytic activity, for example, iron (III) oxide. For example, oxygen, organic peroxide, inorganic Peroxides are listed. Under such conditions, side reactions such as an oxidation reaction of the low-valent iron compound can be prevented.

  The concentration of the zero-valent transition metal compound (D) or the low-valent iron compound (E) used depends on the molecular weight of the target polyarylene sulfide and the zero-valent transition metal compound (D) or the low-valent iron compound (E). Although it varies depending on the type, it is usually 0.001 to 20 mol%, preferably 0.005 to 15 mol%, more preferably 0.01 to 10 mol%, based on sulfur atoms in the polyarylene sulfide prepolymer. If it is 0.001 mol% or more, the polyarylene sulfide prepolymer is sufficiently converted to polyarylene sulfide, and if it is 20 mol% or less, a polyarylene sulfide having the above-mentioned properties can be obtained.

  Further, the zero-valent transition metal compound (D) or the low-valent iron compound (E) remains even after the heat polymerization of the polyarylene sulfide in the present invention. Therefore, the zero-valent transition metal compound (D) or the low-valent iron compound (E) is also 0.001 to 20 mol%, preferably 0.005 to 15 mol, based on the sulfur atom in the polyarylene sulfide. %, More preferably 0.01 to 10 mol%.

  When the zero-valent transition metal compound (D) or the low-valent iron compound (E) is added, it may be added as it is, but it is preferable that the polymerization catalyst is added to the cyclic polyarylene sulfide and then dispersed uniformly. Examples of the uniform dispersion method include a mechanical dispersion method and a dispersion method using a solvent. Specific examples of the mechanical dispersion method include a pulverizer, a stirrer, a mixer, a shaker, and a method using a mortar. Specific examples of the method of dispersing using a solvent include a method of dissolving or dispersing cyclic polyarylene sulfide in an appropriate solvent, adding a predetermined amount of a polymerization catalyst thereto, and then removing the solvent. In addition, when the polymerization catalyst is dispersed, when the polymerization catalyst is a solid, it is preferable that the average particle size of the polymerization catalyst is 1 mm or less because more uniform dispersion is possible.

  In the present invention, the molding material using the zero-valent transition metal compound (D) as a polymerization catalyst is characterized by a high conversion rate of the polyarylene sulfide prepolymer (B ′) to the polyarylene sulfide (B). By using the zero-valent transition metal compound (D) as a polymerization catalyst, a molded product having a high conversion to polyarylene sulfide (B) and excellent mechanical properties and heat resistance can be easily obtained.

  In the present invention, the low atomized iron compound (E) is characterized in that it can be obtained as a polymerization catalyst at a lower cost than the zero-valent transition metal compound (D). By using the low atomized iron compound (E) as a polymerization catalyst, a molding material with higher cost and productivity can be obtained.

<Thermoplastic resin (C)>
The thermoplastic resin used in the present invention is not particularly limited, and includes polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, polytrimethylene terephthalate (PTT) resin, polyethylene naphthalate (PENp) resin, liquid crystal polyester, and the like. Polyester resin, polyethylene (PE) resin, polypropylene (PP) resin, polyolefin resin such as polybutylene resin, styrene resin, urethane resin, polyoxymethylene (POM) resin, polyamide (PA) resin, Polycarbonate (PC) resin, polymethyl methacrylate (PMMA) resin, polyvinyl chloride (PVC) resin, polyphenylene sulfide (PPS) resin, polyphenylene ether (PPE) resin, modified PPE resin, polyimide (PI Resin, polyamideimide (PAI) resin, polyetherimide (PEI) resin, polysulfone (PSU) resin, modified PSU resin, polyethersulfone (PES) resin, polyketone (PK) resin, polyetherketone (PEK) resin, poly Fluorine resins such as ether ether ketone (PEEK) resin, polyether ketone ketone (PEKK) resin, polyarylate (PAR) resin, polyether nitrile (PEN) resin, phenol resin, phenoxy resin, polytetrafluoroethylene, etc. Copolymers, modified products, and resins obtained by blending two or more of them may be used.

  Among them, a resin excellent in heat resistance can be preferably selected from the viewpoint of further enhancing the effects of the present invention. The heat resistance referred to here is, for example, a crystalline resin having a melting point of 200 ° C. or higher, preferably 220 ° C. or higher, more preferably 240 ° C. or higher, more preferably 260 ° C. or higher, or a deflection temperature under load of 120 ° C. or higher. An amorphous resin having a temperature of preferably 140 ° C. or higher, more preferably 160 ° C. or higher, and still more preferably 180 ° C. or higher can be exemplified. Accordingly, examples of preferable resins include polyamide resins, polyimide resins, polyamideimide resins, polyetherimide resins, polyether ketone resins, polyether ether ketone resins, polyether ketone ketone resins, polyether sulfone resins, and PPS resins. Further, polyamide resins, polyetherimide resins, polyamideimide resins, polyetheretherketone resins, and polyphenylene sulfide resins can be exemplified as preferable resins. In addition, when the thermoplastic resin (C) is a PPS resin, the same PAS resin as the component (B) may be used or a different PAS resin may be used. It is preferable to use a PPS resin having a higher molecular weight than the component (B).

  The thermoplastic resin composition exemplified in the above group contains an impact resistance improver such as a fiber reinforcing agent, an elastomer or a rubber component, and other fillers and additives as long as the object of the present invention is not impaired. Also good. Examples of these include inorganic fillers, flame retardants, conductivity imparting agents, crystal nucleating agents, ultraviolet absorbers, antioxidants, vibration damping agents, antibacterial agents, insect repellents, deodorants, anti-coloring agents, heat stabilizers. , Release agents, antistatic agents, plasticizers, lubricants, colorants, pigments, dyes, foaming agents, antifoaming agents, or coupling agents.

<Molding material>
The molding material of the present invention comprises a reinforcing fiber bundle (A), a polyarylene sulfide (B), a thermoplastic resin (C), and a zero-valent transition metal compound (D) or a low-valent iron compound (E).

  Of these, the reinforcing fiber bundle (A) is 1 to 50% by weight, preferably 5 to 45% by weight, more preferably 10 when the total of the constituent components (A) to (C) is 100% by weight. -40% by weight. If the reinforcing fiber bundle (A) is less than 1% by weight, the resulting molded article may have insufficient mechanical properties, and if it exceeds 50% by weight, the fluidity may be reduced during injection molding.

  The polyarylene sulfide (B) is 0.1 to 15% by weight, preferably 0.5 to 10% by weight, when the total of the components (A) to (C) is 100% by weight. Preferably, it is 1 to 8% by weight. If the polyarylene sulfide (B) is less than 0.1% by weight, the moldability of the molding material, that is, the dispersion of the reinforcing fibers at the time of molding may be insufficient, and if it exceeds 15% by weight, the heat that is the matrix resin The mechanical properties of the plastic resin may be reduced.

  Furthermore, the thermoplastic resin (C) is 35 to 98.9% by weight, preferably 45 to 94.5% by weight, when the total of the components (A) to (C) is 100% by weight. Preferably it is 52 to 89 weight%, and the effect of this invention can be achieved by using in this range. If the thermoplastic resin (C) is less than 35% by weight, fluidity may be reduced during injection molding, and if it exceeds 98.9% by weight, the resulting molded article may have insufficient mechanical properties.

  Further, the zero-valent transition metal compound (D) or the low-valent iron compound (E) is 0.001 to 20 mol%, preferably 0.005 to 15 mol%, based on the sulfur atom in the polyarylene sulfide (B). More preferably, it is 0.01-10 mol%.

  The molding material of the present invention is a molding material that is arranged and arranged so that the thermoplastic resin (C) adheres to a composite composed of a continuous reinforcing fiber bundle (A) and a polyarylene sulfide (B).

  A composite of the reinforcing fiber bundle (A) and the polyarylene sulfide (B) is formed by the two. The form of this composite is as shown in FIG. 1, and the polyarylene sulfide (B) is filled between the single fibers of the reinforcing fiber bundle (A). That is, the reinforcing fibers (A) are dispersed like islands in the polyarylene sulfide (B) sea. The specific formation of the complex is as described above.

  The zero-valent transition metal compound (D) or the low-valent iron compound (E) has a role as a heat polymerization catalyst in the sea of the polyarylene sulfide (B) and / or the reinforcing fiber bundle (A) and the polyarylene sulfide ( It is preferably present at the interface with B).

  In the molding material of the present invention, a thermoplastic resin (C) is bonded to a composite in which a polyarylene sulfide (B) excellent in heat resistance and low gas properties is satisfactorily impregnated in a reinforcing fiber bundle (A). Even if, for example, when the molding material of the present invention is injection-molded, the polyarylene sulfide (B) having good fluidity, which is melt-kneaded in the cylinder of the injection molding machine, diffuses into the thermoplastic resin (C), A so-called impregnation aid / dispersion aid that helps the reinforcing fiber bundle (A) to disperse in the thermoplastic resin (C) and at the same time helps the thermoplastic resin (C) to replace and impregnate the reinforcing fiber bundle (A). Has a role as an agent.

  As a preferred embodiment in the molding material of the present invention, as shown in FIG. 2, the reinforcing fiber bundle (A) is arranged substantially parallel to the axial direction of the molding material, and the length of the reinforcing fiber bundle (A) is The length is substantially the same as the length of the molding material.

  Here, “arranged substantially in parallel” means that the long axis of the reinforcing fiber bundle and the long axis of the molding material are oriented in the same direction. The angle deviation is preferably 20 ° or less, more preferably 10 ° or less, and further preferably 5 ° or less. In addition, “substantially the same length” means that, for example, in a pellet-shaped molding material, a reinforcing fiber bundle is cut in the middle of the pellet, or a reinforcing fiber bundle substantially shorter than the entire length of the pellet is substantially included. It is not done. In particular, the amount of reinforcing fiber bundle shorter than the total length of the pellet is not specified, but when the content of reinforcing fiber having a length of 50% or less of the total length of the pellet is 30% by weight or less, the pellet It is evaluated that the reinforcing fiber bundle significantly shorter than the full length is not substantially contained. Furthermore, the content of reinforcing fibers having a length of 50% or less of the total length of the pellet is preferably 20% by weight or less. In addition, a pellet full length is the length of the reinforcing fiber orientation direction in a pellet. Since the reinforcing fiber bundle (A) has a length equivalent to that of the molding material, the reinforcing fiber length in the molded product can be increased, so that excellent mechanical properties can be obtained.

  3 to 6 schematically show examples of the shape of the cross section in the axial center direction of the molding material of the present invention, and FIGS. 7 to 10 show examples of the shape of the cross section in the orthogonal direction of the molding material of the present invention. This is a schematic representation.

  The shape of the cross-section of the molding material is such that the reinforcing fiber bundle (A), the polyarylene sulfide (B) and the zero-valent transition metal compound (D) or the low-valent iron compound (E) are combined with a thermoplastic resin ( As long as C) is arranged so as to adhere, it is not limited to the one shown in the figure, but preferably, as shown in FIGS. A configuration in which (C) is sandwiched between layers is preferable.

  Moreover, as FIG. 7-9 which is a cross section of an orthogonal | vertical direction shows, the structure arrange | positioned at the core sheath structure that a thermoplastic resin (C) coat | covers the circumference | surroundings with respect to a core is preferable. When arranging a plurality of composites as shown in FIG. 11 so as to cover the thermoplastic resin (C), the number of composites is preferably about 2 to 6.

  The boundary between the composite and the thermoplastic resin (C) is adhered, and the thermoplastic resin (C) partially enters the composite near the boundary and is compatible with the polyarylene sulfide (B) in the composite. You may be in the state which is carrying out, or the state which is impregnating the reinforced fiber.

  The axial direction of the molding material may be continuous while maintaining substantially the same cross-sectional shape. Depending on the molding method, such a continuous molding material may be cut into a certain length.

  The molding material of the present invention comprises, for example, a reinforcing fiber bundle (A), a polyarylene sulfide (B), a zero-valent transition metal compound (D), or a low-valent iron compound (E) by a technique such as injection molding or press molding. A final molded product can be produced by kneading the thermoplastic resin (C) into the resulting composite. From the viewpoint of the handling property of the molding material, it is important that the composite and the thermoplastic resin (C) are not separated until molding is performed and the shape as described above is maintained. The composite and the thermoplastic resin (C) are completely different in shape (size, aspect ratio), specific gravity, and weight, so they are classified at the time of transporting and handling the material until molding, and at the time of transferring the material in the molding process. In some cases, the mechanical properties vary, the fluidity decreases, the mold clogs, or the molding process blocks.

  Therefore, as illustrated in FIGS. 7 to 9, the reinforcing fiber bundle (A), the polyarylene sulfide (B), which is a reinforcing fiber, and the zero-valent transition metal compound (D) or the low-valent iron compound (E). The thermoplastic resin (C) is disposed so as to cover the periphery of the composite, that is, the reinforcing fiber bundle (A) and the polyarylene sulfide (B) which are reinforcing fibers. A complex composed of the zero-valent transition metal compound (D) or the low-valent iron compound (E) has a core structure, and the thermoplastic resin (C) has a core-sheath structure in which the periphery of the complex is covered. preferable. With such an arrangement, the composite can make the thermoplastic resin (C) stronger. Further, the thermoplastic resin (C) covers the periphery of the composite composed of the reinforcing fiber bundle (A), the polyarylene sulfide (B) and the zero-valent transition metal compound (D) or the low-valent iron compound (E). The thermoplastic resin (C) and the composite resin and the thermoplastic resin (C) are arranged in layers, which is advantageous because of the ease of manufacture and the ease of handling of the material. More preferably, (C) is arranged so as to cover the periphery of the composite.

  As described above, it is desirable that the reinforcing fiber bundle (A) is completely impregnated with the polyarylene sulfide (B). However, in reality, this is difficult, and the composite composed of the reinforcing fiber and the polyarylene sulfide is not suitable. There are some voids. In particular, when the content of reinforcing fibers is large, the number of voids increases. However, even when a certain amount of voids are present, the effect of promoting impregnation and fiber dispersion of the present invention is achieved. The void ratio is preferably in the range of 0 to 40%. A more preferable void ratio range is 20% or less. When the void ratio is in the above preferred range, the effect of promoting impregnation and fiber dispersion is excellent. The void fraction is measured on the part of the composite by the ASTM D2734 (1997) test method.

  The molding material of the present invention is preferably used after being cut to a length in the range of 1 to 50 mm. By adjusting to the above length, the fluidity and handleability during molding can be sufficiently enhanced. A particularly preferred embodiment of the molding material cut to an appropriate length in this way can be exemplified by long fiber pellets for injection molding.

  Further, the molding material of the present invention can be used depending on the molding method even if it is continuous or long. For example, as a thermoplastic yarn prepreg, it can be wound around a mandrel while heating to obtain a roll-shaped molded product. Examples of such molded products include liquefied natural gas tanks. It is also possible to produce a thermoplastic prepreg by aligning a plurality of the molding materials of the present invention and heating and fusing them. Such a prepreg can be applied to fields where heat resistance, high strength, elastic modulus, and impact resistance are required, such as automobile members.

  The molding material of the present invention can be processed into a final product by an ordinary molding method. Examples of the molding method include press molding, transfer molding, injection molding, and combinations thereof. Examples of molded products include cylinder head covers, bearing retainers, intake manifolds, automobile parts such as pedals, tools such as monkeys and wrenches, and small items such as gears. Moreover, since the molding material of this invention is excellent in fluidity | liquidity, the thin molded product whose thickness of a molded product is 0.5-2 mm can be obtained comparatively easily. Such thin-wall molding is required to be represented by, for example, a casing used for a personal computer, a mobile phone, or a keyboard support that is a member that supports the keyboard inside the personal computer. Examples of members for electrical and electronic equipment. In such a member for an electric / electronic device, when carbon fiber having conductivity is used as the reinforcing fiber, electromagnetic shielding properties are imparted, which is more preferable.

  The molding material described above can be used as an injection molding pellet. In injection molding, when plasticizing a pellet-shaped molding material, temperature, pressure, and kneading are applied, and according to the present invention, polyarylene sulfide (B) has a great effect as a dispersion / impregnation aid. Demonstrate. In this case, a normal in-line screw type injection molding machine can be used, such as using a screw with a low compression ratio or setting a low back pressure during material plasticization. Even when the kneading effect by is weak, the reinforcing fiber is well dispersed in the matrix resin, and a molded product in which the fiber is impregnated with the resin can be obtained.

<Method of manufacturing molding material>
The molding material of the present invention is preferably manufactured through the following steps from the viewpoint that the shape described above can be easily manufactured. That is, the step (I) of obtaining a mixture comprising a polyarylene sulfide prepolymer (B ′) and a zero-valent transition metal compound (D) or a low-valent iron compound (E), and a continuous reinforcing fiber bundle (A) A method for producing a molding material comprising the step (II) of obtaining a composite impregnated in the step, and the step (III) of adhering the composite to a thermoplastic resin (C). This is a method for producing a molding material in which an arylene sulfide prepolymer (B ′) is polymerized by heating in the presence of a zero-valent transition metal compound (D) or a low-valent iron compound (E) to convert it into a polyarylene sulfide polymer (B). .

<Process (I)>
In the step (I), an apparatus for obtaining a mixture is one having a mechanism for mixing the charged polyarylene sulfide prepolymer (B ′) with the zero-valent transition metal compound (D) or the low-valent iron compound (E). If there is no particular limitation, it is preferable to provide a heating source for heating and melting from the viewpoint of uniformly mixing the component (B ′) and the component (D) or the component (E). Moreover, in order to move to a process (II) immediately after obtaining a molten mixture, it is more preferable to provide a liquid feeding mechanism. Examples of the driving method for liquid feeding include a self-weight type, a pneumatic type, a screw type, and a pump type.

  In addition, the atmosphere during heating is preferably performed in a non-oxidizing atmosphere, and is preferably performed under reduced pressure. This tends to suppress the occurrence of undesirable side reactions such as cross-linking reactions and decomposition reactions between polyarylene sulfide prepolymers, between polyarylene sulfides produced by heating, and between polyarylene sulfides and polyarylene sulfide prepolymers. . Note that the non-oxidizing atmosphere is an atmosphere in which the oxygen concentration in the gas phase in contact with the polyarylene sulfide prepolymer is 5% by volume or less, preferably 2% by volume or less, and more preferably contains substantially no oxygen, that is, nitrogen, helium, This indicates an atmosphere of an inert gas such as argon. Among these, a nitrogen atmosphere is particularly preferable from the viewpoints of economy and ease of handling. The reduced pressure condition means that the reaction system is lower than the atmospheric pressure, and the upper limit is preferably 50 kPa or less, more preferably 20 kPa or less, and even more preferably 10 kPa or less. An example of the lower limit is 0.1 kPa or more, and 0.2 kPa or more is more preferable. When the decompression condition is at least the preferred lower limit, the cyclic compound of the formula (o) having a low molecular weight contained in the cyclic polyarylene sulfide is less likely to volatilize. It is in.

  In the step (I), when melt-kneading, it is preferable to set the temperature and time so as not to cause the heat polymerization reaction of the polyarylene sulfide prepolymer as much as possible. The temperature at the time of melt kneading is 180 to 270 ° C, preferably 190 to 260 ° C, and more preferably 200 ° C to 250 ° C. When heated at the above preferred temperature, the polyarylene sulfide prepolymer easily melts in a short time, while the polymerization of the polyarylene sulfide prepolymer does not proceed rapidly, and an increase in viscosity due to the formation of polyarylene sulfide occurs. The impregnation property in the subsequent step (II) is also good.

  In the step (I), the time for melt-kneading is not particularly limited, but in order to prevent the polyarylene sulfide prepolymer from proceeding and thickening, the polyarylene sulfide prepolymer and the zero-valent transition metal compound It is preferable to move to step (II) as soon as possible after mixing (D) or the low-valent iron compound (E). The time range is 0.01 to 300 minutes, preferably 1 to 120 minutes, more preferably 5 to 60 minutes. When the heating time is preferable, the polyarylene sulfide prepolymer (B ′) and the zero-valent transition metal compound (D) or the low-valent iron compound (E) are sufficiently mixed, while the viscosity due to the formation of the polyarylene sulfide is sufficient. The rise is difficult to occur, and the impregnation property in the subsequent step (II) is also good.

<Process (II)>
In the step (II), the apparatus used is not particularly limited as long as it has a mechanism for impregnating the continuous reinforcing fiber bundle with the mixture obtained in the step (I). An apparatus for passing the reinforcing fiber bundle through the mold die while being supplied to the mold die, an apparatus for supplying the molten mixture to the melting bath with a gear pump, and passing the reinforcing fiber bundle while squeezing in the melting bath; Examples thereof include a device for supplying the molten mixture to the kiss coater with a plunger pump and applying it to the reinforcing fiber bundle, and a method for supplying the molten mixture onto a heated rotating roll and passing the reinforcing fiber bundle through the roll surface. These apparatuses may be used in combination for the purpose of improving the impregnation property, and the obtained composite may be looped and passed through the same apparatus a plurality of times.

  In the step (II), the temperature at which the melt-kneaded material is impregnated is 180 to 320 ° C, preferably 190 to 300 ° C, more preferably 200 to 260 ° C. When heated at the above preferred temperature, the polyarylene sulfide prepolymer coagulates, does not thicken or solidify easily, and has excellent impregnation properties, while the polyarylene sulfide prepolymer, between the polyarylene sulfide prepolymer generated by heating, and the polyarylene sulfide Undesirable side reactions such as a crosslinking reaction and a decomposition reaction hardly occur between the arylene sulfide and the polyarylene sulfide prepolymer.

  In the step (II), the time for impregnating the melt-kneaded product is 0.01 to 1000 minutes, preferably 0.02 to 120 minutes, more preferably 0.05 to 60 minutes, still more preferably 0.1 to 0.1 minutes. 10 minutes. With the above preferred impregnation time, the reinforcing fiber bundle is sufficiently impregnated with the melt-kneaded product, while the productivity of the molding material is also good.

<Step (III)>
In the step (III), the apparatus used is not particularly limited as long as it has a mechanism for adhering a thermoplastic resin to the composite obtained in the step (II). A device that passes the composite through the mold die while supplying it to a mold die such as a slit die, or a molten thermoplastic resin is supplied to the melting bath by a gear pump, and the composite passes through the melting bath. A device that supplies the melted thermoplastic resin to the kiss coater with a plunger pump and applies it to the composite, or a melted thermoplastic resin that is fed onto a heated rotating roll and composites on the roll surface. A method of passing the body can be exemplified.

  In step (III), the temperature at which the composite and the thermoplastic resin are bonded is not general because it varies depending on various properties such as the molecular structure, molecular weight, and composition of the thermoplastic resin used, but the lower limit is the heat used. The melting point of a plastic resin can be illustrated. As the upper limit, in addition to the melting point, 80 ° C., preferably 50 ° C., more preferably 30 ° C., and further preferably 20 ° C. can be exemplified. In such a temperature range, the thermoplastic resin can be easily bonded to the composite and can suppress undesirable phenomena in production such as thermal decomposition of the thermoplastic resin. Such a melting point can be determined by a differential scanning calorimeter (DSC) or the like.

  In the step (III), the time for the composite to pass through the device for bonding the composite and the thermoplastic resin is not particularly limited, but is 0.0001 to 120 minutes, preferably 0.0002 to 60 minutes, More preferably, 0.002 to 30 minutes can be exemplified. If it is set as the said preferable passage time, adhesion | attachment with a composite body and a thermoplastic resin will be easy, on the other hand, productivity of a molding material is also favorable.

  In the method for producing a molding material of the present invention, the polyarylene sulfide prepolymer may be converted into the polyarylene sulfide in any of the steps (I) to (III). In order to efficiently impregnate the reinforcing fiber bundle, it is preferable to selectively polymerize the polyarylene sulfide prepolymer after the step (II). In order to satisfy such requirements, conditions such as the apparatus, temperature, and time of the above-described steps (I) to (III) are suitable.

  In addition, after the steps (I) to (III), the polyarylene sulfide prepolymer remaining in the molding material after further heat treatment at 180 to 320 ° C., preferably 190 to 300 ° C., more preferably 200 to 260 ° C. It is also significant to heat polymerize.

  The following examples illustrate the present invention more specifically.

  First, the evaluation method used in the present invention is described below.

(1) Average molecular weight of polyarylene sulfide As for the average molecular weight of polyarylene sulfide, polystyrene-reduced weight average molecular weight (Mw) and number average molecular weight (Mn) were calculated using gel permeation chromatography (GPC). Moreover, the dispersity (Mw / Mn) was calculated using the molecular weight. The measurement conditions for GPC are shown below.
Apparatus: Senshu Science SSC-7100 (Column name: Senshu Science GPC3506)
Eluent: 1-chloronaphthalene, flow rate: 1.0 mL / min
Column temperature: 210 ° C., detector temperature: 210 ° C.

(2) Conversion rate of polyarylene sulfide prepolymer The conversion rate of the polyarylene sulfide prepolymer to polyphenylene sulfide was calculated by the following method using high performance liquid chromatography (HPLC).
10 mg of polyphenylene sulfide was dissolved in about 5 g of 1-chloronaphthalene at 250 ° C. The resulting solution was cooled to room temperature and a precipitate formed. The 1-chloronaphthalene insoluble component was filtered using a membrane filter having a pore size of 0.45 μm to obtain a 1-chloronaphthalene soluble component. Unreacted cyclic polyarylene sulfide was quantified by HPLC measurement of the obtained soluble component, and the conversion rate of the polyarylene sulfide prepolymer to polyarylene sulfide was calculated. The measurement conditions for HPLC are shown below.
Apparatus: Shimadzu Corporation LC-10Avp series Column: Mightysil RP-18 GP150-4.6 (5 μm)
Detector: Photodiode array detector (UV = 270 nm).

(3) Weight reduction due to heating of polyarylene sulfide The weight reduction rate was measured under the following conditions using a thermogravimetric analyzer (Perkin Elmer TGA7). In addition, the sample used the fine granule of 2 mm or less.
Measurement atmosphere: Nitrogen (purity: 99.99% or higher) Sample flow weight: about 10 mg
Measurement condition:
(A) Hold for 1 minute at a program temperature of 50 ° C. (b) Increase the temperature from the program temperature of 50 ° C. to 400 ° C. The temperature increase rate at this time is 20 ° C./min.

  The weight reduction rate ΔWr was calculated from the sample weight at the time of reaching 330 ° C. using the above-described formula (1) with the sample weight at 100 ° C. as the reference at the temperature rise of (b).

(4) Average fiber length of reinforcing fibers contained in a molded product obtained using the molding material A part of the molded product was cut out and heated and pressed at 300 ° C. to obtain a film having a thickness of 30 μm. The obtained film was magnified 150 times with an optical microscope, and fibers dispersed in the film were observed. The length was measured to the 1 micrometer unit, and the weight average fiber length (Lw) and the number average fiber length (Ln) were calculated | required by following Formula.
Weight average fiber length (Lw) = Σ (Li × Wi / 100)
Number average fiber length (Ln) = (ΣLi) / Ntotal
Li: measured fiber length (i = 1, 2, 3,..., N)
Wi: Weight fraction of fiber having fiber length Li (i = 1, 2, 3,..., N)
Ntotal: the total number of fibers measured.

(5) Density of molded product obtained using molding material Measured in accordance with Method A (underwater substitution method) described in 5 of JIS K7112 (1999). A test piece of 1 cm × 1 cm was cut out from the molded product, put into a heat-resistant glass container, this container was vacuum-dried at a temperature of 80 ° C. for 12 hours, cooled to room temperature with a desiccator so as not to absorb moisture, and used for evaluation. Ethanol was used as the immersion liquid.

(6) Bending test of molded product obtained using molding material In accordance with ASTM D790 (1997), a support span is set to 100 mm using a three-point bending test jig (indenter 10 mm, fulcrum 4 mm), and crosshead Flexural strength and flexural modulus were measured under the test conditions of a speed of 2.8 mm / min. As a testing machine, “Instron” (registered trademark) universal testing machine 4201 type (manufactured by Instron) was used.

(7) Izod Impact Test of Molded Product Obtained Using Molding Material An Izod impact test with a mold notch was conducted according to ASTM D256 (1993). The Izod impact strength (J / m) was measured when the thickness of the used test piece was 3.2 mm and the moisture content of the test piece was 0.1% by weight or less.

(8) Assessment of equipment contamination due to cracked gas when injection molding is performed using molding materials Regarding equipment contamination when performing injection molding at a predetermined temperature, the occurrence of off-flavor from the injection molding machine and the contamination of the mold surface Judgment was made by visual observation. The shape of the molded product was a thin flat plate molded product having a width of 150 mm, a length of 150 mm, and a thickness of 1.2 mm, and the measurement was performed on 20 samples. Judgment criteria are evaluated in the following four stages, and ◯ or higher is acceptable.
○○: There is no off-flavor, and no dirt is seen on the mold surface.
○: Odor is not generated, but a small amount of dirt is confirmed on the mold surface.
Δ: Odor occurs. A small amount of dirt is confirmed on the mold surface.
X: Odor occurs. Moreover, dirt is confirmed on the mold surface.

(9) <Measurement of X-ray absorption fine structure (XAFS) The X-ray absorption fine structure of the iron compound was measured under the following conditions.
Experimental Facility: High Energy Accelerator Research Organization Synchrotron Radiation Research Facility Spectrometer: Si (111) 2 crystal spectrometer Mirror: Condenser mirror Absorption edge: Fe K (7113 eV) Absorption edge detector: Ion chamber and rifle detector.

(Reference Example 1)
<Preparation of polyphenylene sulfide prepolymer>
In an autoclave equipped with a stirrer, 118 kg (1000 mol) of 47.5% sodium hydrosulfide, 42.3 kg (1014 mol) of 96% sodium hydroxide, N-methyl-2-pyrrolidone (hereinafter sometimes abbreviated as NMP) 163 kg (1646 mol) of sodium acetate, 24.6 kg (300 mol) of sodium acetate, and 150 kg of ion-exchanged water were gradually heated to 240 ° C. over 3 hours while passing nitrogen at normal pressure, and water was passed through a rectifying column. After distilling 211 kg and 4 kg of NMP, the reaction vessel was cooled to 160 ° C. In addition, 0.02 mol of hydrogen sulfide per 1 mol of sulfur atoms charged during the liquid removal operation was scattered out of the system.

  Next, 147 kg (1004 mol) of p-dichlorobenzene and 129 kg (1300 mol) of NMP were added, and the reaction vessel was sealed under nitrogen gas. While stirring at 240 rpm, the temperature was raised to 270 ° C. at a rate of 0.6 ° C./min and held at this temperature for 140 minutes. Water was cooled to 250 ° C. at a rate of 1.3 ° C./min while 18 kg (1000 mol) of water was injected over 15 minutes. Thereafter, the mixture was cooled to 220 ° C. at a rate of 0.4 ° C./min, and then rapidly cooled to near room temperature to obtain a slurry (Sa). This slurry (Sa) was diluted with 376 kg of NMP to obtain a slurry (Sb).

  14.3 kg of slurry (Sb) heated to 80 ° C. was filtered off with a sieve (80 mesh, opening 0.175 mm) to obtain 10 kg of crude PPS resin and slurry (Sc). The slurry (Sc) was charged into a rotary evaporator, replaced with nitrogen, treated at 100 to 160 ° C. under reduced pressure for 1.5 hours, and then treated at 160 ° C. for 1 hour in a vacuum dryer. The amount of NMP in the obtained solid was 3% by weight.

  After adding 12 kg of ion exchange water (1.2 times the amount of slurry (Sc)) to this solid, it was stirred at 70 ° C. for 30 minutes to make a slurry again. This slurry was subjected to suction filtration with a glass filter having an opening of 10 to 16 μm. 12 kg of ion-exchanged water was added to the obtained white cake, and the mixture was stirred again at 70 ° C. for 30 minutes to make a slurry again. Similarly, after suction filtration, vacuum drying was performed at 70 ° C. for 5 hours to obtain 100 g of a polyphenylene sulfide oligomer. The above operation was repeated until the polyphenylene sulfide prepolymer reached a predetermined amount.

  4 g of the obtained polyphenylene sulfide oligomer was collected and subjected to Soxhlet extraction with 120 g of chloroform for 3 hours. Chloroform was distilled off from the obtained extract, and 20 g of chloroform was again added to the resulting solid, which was dissolved at room temperature to obtain a slurry-like mixture. This was slowly added dropwise to 250 g of methanol while stirring, and the precipitate was suction filtered through a glass filter having an opening of 10 to 16 μm, and the resulting white cake was vacuum dried at 70 ° C. for 3 hours to obtain a white powder.

  The weight average molecular weight of this white powder was 900. From the absorption spectrum in the infrared spectroscopic analysis of the white powder, the white powder was found to be a polyphenylene sulfide prepolymer. Moreover, as a result of analyzing the thermal characteristics of this white powder using a differential scanning calorimeter (temperature increase rate 40 ° C./min), it shows a broad endotherm at about 200 to 260 ° C., and the peak temperature is 215 ° C. I understood it.

  Moreover, this white powder was obtained from cyclic polyphenylene sulfide having 4 to 11 repeating units and cyclic polyphenylene sulfide having 2 to 11 repeating units based on mass spectral analysis of components separated by high performance liquid chromatography and molecular weight information by MALDI-TOF-MS. It was a mixture of chain polyphenylene sulfide, and the weight ratio of cyclic polyphenylene sulfide to linear polyphenylene sulfide was found to be 9: 1.

(Reference Example 3)
In an autoclave equipped with a stirrer, 47.5% sodium hydrosulfide 8.27 kg (70.0 mol), 96% sodium hydroxide 2.96 kg (71.0 mol), N-methyl-2-pyrrolidone (NMP) 11 .44 kg (116 mol), 1.72 kg (21.0 mol) of sodium acetate, and 10.5 kg of ion-exchanged water were charged and gradually heated to about 240 ° C. over about 3 hours while flowing nitrogen at normal pressure. After distilling 14.8 kg of water and 280 g of NMP through the distillation column, the reaction vessel was cooled to 160 ° C. In addition, 0.02 mol of hydrogen sulfide per 1 mol of the sulfur component charged during this liquid removal operation was scattered out of the system.

  Next, 10.3 kg (70.3 mol) of p-dichlorobenzene and 9.00 kg (91.0 mol) of NMP were added, and the reaction vessel was sealed under nitrogen gas. While stirring at 240 rpm, the temperature was raised to 270 ° C. at a rate of 0.6 ° C./min and held at this temperature for 140 minutes. While 1.26 kg (70 mol) of water was injected over 15 minutes, it was cooled to 250 ° C. at a rate of 1.3 ° C./min. Thereafter, the mixture was cooled to 220 ° C. at a rate of 0.4 ° C./min, and then rapidly cooled to near room temperature to obtain a slurry (Sa). This slurry (Sa) was diluted with 20.0 kg of NMP to obtain a slurry (Sb).

  10 kg of the slurry (Sb) heated to 80 ° C. is filtered through a sieve (80 mesh, opening 0.175 mm), granular PPS resin containing the slurry as a mesh-on component, and about 7 of the slurry (Sc) as a filtrate component. .5 kg was obtained.

  After 1000 g of the obtained slurry (Sc) was charged into a rotary evaporator and replaced with nitrogen, it was treated under reduced pressure at 100 to 150 ° C. for 1.5 hours, and then treated with a vacuum dryer at 150 ° C. for 1 hour to obtain solids. Got.

  After adding 1200 g of ion-exchanged water (1.2 times the amount of slurry (Sc)) to this solid, it was stirred at 70 ° C. for 30 minutes to make a slurry again. Radiolite # 800S (manufactured by Showa Chemical Industry Co., Ltd.) 3 g of ion-exchanged water dispersed in 3 g of the dispersion liquid is suction filtered with a glass filter having a mesh opening of 10 to 16 μm. Was used for solid-liquid separation of the slurry. To the obtained brown cake, 1200 g of ion-exchanged water was added and stirred at 70 ° C. for 30 minutes to make a slurry again. Similarly, after suction filtration, vacuum drying was performed at 70 ° C. for 5 hours to obtain 14.0 g of a polyphenylene sulfide mixture. .

  10 g of the obtained polyphenylene sulfide mixture was collected, and 240 g of chloroform was used as a solvent, and the polyphenylene sulfide mixture was contacted with the solvent by a Soxhlet extraction method at a bath temperature of about 80 ° C. for 5 hours to obtain an extract. The obtained extract was in the form of a slurry partially containing solid components at room temperature. About 200 g of chloroform was distilled off from the extract slurry using an evaporator, and this was slowly added dropwise to 500 g of methanol over about 10 minutes while stirring. After completion of dropping, stirring was continued for about 15 minutes. The precipitate was collected by suction filtration with a glass filter having an opening of 10 to 16 μm, and the resulting white cake was vacuum dried at 70 ° C. for 3 hours to obtain 3.0 g of a white powder. The yield of white powder was 31% based on the polyphenylene sulfide mixture used.

  The weight average molecular weight of this white powder was 900. From the absorption spectrum in the infrared spectroscopic analysis of this white powder, it was confirmed that the white powder was a compound composed of phenylene sulfide units. Moreover, this white color is obtained from mass spectrum analysis of components separated from high performance liquid chromatography (device; LC-10, Shimadzu Corporation LC-10, column; C18, detector; photodiode array) and molecular weight information by MALDI-TOF-MS. The powder was found to contain about 94% by weight fraction of a cyclic compound having a p-phenylene sulfide unit as a main constituent unit and 4 to 12 repeating units.

Example 1
To the polyphenylene sulfide prepolymer prepared in Reference Example 1, tetrakis (triphenylphosphine) palladium as a zero-valent transition metal compound was added so as to be 0.5 mol% with respect to sulfur atoms in the polyphenylene sulfide prepolymer, and 250 The mixture was melted in a melting bath at 0 ° C. to obtain a molten mixture. The obtained molten mixture was supplied to the kiss coater with a gear pump. A polyphenylene sulfide prepolymer was applied from a kiss coater on a roll heated to 250 ° C. to form a film.

  A carbon fiber “Torayca” (registered trademark) T700S-24K (manufactured by Toray Industries, Inc.) was passed through the roll while contacting it, and a certain amount of polyphenylene sulfide prepolymer was adhered per unit length of the carbon fiber bundle. .

  The carbon fiber with the polyphenylene sulfide prepolymer attached is fed into a furnace heated to 260 ° C. and passed between 10 rolls (φ50 mm) alternately arranged in a straight line rotating freely in a bearing. In addition, ten roll bars (φ200 mm) installed in the furnace in a twisted manner are passed through a plurality of times, and the polyphenylene sulfide prepolymer is sufficiently impregnated into the carbon fiber bundle over a total of 10 minutes. Converted to. Next, after drawing out from the furnace and cooling by blowing air, it was wound up with a drum winder to obtain a composite composed of continuous reinforcing fiber bundle (A) and polyarylene sulfide (B).

  In addition, 10 strands 10 mm long were cut from the wound composite, and a Soxhlet extractor was used and 1-chloronaphthalene was used for 6 hours at 210 ° C. to separate carbon fibers and polyarylene sulfide. Refluxing was performed, and the extracted polyarylene sulfide was subjected to molecular weight measurement. The obtained PPS had a weight average molecular weight (Mw) of 19,700 and a dispersity (Mw / Mn) of 1.95. Next, the conversion of the polyarylene sulfide prepolymer in the extracted polyarylene sulfide was measured and found to be 93%.

  Subsequently, “Torelina” (registered trademark) A900 (PPS resin manufactured by Toray Industries, Inc., melting point 278 ° C.) as component (C) was melted at 330 ° C. with a single screw extruder and attached to the tip of the extruder. Simultaneously with extrusion into the crosshead die, the obtained composite was continuously fed into the crosshead die, thereby coating the composite with the molten component (C). At this time, the amount of the component (C) was adjusted so that the content of the reinforcing fiber was 20% by weight.

  The strand obtained by the method described above was cooled and then cut into a length of 7 mm with a cutter to obtain a columnar pellet (long fiber pellet) which is a molding material of the present invention. This columnar pellet had a core-sheath structure.

  The obtained long fiber pellets showed no fuzz due to transportation and showed good handleability. The obtained long fiber pellet was dried under vacuum at 150 ° C. for 5 hours or more. The dried long fiber pellets were molded using a mold for each test piece using a J150EII-P type injection molding machine manufactured by Nippon Steel Works. The conditions were as follows: cylinder temperature: 320 ° C., mold temperature: 150 ° C., and cooling time 30 seconds. After the molding, the test piece was dried at 80 ° C. for 12 hours under vacuum, and the dried test piece was stored in a desiccator at room temperature for 3 hours. The evaluation results are shown in Table 1.

(Example 2)
A columnar pellet (long fiber pellet), which is the molding material of the present invention, was produced in the same manner as in Example 1 except that the furnace temperature was 300 ° C. This columnar pellet had a core-sheath structure. From the resulting composite, polyarylene sulfide was extracted in the same manner as in Example 1 and subjected to each measurement. The resulting polyarylene sulfide had a weight average molecular weight (Mw) of 24,800 and a dispersity (Mw / Mn) of 2.30. Next, the conversion of the polyarylene sulfide prepolymer in the extracted polyarylene sulfide was measured and found to be 93%.

  Moreover, injection molding was performed in the same manner as in Example 1 using the obtained long fiber pellets and subjected to each evaluation. Table 1 shows the process conditions and evaluation results.

(Example 3)
Instead of tetrakis (triphenylphosphine) palladium as the zero-valent transition metal compound, tris (dibenzylideneacetone) dipalladium was used, and the amount added was changed to 1 mol% with respect to the sulfur atom in the polyphenylene sulfide prepolymer. A columnar pellet (long fiber pellet), which is a molding material of the present invention, was produced in the same manner as in Example 1 except that. This columnar pellet had a core-sheath structure. From the resulting composite, polyarylene sulfide was extracted in the same manner as in Example 1 and subjected to each measurement. The resulting polyarylene sulfide had a weight average molecular weight (Mw) of 49,500 and a dispersity (Mw / Mn) of 1.83. Next, the conversion of the polyarylene sulfide prepolymer in the extracted polyarylene sulfide was measured and found to be 81%.

  Moreover, injection molding was performed in the same manner as in Example 1 using the obtained long fiber pellets and subjected to each evaluation. Table 1 shows the process conditions and evaluation results.

Example 4
A columnar pellet (long fiber pellet), which is the molding material of the present invention, was produced in the same manner as in Example 3 except that the furnace temperature was 300 ° C. This columnar pellet had a core-sheath structure. From the resulting composite, polyarylene sulfide was extracted in the same manner as in Example 1 and subjected to each measurement. The resulting polyarylene sulfide had a weight average molecular weight (Mw) of 44,100 and a dispersity (Mw / Mn) of 1.89. Next, the conversion of the polyarylene sulfide prepolymer in the extracted polyarylene sulfide was measured and found to be 87%.

  Moreover, injection molding was performed in the same manner as in Example 1 using the obtained long fiber pellets and subjected to each evaluation. Table 1 shows the process conditions and evaluation results.

(Example 5)
The molding of the present invention was carried out in the same manner as in Example 1 except that bis [1,2-bis (diphenylphosphino) ethane] palladium was used as the zero-valent transition metal compound instead of tetrakis (triphenylphosphine) palladium. A columnar pellet (long fiber pellet) as a material was produced. This columnar pellet had a core-sheath structure. From the resulting composite, polyarylene sulfide was extracted in the same manner as in Example 1 and subjected to each measurement. The resulting polyarylene sulfide had a weight average molecular weight (Mw) of 31,900 and a dispersity (Mw / Mn) of 2.15. Next, the conversion of the polyarylene sulfide prepolymer in the extracted polyarylene sulfide was measured and found to be 99%.

  Moreover, injection molding was performed in the same manner as in Example 1 using the obtained long fiber pellets and subjected to each evaluation. Table 1 shows the process conditions and evaluation results.

(Comparative Example 1)
The polyphenylene sulfide in the composite was changed so that the content of the polyphenylene sulfide was changed from 10% to 30% by weight and the content of the thermoplastic resin was changed from 70% to 50% by weight without containing the zero-valent transition metal compound. Columnar pellets (long fiber pellets), which are molding materials, were produced in the same manner as in Example 1 except that the amount of prepolymer attached and the amount of component (C) coated on the composite were changed. This columnar pellet had a core-sheath structure. From the resulting composite, polyarylene sulfide was extracted in the same manner as in Example 1 and subjected to each measurement. The conversion of the polyarylene sulfide prepolymer in the obtained polyarylene sulfide was measured and found to be only 2%.

  Moreover, injection molding was performed in the same manner as in Example 1 using the obtained long fiber pellets and subjected to each evaluation. Table 1 shows the process conditions and evaluation results.

(Comparative Example 2)
Columnar pellets (long fiber pellets), which are molding materials, were produced in the same manner as in Example 1 except that the zero-valent transition metal compound was not included. This columnar pellet had a core-sheath structure. From the resulting composite, polyarylene sulfide was extracted in the same manner as in Example 1 and subjected to each measurement. The conversion of the polyarylene sulfide prepolymer in the obtained polyarylene sulfide was measured and found to be only 2%.

  Moreover, injection molding was performed in the same manner as in Example 1 using the obtained long fiber pellets and subjected to each evaluation. Table 1 shows the process conditions and evaluation results.

(Comparative Example 3)
A columnar pellet (long fiber pellet) as a molding material was produced in the same manner as in Example 2 except that the zero-valent transition metal compound was not included. This columnar pellet had a core-sheath structure. From the resulting composite, polyarylene sulfide was extracted in the same manner as in Example 1 and subjected to each measurement. When the conversion of the polyarylene sulfide prepolymer in the obtained polyarylene sulfide was measured, it was 12%.

  Moreover, injection molding was performed in the same manner as in Example 1 using the obtained long fiber pellets and subjected to each evaluation. Table 1 shows the process conditions and evaluation results.

(Comparative Example 4)
Columnar pellets (long fiber pellets) that are molding materials were produced in the same manner as in Example 2, except that diphenyl sulfide was used instead of the zero-valent transition metal compound. This columnar pellet had a core-sheath structure. From the resulting composite, polyarylene sulfide was extracted in the same manner as in Example 1 and subjected to each measurement. The resulting polyarylene sulfide had a weight average molecular weight (Mw) of 14,700 and a dispersity (Mw / Mn) of 1.33. Next, the conversion of the polyarylene sulfide prepolymer in the extracted polyarylene sulfide was measured and found to be 16%.

  Moreover, the obtained long fiber pellet was subjected to injection molding in the same manner as in Example 1 and subjected to each evaluation. Table 1 shows the process conditions and evaluation results.

  From the examples and comparative examples in Table 1, the following is clear. Since the long fiber pellets of Examples 1 to 5 contain a zero-valent transition metal catalyst, the conversion rate to polyarylene sulfide is significantly higher than those of Comparative Examples 1 to 3, and the handling property of the molding material is excellent. It can be seen that the mechanical properties and appearance quality of the obtained molded product are excellent. In addition, since Comparative Example 1 contains a large amount of polyarylene sulfide prepolymer having a low conversion rate, the mechanical properties are inferior and the equipment contamination during molding is particularly large. Moreover, it turns out by the comparison with Examples 1-5 and the comparative example 4 that the contribution to the conversion of the polyarylene sulfide by a zerovalent transition metal catalyst is dominant.

(Example 6)
Tetrakis (triphenylphosphine) palladium as a zero-valent transition metal compound was added to the polyphenylene sulfide prepolymer prepared in Reference Example 1 so as to be 1 mol% with respect to sulfur atoms in the polyphenylene sulfide prepolymer, The mixture was melted in a melting bath to obtain a molten mixture. The obtained molten mixture was supplied to the kiss coater with a gear pump. A polyphenylene sulfide prepolymer was applied from a kiss coater on a roll heated to 250 ° C. to form a film.

  A carbon fiber “Torayca” (registered trademark) T700S-24K (manufactured by Toray Industries, Inc.) was passed through the roll while contacting it, and a certain amount of polyphenylene sulfide prepolymer was adhered per unit length of the carbon fiber bundle. .

  Carbon fiber with polyphenylene sulfide prepolymer attached is fed into a furnace heated to 300 ° C. and passed between 10 rolls (φ50 mm) arranged alternately in a straight line, rotating freely with bearings. In addition, ten roll bars (φ200 mm) installed in the furnace in a twisted manner are passed through a plurality of loops, and the polyphenylene sulfide prepolymer is sufficiently impregnated into the carbon fiber bundle over a total of 60 minutes. Converted to. Next, after drawing out from the furnace and cooling by blowing air, it was wound up with a drum winder to obtain a composite composed of continuous reinforcing fiber bundle (A) and polyarylene sulfide (B).

  In addition, 10 strands 10 mm long were cut from the wound composite, and a Soxhlet extractor was used and 1-chloronaphthalene was used for 6 hours at 210 ° C. to separate carbon fibers and polyarylene sulfide. Refluxing was performed, and the extracted polyarylene sulfide was subjected to molecular weight measurement. The obtained PPS had a weight average molecular weight (Mw) of 17,800 and a dispersity (Mw / Mn) of 2.11. Next, the conversion of the polyarylene sulfide prepolymer in the extracted polyarylene sulfide was measured and found to be 93%. Next, the weight reduction rate ΔWr of the extracted polyarylene sulfide was measured and found to be 0.12%.

  Subsequently, “Torelina” (registered trademark) A900 (PPS resin manufactured by Toray Industries, Inc., melting point 278 ° C.) as the component (C) was melted at 330 ° C. with a single screw extruder and attached to the tip of the extruder. Simultaneously with extrusion into the crosshead die, the obtained composite was continuously fed into the crosshead die, thereby coating the composite with the molten component (C). At this time, the amount of the component (C) was adjusted so that the content of the reinforcing fiber was 20% by weight.

  The strand obtained by the method described above was cooled and then cut into a length of 7 mm with a cutter to obtain a columnar pellet (long fiber pellet) which is a molding material of the present invention. This columnar pellet had a core-sheath structure.

  The obtained long fiber pellets showed no fuzz due to transportation and showed good handleability. The obtained long fiber pellet was dried under vacuum at 150 ° C. for 5 hours or more. The dried long fiber pellets were molded using a mold for each test piece using a J150EII-P type injection molding machine manufactured by Nippon Steel Works. The conditions were as follows: cylinder temperature: 320 ° C., mold temperature: 150 ° C., and cooling time 30 seconds. After the molding, the test piece was dried at 80 ° C. for 12 hours under vacuum, and the dried test piece was stored in a desiccator at room temperature for 3 hours. The evaluation results are shown in Table 2.

(Example 7)
A columnar pellet (which is a molding material of the present invention) in the same manner as in Example 6 except that tris (dibenzylideneacetone) dipalladium was used in place of tetrakis (triphenylphosphine) palladium as the zero-valent transition metal compound. Long fiber pellets) were produced. This columnar pellet had a core-sheath structure. From the resulting composite, polyarylene sulfide was extracted in the same manner as in Example 1 and subjected to each measurement. The resulting polyarylene sulfide had a weight average molecular weight (Mw) of 42,200 and a dispersity (Mw / Mn) of 1.9. Next, the conversion of the polyarylene sulfide prepolymer in the extracted polyarylene sulfide was measured and found to be 90%. Next, the weight loss rate ΔWr of the extracted polyarylene sulfide was measured and found to be 0.06%.

  Moreover, the obtained long fiber pellet was subjected to injection molding in the same manner as in Example 1 and subjected to each evaluation. Each process condition and evaluation result are shown in Table 2.

(Example 8)
Columnar pellets (long length) which are molding materials of the present invention are the same as in Example 6 except that tetrakis (triphenylphosphine) nickel is used in place of tetrakis (triphenylphosphine) palladium as the zero-valent transition metal compound. Fiber pellets). This columnar pellet had a core-sheath structure. From the resulting composite, polyarylene sulfide was extracted in the same manner as in Example 1 and subjected to each measurement. The resulting polyarylene sulfide had a weight average molecular weight (Mw) of 43,500 and a dispersity (Mw / Mn) of 1.69. Next, the conversion of the polyarylene sulfide prepolymer in the extracted polyarylene sulfide was measured and found to be 72%. Next, the weight loss rate ΔWr of the extracted polyarylene sulfide was measured and found to be 0.19%.

  Moreover, the obtained long fiber pellet was subjected to injection molding in the same manner as in Example 1 and subjected to each evaluation. Each process condition and evaluation result are shown in Table 2.

(Comparative Example 5)
A columnar pellet (long fiber pellet) as a molding material was produced in the same manner as in Example 6 except that the zero-valent transition metal compound was not included. This columnar pellet had a core-sheath structure. From the resulting composite, polyarylene sulfide was extracted in the same manner as in Example 1 and subjected to each measurement. The resulting polyarylene sulfide had a weight average molecular weight (Mw) of 62,300 and a dispersity (Mw / Mn) of 1.77. Next, the conversion of the polyarylene sulfide prepolymer in the extracted polyarylene sulfide was measured and found to be 54%.

  Moreover, the obtained long fiber pellet was subjected to injection molding in the same manner as in Example 1 and subjected to each evaluation. Each process condition and evaluation result are shown in Table 2.

(Comparative Example 6)
A columnar pellet (long fiber pellet) as a molding material was produced in the same manner as in Comparative Example 5 except that the furnace temperature was 340 ° C. This columnar pellet had a core-sheath structure. From the resulting composite, polyarylene sulfide was extracted in the same manner as in Example 1 and subjected to each measurement. The resulting polyarylene sulfide had a weight average molecular weight (Mw) of 68,200 and a dispersity (Mw / Mn) of 2.04. Next, the conversion of the polyarylene sulfide prepolymer in the extracted polyarylene sulfide was measured and found to be 92%.

  Moreover, the obtained long fiber pellet was subjected to injection molding in the same manner as in Example 1 and subjected to each evaluation. Each process condition and evaluation result are shown in Table 2.

(Comparative Example 7)
Columnar pellets (long fiber pellets) that are molding materials were produced in the same manner as in Example 6 except that diphenyl sulfide was used instead of the zero-valent transition metal compound. This columnar pellet had a core-sheath structure. From the resulting composite, polyarylene sulfide was extracted in the same manner as in Example 1 and subjected to each measurement. The resulting polyarylene sulfide had a weight average molecular weight (Mw) of 49,900 and a dispersity (Mw / Mn) of 1.77. Next, the conversion of the polyarylene sulfide prepolymer in the extracted polyarylene sulfide was measured and found to be 63%.

  Moreover, the obtained long fiber pellet was subjected to injection molding in the same manner as in Example 1 and subjected to each evaluation. Each process condition and evaluation result are shown in Table 2.

(Comparative Example 8)
Columnar pellets (long fiber pellets) as a molding material were produced in the same manner as in Example 6 except that thiophenol sodium salt was used instead of the zero-valent transition metal compound. This columnar pellet had a core-sheath structure. From the resulting composite, polyarylene sulfide was extracted in the same manner as in Example 1 and subjected to each measurement. The resulting polyarylene sulfide had a weight average molecular weight (Mw) of 26,900 and a dispersity (Mw / Mn) of 1.68. Next, the conversion of the polyarylene sulfide prepolymer in the extracted polyarylene sulfide was measured and found to be 35%.

  Moreover, the obtained long fiber pellet was subjected to injection molding in the same manner as in Example 1 and subjected to each evaluation. Each process condition and evaluation result are shown in Table 2.

(Reference Example 2)
Using a commercially available “Torelina” (registered trademark) A900 (PPS resin manufactured by Toray Industries, Inc., melting point 278 ° C.), the weight reduction rate ΔWr was measured and found to be 0.25%.

  From the examples and comparative examples in Table 2, the following is clear. The molding materials of the present invention obtained in Examples 6 to 8 have a higher conversion rate of polyarylene sulfide of the polyphenylene sulfide prepolymer than the molding materials of Comparative Examples 5, 7, and 8, and the handling property of the molding material is high. Excellent mechanical properties and appearance quality of the molded product. In addition, it can be seen that the molding materials of the present invention obtained in Examples 6 and 7 can achieve the same conversion rate at a lower furnace temperature than the molding material of Comparative Example 6. This effect is due to the presence or absence of a zero-valent transition metal compound. Moreover, it turns out that the polyarylene sulfide used by this invention can reduce generation | occurrence | production of a decomposition gas by comparing Examples 6-8 with Reference Example 2.

Example 9
To the polyphenylene sulfide prepolymer (B ′) prepared in Reference Example 3, iron (III) chloride anhydride as a low-valent iron compound source was added to 1 mol% with respect to sulfur atoms in the polyphenylene sulfide prepolymer. And melted in a 250 ° C. melting bath to obtain a molten mixture. The obtained molten mixture was supplied to the kiss coater with a gear pump. A polyphenylene sulfide prepolymer (B ′) was applied from a kiss coater on a roll heated to 250 ° C. to form a film.

  A carbon fiber “Torayca” (registered trademark) T700S-24K (manufactured by Toray Industries, Inc.) is passed through the roll while being in contact therewith, and a certain amount of polyphenylene sulfide prepolymer (B ′ ).

  Ten rolls (φ50 mm) arranged alternately in a line on a straight line, with carbon fibers attached with polyphenylene sulfide prepolymer (B ′) fed into a furnace heated to 300 ° C. and freely rotated by bearings 10 roll bars (φ200mm) installed in the furnace in a twisted manner are passed through in multiple loops, and the carbon fiber bundle is fully impregnated with polyphenylene sulfide prepolymer over a total of 60 minutes The polyphenylene sulfide (B) was converted. Next, after drawing out from the furnace and cooling by blowing air, it was wound up with a drum winder to obtain a composite composed of continuous reinforcing fiber bundle (A) and polyarylene sulfide (B). In this process, the chlorine component was confirmed as a result of examining the gas component in the furnace with a detector tube.

  In addition, 10 strands 10 mm long were cut from the wound composite, and refluxed at 210 ° C. for 6 hours with 1-chloronaphthalene using a Soxhlet extractor to extract polyarylene sulfide (B). did. Next, the conversion of the polyarylene sulfide prepolymer (B ′) in the extracted polyarylene sulfide (B) was measured and found to be 81%.

  Moreover, when 10 strands 10 mm long were cut from the wound composite and dissolved in 1 chloronaphthalene at 250 ° C., carbon fibers and an iron compound were obtained as insoluble portions. The iron compound was isolated from this insoluble part, XAFS measurement was performed, and the valence state of the iron compound and the structure near the iron atom were analyzed. As a result, in the absorption spectrum for XANES, a main peak was observed at the same position as that of iron (II) chloride, but the shape was different, and in the radial distribution function, iron (III) chloride and chloride were around 0.16 nm. A main peak that is considered to have the same characteristics as iron (II) tetrahydrate, and a sub-peak that is considered to have the same characteristics as iron (II) chloride and iron (II) chloride tetrahydrate are observed around 0.21 nm. It was confirmed that an iron (II) chloride component, which is a divalent iron compound, was present together with the trivalent iron compound.

  Subsequently, “Torelina” (registered trademark) A900 (PPS resin manufactured by Toray Industries, Inc., melting point 278 ° C.) as component (C) was melted at 330 ° C. with a single screw extruder and attached to the tip of the extruder. Simultaneously with extrusion into the crosshead die, the obtained composite was continuously fed into the crosshead die, thereby coating the composite with the molten component (C). At this time, the amount of the component (C) was adjusted so that the content of the reinforcing fiber was 20% by weight.

  The strand obtained by the method described above was cooled and then cut into a length of 7 mm with a cutter to obtain a columnar pellet (long fiber pellet) which is a molding material of the present invention. This columnar pellet had a core-sheath structure.

  The obtained long fiber pellets showed no fuzz due to transportation and showed good handleability. The obtained long fiber pellets were dried under vacuum at 150 ° C. for 5 hours or more. The dried long fiber pellets were molded using a mold for each test piece using a J150EII-P type injection molding machine manufactured by Nippon Steel Works. The conditions were as follows: cylinder temperature: 320 ° C., mold temperature: 150 ° C., and cooling time 30 seconds. After the molding, the test piece was dried at 80 ° C. for 12 hours under vacuum, and the dried test piece was stored in a desiccator at room temperature for 3 hours. The evaluation results are shown in Table 3.

(Comparative Example 9)
Except that iron oxide (III) was used in place of the low-valent iron compound (E) and the amount added was changed to 0.5 mol% with respect to sulfur atoms in the polyphenylene sulfide prepolymer, the examples In the same manner as in No. 9, columnar pellets (long fiber pellets) as a molding material were produced. This columnar pellet had a core-sheath structure. From the resulting composite, polyarylene sulfide (B) was extracted in the same manner as in Example 9, and subjected to each measurement. The conversion of the polyarylene sulfide prepolymer (B ′) in the extracted polyarylene sulfide (B) was measured and found to be 36%. Further, XAFS measurement was performed to analyze the valence state of the iron compound and the structure near the iron atom. As a result, the absorption spectrum related to XANES has the same spectrum shape as that of iron (III) oxide, and the radial distribution function shows the same Fe − as that of iron oxide (III) around 0.15 nm and 0.26 nm. The peak considered to originate in O bond, Fe-Fe bond, etc. was recognized, and it turned out that iron oxide (III) is a main component.

  Further, the obtained long fiber pellets were subjected to injection molding in the same manner as in Example 9 and subjected to each evaluation. Each process condition and evaluation result are shown in Table 3.

(Comparative Example 10)
Columnar pellets (long fiber pellets) that are molding materials were produced in the same manner as in Example 9, except that the low-valent iron compound (E) was not included. This columnar pellet had a core-sheath structure. Polyarylene sulfide (B ′) was extracted from the obtained complex in the same manner as in Example 9, and subjected to each measurement. When the conversion of the polyarylene sulfide prepolymer (B) in the extracted polyarylene sulfide (B ′) was measured, it was 44%.

  Further, the obtained long fiber pellets were subjected to injection molding in the same manner as in Example 9 and subjected to each evaluation. Each process condition and evaluation result are shown in Table 3.

(Comparative Example 11)
Columnar pellets (long fiber pellets) that are molding materials were produced in the same manner as in Example 9 except that sodium thiophenol was used instead of the low-valent iron compound (E). This columnar pellet had a core-sheath structure. Polyarylene sulfide (B ′) was extracted from the obtained complex in the same manner as in Example 9, and subjected to each measurement. When the conversion of the polyarylene sulfide prepolymer (B) in the extracted polyarylene sulfide (B ′) was measured, it was 35%.

  Further, the obtained long fiber pellets were subjected to injection molding in the same manner as in Example 9 and subjected to each evaluation. Each process condition and evaluation result are shown in Table 3.

  The following is clear from the examples and comparative examples in Table 3.

  Since the molding material of the present invention of Example 9 includes the low-valent iron compound (E), the polyarylene sulfide prepolymer (B) in the molding material production process is more compared to the molding materials of Comparative Examples 9 to 11. It can be seen that the conversion to polyarylene sulfide (B ′) is high. Furthermore, since the conversion rate of the polyarylene sulfide prepolymer (B) to the polyarylene sulfide (B ′) in the production process of the molding material of the present invention of Example 9 is high, there is no equipment contamination at the time of molding. It can be seen that the mechanical properties of the molded product are excellent.

  The molding material of the present invention has a good dispersion of the reinforcing fibers in the molded product during injection molding, and can easily produce a molded product with excellent heat resistance and mechanical properties without environmental pollution. Not only molding methods such as injection molding, blow molding and insert molding, but also a wide range of molding methods such as plunger molding, press molding and stamping molding can be applied, but the application range is not limited to these. .

1 Reinforcing fiber bundle (A)
2 Polyarylene sulfide (B) and zero-valent transition metal compound (D) or low-valent iron compound (E)
3 Composite composed of reinforcing fiber bundle (A), polyarylene sulfide (B) and zero-valent transition metal compound (D) or low-valent iron compound (E) 4 Thermoplastic resin (C)

Claims (20)

Thermoplastic resin (C) 35 to 98.9% by weight is bonded to a composite composed of continuous reinforcing fiber bundle (A) 1 to 50% by weight and polyarylene sulfide (B) 0.1 to 15% by weight. A molding material, wherein the composite further comprises 0.001 to 20 mol% of a zero-valent transition metal compound (D) with respect to the sulfur atoms in the component (B). 2. The molding material according to claim 1, wherein the component (D) is a compound containing a metal in groups 8 to 11 and 4 to 6 in the periodic table. The molding material according to claim 1, wherein the component (D) is a compound containing palladium or nickel. Thermoplastic resin (C) 35 to 98.9% by weight is bonded to a composite composed of continuous reinforcing fiber bundle (A) 1 to 50% by weight and polyarylene sulfide (B) 0.1 to 15% by weight. A molding material, wherein the composite further comprises 0.001 to 20 mol% of a low-valent iron compound (E) based on sulfur atoms in the component (B). The molding material according to claim 4, wherein the component (E) is a divalent iron compound. The component (B) is a polyarylene sulfide obtained by heat polymerization of a polyarylene sulfide prepolymer (B ′), and the component (B ′) further contains at least 50% by weight of a cyclic polyarylene sulfide. The molding material according to any one of claims 1 to 5, which contains and has a weight average molecular weight of less than 10,000. The molding material in any one of Claims 1-6 whose conversion rate to the said component (B) of the said component (B ') is 70% or more. The component (B) is a polyarylene sulfide having a weight average molecular weight of 10,000 or more and a dispersity expressed by weight average molecular weight / number average molecular weight of 2.5 or less. The molding material in any one of. The molding material in any one of Claims 1-8 in which the weight reduction at the time of the said component (B) heating satisfy | fills following formula.
ΔWr = (W1-W2) /W1×100≦0.20 (%)
(Here, ΔWr is the weight loss rate (%), and thermogravimetric analysis was performed at a temperature rising rate of 20 ° C./min from 50 ° C. to an arbitrary temperature of 330 ° C. or higher in a non-oxidizing atmosphere at normal pressure. (It is a value obtained from the sample weight (W2) when reaching 330 ° C. with reference to the sample weight (W1) when reaching 100 ° C.) The molding material according to any one of claims 1 to 9, wherein the component (A) contains at least 10,000 single fibers of carbon fibers. The molding according to any one of claims 1 to 10, wherein the component (C) is at least one selected from a polyamide resin, a polyetherimide resin, a polyamideimide resin, a polyetheretherketone resin, and a polyphenylene sulfide resin. material. The component (A) is arranged substantially parallel to the axial direction, and the length of the component (A) is substantially the same as the length of the molding material. Molding material. A complex comprising the component (A), the component (B) and the component (D) or the component (E) has a core structure, and the component (C) covers the periphery of the complex. The molding material according to claim 12. The molding material according to claim 13, wherein the molding material is in the form of long fiber pellets. The molding material in any one of Claims 1-14 whose length exists in the range of 1-50 mm. The said component (C) is arrange | positioned and adhere | attached on the composite which consists of the said component (A), the said component (B), the said component (D), or the said component (E), and is adhere | attached. The molding material in any one. A step (I) for obtaining a mixture comprising the component (B ′) and the component (D) or the component (E), a step (II) for obtaining a composite obtained by impregnating the component (A) with the mixture, A process for producing a molding material comprising the step (III) of adhering a composite to the component (C), wherein the component (B ′) is replaced with the component (D) or the component in the step (II) and thereafter. (E) The manufacturing method of the molding material in any one of Claims 1-16 made to heat-polymerize in presence and to convert into the said component (B). The manufacturing method of the molding material of Claim 17 which performs the said process (I) under the temperature of 180-270 degreeC. The manufacturing method of the molding material in any one of Claim 17 or 18 which performs the said process (II) under the temperature of 180-320 degreeC. The manufacturing method of the molding material in any one of Claims 17-19 which heat-process at the temperature of 180-320 degreeC after passing through said process (I)-(III).

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