JP2008222996A - Noncrystalline resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a noncrystalline resin composition having high fluidity and being excellent in processability in undergoing melt processing such as that for a resin molded product, sheet, film, fiber or pipe. <P>SOLUTION: The resin composition is formed by compounding (A) 100 pts.wt. of a noncrystalline resin such as a noncrystalline nylon resin, polycarbonate (PC) resin, polyarylate resin, ABS resin, poly(meth)acrylate resin or poly(meth)acrylate copolymer with (B) 0.1-50 pts.wt. of a cyclic polyphenylene sulfide compound having a specific structure. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an amorphous resin, and by blending a cyclic polyphenylene sulfide compound having a specific ring structure, the present invention has excellent fluidity, and is used during melt processing of resin molded products, sheets, films, fibers, pipes, and the like. An amorphous resin composition having excellent processability is provided. Furthermore, the amorphous resin composition of the present invention is a transparent resin that is excellent in workability during melt processing and maintains excellent transparency by selecting an amorphous transparent resin from among the amorphous resins to be used. A composition is provided.

  Thermoplastic resins, especially engineering plastics with excellent mechanical properties and heat resistance, are used in various applications by taking advantage of their superior properties. Among these, amorphous resins are used in a wide range of fields including optical materials, household electrical appliances, office automation equipment, automobiles, and other parts, taking advantage of their transparency and dimensional stability.

  In recent years, these resins have been widely used in higher performance optical materials such as optical lenses, prisms, mirrors, optical disks, optical fibers, liquid crystal display sheets and films, light guide plates, etc. The optical properties, moldability, and heat resistance required for these products are also higher.

  However, when the amorphous resin is processed into a film or the like, if the fluidity is poor, the die pressure fluctuates due to the influence of the resin pressure at the time of melt processing derived from the resin viscosity. Therefore, in the case of film processing, there is a problem that uneven thickness of the film occurs, and in particular, thin film processing of the film becomes difficult.

  At present, these transparent resins are also used as lamp members for automobiles such as tail lamps and head lamps, but in recent years, tail lamp lenses, inner lenses, There is a tendency to reduce the distance between various lenses such as headlamps and shielded beams and the light source, and to increase the size and thickness of parts accompanying weight reduction, and excellent moldability such as improved fluidity is required. ing.

  In order to improve the fluidity, a general method is to lower the resin molecular weight or to lower the resin viscosity by raising the processing temperature, but when the molecular weight is lowered, the fluidity is improved. However, since the required properties such as heat resistance, chemical resistance, and mechanical properties are lowered, there is a limit to the method for reducing the molecular weight. In addition, increasing the processing temperature improves the fluidity at the time of melting, but there is a problem of a decrease in residence stability due to higher temperatures.Therefore, the improvement in processability and residence stability due to the improvement in fluidity can be achieved only at the processing temperature. It was difficult to achieve both.

  On the other hand, it has been proposed that fluidity can be improved by mixing an amorphous copolymer, an azocarbonic acid metal salt, or a hyperbranched polymer as a fluidity improver with an amorphous resin. Various studies have been made so far.

  Patent Documents 1 to 4 describe resin compositions in which an amorphous copolymer is synthesized and used as a fluidity modifier for an amorphous resin. The effect is not enough.

  In addition, if the additive blended to achieve these purposes is a high molecular weight substance, it is difficult to obtain an effect of fluidization, and if it is a low molecular weight substance, the fluidity is improved, but the mechanical properties are reduced. There is a problem that thermal decomposition occurs due to retention during molding process melting and decomposition gas and decomposition products thereof cause poor surface appearance, and mechanical properties and fluidity improvement effects are lost.

  In Patent Document 5, a resin composition using a hyperbranched polymer is described, and although it has a certain degree of fluidity improvement effect, the improvement effect is not sufficient, and a decrease in mechanical properties occurs with improvement in fluidity. Therefore, further development of good fluidization methods is required.

  Patent Document 6 discloses a resin composition in which a metal salt of an azocarbon acid is mixed. Although this known technique also has a certain degree of fluidity improving effect, the improving effect is not sufficient.

  That is, in the methods described in Patent Documents 1 to 6, although an improvement effect of good fluidization is recognized, the improvement effect is not yet sufficient. In addition, additives added to achieve these objectives cause problems such as thermal decomposition and chemical reaction with the matrix resin during molding, resulting in the generation of decomposition gas and resin composition. There was a problem that mechanical properties and fluidity improvement effects were lost by retaining the materials for a long time.

  Furthermore, among the amorphous resins, the amorphous transparent resins are widely used for higher performance optical materials as described above. Additives are added to improve moldability and heat resistance. Then, not only the problem of poor dispersion but also the problem that the transparency is remarkably lowered due to the difference in refractive index between the resin and the additive or the compounding agent. That is, any of the methods described in Patent Documents 1 to 6 has an essential problem that the transparency, which is the original optical characteristic of the amorphous transparent resin, is significantly reduced.

Although different from the solution of the present invention, by adding cyclic polyphenylene sulfide as a melt stabilizer to the polyphenylene sulfide resin composition containing linear polyphenylene sulfide and a filler, deterioration during melt processing is suppressed, Although the technique which suppresses the fall of a mechanical property is disclosed by patent document 7, in order to suppress the thermal deterioration at the time of the melt processing of the polyphenylene sulfide reinforced with the filler, this technique is a melt stabilizer for cyclic polyphenylene sulfide. This is a technique that is used as a non-crystalline resin and is different from the technique that was conceived to improve the fluidity of amorphous resins.
JP 2006-236557 A (Claims) JP 2006-257127 A (Claims) International Publication No. 2005/030819 (Claims) JP-A-10-7874 (Claims) International Publication No. 2006/42705 (Claims) JP-A-6-299056 (Claims) JP-A-10-77408 (Claims)

  The present invention relates to an amorphous resin composition that solves the above-mentioned problems while maintaining the characteristics of an amorphous resin and has excellent fluidity during melt processing, and further relates to a resin molded product, a sheet, a film, and a pipe The present invention relates to an amorphous resin composition suitable for melt processability. Furthermore, the amorphous resin composition of the present invention is a resin composition having excellent transparency as well as workability during melt processing when an amorphous transparent resin is used among the amorphous resins used. It is about.

  With regard to the amorphous resin composition, the authors have excellent fluidity by blending a cyclic polyphenylene sulfide compound having a specific ring structure, and can maintain excellent fluidity even by prolonged residence, Furthermore, it is excellent in melt processability when processed into a molded product such as a resin molded product or a film. Further, among the amorphous resins to be used, when the amorphous resin having transparency is selected, the cyclic of the present invention By blending the polyphenylene sulfide compound, the inventors succeeded in obtaining a resin composition having excellent fluidity while maintaining high transparency. That is, the present invention provides the following.

That is, the present invention
1. (A) A resin composition obtained by blending 0.1 to 50 parts by weight of a cyclic polyphenylene sulfide compound represented by the general formula (1) with respect to 100 parts by weight of an amorphous resin,

(M may be an integer of 4 to 20, m may be a mixture of 4 to 20)
2. (A) The amorphous resin is at least one selected from amorphous nylon resin, polycarbonate (PC) resin, polyarylate resin, ABS resin, poly (meth) acrylate resin, and poly (meth) acrylate copolymer The resin composition according to 1, which is
3. (B) In the cyclic polyphenylene sulfide compound, the resin composition according to any one of 1 and 2, wherein the content of the cyclic polyphenylene sulfide alone of m = 6 is less than 50% by weight,
4). (B) In the cyclic polyphenylene sulfide compound, the content of the cyclic polyphenylene sulfide alone of m = 6 is less than 30% by weight, The resin composition according to any one of 1 to 3,
5. M of the cyclic polyphenylene sulfide compound represented by the general formula (1) is 4 to 12, the resin composition according to any one of 1 to 4,
6). A method for producing a resin composition according to any one of 1 to 5, characterized by melt-kneading, and a molded product obtained by melt-molding the resin composition according to any one of 7.1 to 6.

  According to the present invention, it has excellent fluidity, surface appearance, excellent retention stability, excellent melt processability during injection molding and film processing, and uses amorphous transparent resin among amorphous resins In such a case, a resin composition having high transparency can be provided.

  Hereinafter, the present invention will be described in detail.

(1) Amorphous resin The amorphous resin (A) used in the present invention is not particularly limited as long as it is an amorphous resin that can be melt-molded. However, in terms of heat resistance, the glass transition temperature is low. The temperature is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, further preferably 70 ° C. or higher, and particularly preferably 80 ° C. or higher. The upper limit is not particularly limited, but is preferably 300 ° C. or less, more preferably 280 ° C. or less from the viewpoint of moldability.

  In addition, in this invention, the glass transition temperature of an amorphous resin (A) is 20 degreeC / min temperature rise from 30 degreeC-more than the glass transition temperature estimated from the amorphous resin (A) in differential calorimetry. The glass is observed when the temperature is raised under conditions and held for 1 minute, then cooled to 0 ° C. under a temperature drop condition of 20 ° C./minute, held for 1 minute, and then measured again under the temperature rise condition at 20 ° C./minute. Refers to the transition temperature (Tg).

  Specific examples include at least one selected from amorphous nylon resin, polycarbonate (PC) resin, polyarylate resin, ABS resin, poly (meth) acrylate resin, and poly (meth) acrylate copolymer. Or you may use 2 or more types together.

  Among these amorphous resins, polycarbonate (PC) resin having particularly high transparency, and among ABS resins, transparent ABS resin, polyarylate resin, poly (meth) acrylate resin, and poly (meth) acrylate copolymer are preferably used. can do.

  Among the above amorphous resins, the amorphous nylon resin is an amorphous polyamide resin excellent in heat resistance and strength, and the polyamide is a polymer mainly composed of amino acid, lactam or diamine and dicarboxylic acid. Or a copolymer. Examples of amino acids include 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, paraaminomethylbenzoic acid, and the like. Examples of lactam include ε-caprolactam and ω-laurolactam.

  Examples of the diamine include tetramethylene diamine, hexamethylene diamine, undecamethylene diamine, dodecamethylene diamine, 2,2,4-trimethylhexamethylene diamine, 2,4,4-trimethylhexamethylene diamine, 5-methylnonamethylene diamine, 2,4-dimethyloctamethylenediamine, metaxylylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 3, 8-bis (aminomethyl) tricyclodecane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) ) Piperazine, Ami Such as ethyl piperazine, and the like.

  Dicarboxylic acids include adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5- Examples include sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, and diglycolic acid.

  Specific examples of amorphous nylon include nylon 6I (hexamethylenediamine / isophthalic acid) / 6T (hexamethylenediamine / terephthalic acid), nylon 6I / 6T / PACMT (bis (4-aminocyclohexyl) methane / terephthalic acid). , Nylon 6T / 6I / MACMT (bis (3-methyl-4-aminocyclohexyl) methane / terephthalic acid), nylon 6T / 6I / MXDT (metaxylylenediamine / terephthalic acid), nylon 12 (ω-laurolactam) / PACM (bis (4-aminocyclohexyl) methane), nylon 12 / MACMT, nylon 12 / MACMI (bis (3-methyl-4-aminocyclohexyl) methane / isophthalic acid), etc. To mention copolymers and mixtures Kill.

  The molecular weight of the polyamide used in the present invention is not particularly limited, but is preferably 1,000 or more, more preferably 5,000 or more in order to obtain good mechanical properties, and good fluidity during molding. In order to obtain it, the upper limit is preferably 300,000 or less. The molecular weight here refers to a number average molecular weight obtained by measurement by a known molecular weight measurement method, for example, gel permeation chromatography (GPC).

  The polycarbonate resin is a resin having a carbonate bond, and is a polymer or copolymer obtained by reacting an aromatic hydroxy compound or a small amount of a polyhydroxy compound with a carbonate precursor. As aromatic hydroxy compounds, 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A), 2,2-bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) Propane, 2,2-bis (hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, hydroquinone, resorcinol, 4,6-dimethyl-2,4,6 -Tri (4-hydroxyphenyl) heptene, 2,4,6-dimethyl-2,4,6-tri (4 Hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene, 1,3,5-tri (4-hydroxyphenyl) benzene, 1,1,1-tri (4 -Hydroxyphenyl) ethane, 3,3-bis (4-hydroxyaryl) oxindole, 5-chloro-3,3-bis (4-hydroxyaryl) oxindole, 5,7-dichloro-3,3-bis ( 4-hydroxyaryl) oxindole, 5-bromo-3,3-bis (4-hydroxyaryl) oxindole, etc. may be mentioned, and these may be used alone or in combination of two or more.

  As the carbonate precursor, carbonyl halide, carbonate ester, haloformate or the like is used, and specific examples include phosgene, diphenyl carbonate and the like.

  The molecular weight of the polycarbonate used in the present invention is not particularly limited, but from the viewpoint of excellent impact resistance and moldability, a ratio when 0.7 g of polycarbonate resin is dissolved in 100 ml of methylene chloride and measured at 20 ° C. Those having a viscosity of 0.1 to 4.0, particularly 0.5 to 3.0 are preferred, and those having a viscosity of 0.8 to 2.0 are most preferred.

  The polyarylate resin is an amorphous wholly aromatic polyester, and typically, an aromatic dihydroxy compound such as bisphenol A or a derivative thereof and an aromatic dicarboxylic acid such as terephthalic acid or a derivative thereof are used. Is an amorphous high Tg polymer obtained from

  The aromatic dicarboxylic acid used for the preparation of the polyarylate is not particularly limited as long as it reacts with the aromatic dihydroxy compound to give a sufficient polymer, and is used alone or in combination of two or more. Representative examples include terephthalic acid and isophthalic acid.

  As aromatic hydroxy compounds, 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A), 2,2-bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) Propane, 2,2-bis (hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, hydroquinone, resorcinol, 4,6-dimethyl-2,4,6 -Tri (4-hydroxyphenyl) heptene, 2,4,6-dimethyl-2,4,6-tri (4 Hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene, 1,3,5-tri (4-hydroxyphenyl) benzene, 1,1,1-tri (4 -Hydroxyphenyl) ethane, 3,3-bis (4-hydroxyaryl) oxindole, 5-chloro-3,3-bis (4-hydroxyaryl) oxindole, 5,7-dichloro-3,3-bis ( 4-hydroxyaryl) oxindole, 5-bromo-3,3-bis (4-hydroxyaryl) oxindole, etc. may be mentioned, and these may be used alone or in combination of two or more.

  Typical polyarylate resins include those in which the aromatic dicarboxylic acid component is composed of terephthalic acid and isophthalic acid, and the aromatic hydroxy compound is composed of 2,2-bis (4-hydroxyphenyl) propane (bisphenol A). .

  The molecular weight of the polyarylate resin in the present invention is not particularly limited, and the specific viscosity measured at 25 ° C. in a chloroform solvent having a sample concentration of 0.4 g / 100 ml is preferably in the range of 0.1 to 6.0 dl / g. In particular, a polyarylate resin in the range of 0.2 to 5.0 dl / g is preferable.

  ABS resin is a graft polymer obtained by polymerizing a monomer mixture of an aromatic vinyl monomer, a vinyl cyanide monomer, and other monomers copolymerizable with these in the presence of a rubbery polymer. Means coalescence. Here, as the rubbery polymer, a polymer or copolymer having a conjugated diene as a main component is suitable. Specifically, polybutadiene rubber, styrene-butadiene copolymer, hydrogenated styrene-butadiene rubber, acrylonitrile-butadiene copolymer, butyl acrylate-butadiene copolymer, and isoprene rubber can be used.

  In addition, examples of aromatic vinyl monomers used include styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, t-butylstyrene, o-ethylstyrene, o-chlorostyrene, and o, p-dichlorostyrene. In particular, styrene is preferably used. Examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile and ethacrylonitrile, and acrylonitrile is particularly preferable.

  Further, other monomers copolymerizable with these include unsaturated carboxylic acid monomers, unsaturated carboxylic acid anhydride monomers, unsaturated carboxylic acid ester monomers, or maleimide monomers. It is also possible to use a polymer or the like, and it is also possible to use transparent ABS imparted with transparency by copolymerization thereof. Moreover, it is possible to blend said graft polymer and a styrene-type polymer as needed. Here, the styrene polymer means a copolymer obtained by polymerizing a monomer mixture of an aromatic vinyl monomer, a vinyl cyanide monomer, and other monomers copolymerizable therewith. To do. Each monomer can use the same thing as said graft polymer.

  The molecular weight of the ABS resin is not particularly limited, but the intrinsic viscosity is preferably 0.2 to 1 dl / g measured by extracting an acetone-soluble component and measuring at 30 ° C. in a solvent of 0.4 g / 100 cc of methyl ethyl ketone. A range of 3 to 0.6 dl / g is preferred.

  The poly (meth) acrylate resin has at least one monomer selected from acrylic acid and methacrylic acid as a structural unit, and two or more monomers may be copolymerized and used. . Examples of acrylates and methacrylates used to constitute poly (meth) acrylates include methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, and acrylic. Lauryl acid, dodecyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, benzyl methacrylate, lauryl methacrylate, dodecyl methacrylate, trifluoroethyl methacrylate, cyclohexyl methacrylate, methacrylic acid Examples thereof include methacrylic acid such as hydroxyethyl, and these may be used alone or in combination of two or more, and methyl methacrylate is preferred for imparting higher high-temperature rigidity.

  When polymethyl methacrylate is used as the poly (meth) acrylate, there is no particular limitation on the molecular weight of the resin, but in order to obtain good mechanical properties, it is preferably 5,000 or more, more preferably 10,000 or more, and molding. In order to obtain good fluidity at the time, the upper limit is preferably 500,000 or less. The molecular weight here refers to a number average molecular weight obtained by measurement by a known molecular weight measurement method, for example, gel permeation chromatography (GPC).

  Examples of the poly (meth) acrylate copolymer include a resin mainly composed of a copolymer composed of an unsaturated carboxylic acid alkyl ester unit, a glutaric anhydride unit, and other monomer units.

  The method for producing a thermoplastic copolymer containing glutaric anhydride units is basically produced by the following two steps. That is, an unsaturated carboxylic acid alkyl ester monomer and an unsaturated carboxylic acid monomer that give a glutaric anhydride unit in a subsequent heating step are copolymerized, and then the copolymer is added to the presence of an appropriate catalyst. The manufacturing method which consists of the process manufactured by making it heat in the absence or absence and performing an intramolecular cyclization reaction by dehydration and / or dealcohol is mentioned.

  Typically, the carboxyl group of the unsaturated carboxylic acid unit is dehydrated by heating the copolymer, or glutaric acid is removed by elimination of alcohol from the adjacent unsaturated carboxylic acid unit and unsaturated carboxylic acid alkyl ester unit. Anhydride units are produced.

  The unsaturated carboxylic acid monomer to be copolymerized is not particularly limited, and any unsaturated carboxylic acid monomer that can be copolymerized with other vinyl compounds can be used. As a preferable unsaturated carboxylic acid monomer, the following general formula (2)

(However, R ³ represents either hydrogen or an alkyl group having 1 to 5 carbon atoms)
In particular, acrylic acid and methacrylic acid are preferred, and methacrylic acid is more preferred from the viewpoint of excellent thermal stability. These can be used alone or in combination.

  The unsaturated carboxylic acid alkyl ester to be copolymerized is not particularly limited, but preferred specific examples include methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, benzyl acrylate, and acrylic acid. 2-ethylhexyl, lauryl acrylate, dodecyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, benzyl methacrylate, lauryl methacrylate, dodecyl methacrylate, trifluoroethyl methacrylate, etc. A monomer can be illustrated. Of these, methyl methacrylate and ethyl methacrylate are preferable, and methyl methacrylate is particularly preferable from the viewpoint of excellent optical characteristics and thermal stability. These may be used alone or as a mixture of two or more. Further, other vinyl monomers may be used as long as the effects of the present invention are not impaired.

  Specific examples of preferred copolymers include copolymers of methyl methacrylate and methacrylic acid. These copolymers or a structure containing glutaric anhydride units by heat treatment may be mentioned, and a structure containing glutaric anhydride units is preferable in consideration of higher temperature rigidity and chemical resistance.

  When using a resin whose main component is a copolymer comprising these unsaturated carboxylic acid alkyl ester units, glutaric anhydride units and other monomer units, the molecular weight is not particularly limited, but good mechanical properties are obtained. Therefore, it is preferably 5,000 or more, more preferably 10,000 or more, and the upper limit is preferably 500,000 or less in order to obtain good fluidity during molding. The molecular weight here refers to a number average molecular weight obtained by measurement by a known molecular weight measurement method, for example, gel permeation chromatography (GPC).

  Next, the cyclic polyphenylene sulfide compound used in the present invention will be described.

(2) Cyclic polyphenylene sulfide compound The cyclic polyphenylene sulfide compound of the present invention is a cyclic polyphenylene sulfide compound represented by the following general formula (1) and represented by an integer of m = 4 to 20, where m is 4 to 20: A mixture of

(M may be an integer of 4 to 20, m may be a mixture of 4 to 20)

  The repeating unit m in the above formula is an integer of 4 to 20, preferably 4 to 15, and more preferably 4 to 12.

  In addition, cyclic polyphenylene sulfide alone having a single m has a difference in easiness of crystallization, but is obtained as a crystal, and therefore tends to have a high melting point. On the other hand, in the case of a mixture having different m, the melting temperature is specifically lowered and the melt processing temperature can be reduced as compared with the cyclic polyphenylene sulfide alone, and the cyclic polyphenylene sulfide compound (mixture of m = 4 to 20) ) Is added to the amorphous resin, the fluidity improvement effect during melt processing, which is the object of the present invention, is particularly excellent. This can be achieved when the resin composition of the present invention is melt processed. Even if the heating temperature is low, the characteristics of excellent melt processability are exhibited. Further, among amorphous resins, when an amorphous transparent resin having excellent transparency is used, a characteristic that high transparency can be maintained is exhibited.

  For example, since m = 6 cyclic polyphenylene sulfide alone (cyclohexa (p-phenylene sulfide)) has a high melting point of 348 ° C., there is a problem that the cyclic material does not melt unless the melt processing temperature is raised. Even when the processing temperature is increased, when melt-kneading into an amorphous resin, there still remains a problem that the resin is not sufficiently melt-dispersed and becomes an aggregate in the resin or the transparency is lowered.

  Therefore, when blending cyclic polyphenylene sulfide alone in an amorphous resin, a method of dissolving and supplying the cyclic polyphenylene sulfide compound in a solvent for dissolving the cyclic polyphenylene sulfide compound, once the crystallized cyclic polyphenylene sulfide alone is melted at a melting point or higher, and then rapidly cooled. By suppressing the crystallization and supplying a non-crystallized powder, or by setting the premelter above the melting point of the cyclic polyphenylene sulfide alone, only the cyclic polyphenylene sulfide alone is melted in the premelter as a melt. A supply method or the like can be employed.

Due to the characteristics of the cyclic polyphenylene sulfide compound, the cyclic polyphenylene sulfide compound used in the present invention is preferably a cyclic polyphenylene sulfide compound having a different m from the viewpoint of production, melt processability and transparency maintenance.
The content of cyclic polyphenylene sulfide of m = 6 with respect to the cyclic polyphenylene sulfide compound is preferably less than 50% by weight, more preferably less than 40% by weight, and particularly preferably less than 30% by weight. (M = 6 cyclic polyphenylene sulfide simple substance (weight) / (cyclic polyphenylene sulfide compound (weight) × 100).

  Due to the characteristics of the cyclic polyphenylene sulfide, the cyclic polyphenylene sulfide compound used in the present invention is a mixture of cyclic polyphenylene sulfides having different m from the viewpoint of improving the fluidity during melt processing and maintaining the transparency.

  The ratio of each different m in the cyclic polyphenylene sulfide compound is not particularly limited, but in order to achieve the effects of the present invention, the cyclic polyphenylene sulfide compound has the highest melting point and m = 6 cyclic that is easy to crystallize. The content of polyphenylene sulfide alone is preferably less than 50% by weight, more preferably 40% by weight, and particularly preferably less than 30% by weight (m = 6 cyclic polyphenylene sulfide (weight) / (cyclic polyphenylene sulfide mixture ( (Weight) × 100) Here, the content of the cyclic polyphenylene sulfide alone of m = 6 in the cyclic polyphenylene sulfide mixture was determined by dividing the cyclic polyphenylene sulfide mixture into components by high performance liquid chromatography equipped with a UV detector. Has polyphenylene sulfide structure The ratio of the peak area attributed to the cyclic polyphenylene sulfide alone of m = 6 to the total peak area attributed to the compound having a polyphenylene sulfide structure is at least the phenylene sulfide structure. A compound having, for example, a cyclic polyphenylene sulfide compound or a linear polyphenylene sulfide and having a structure other than phenylene sulfide in a part thereof (for example, as a terminal structure) also belongs to the compound having a polyphenylene sulfide structure. In addition, the qualitative characteristics of each peak divided into components by this high performance liquid chromatography can be obtained by separating each peak by preparative liquid chromatography and performing an absorption spectrum or mass analysis in infrared spectroscopic analysis.

  Such a cyclic polyphenylene sulfide compound is obtained by obtaining a polyphenylene sulfide mixture containing polyphenylene sulfide and a cyclic polyphenylene sulfide compound by a known method for producing polyphenylene sulfide, and then extracting the cyclic polyphenylene sulfide compound from the polyphenylene sulfide mixture. be able to. The manufacturing method will be described below.

(3) Production method of polyphenylene sulfide mixture used as raw material of cyclic polyphenylene sulfide compound As a production method of polyphenylene sulfide mixture, a known technique can be used, for example, polyhalogenated fragrance represented by at least p-dichlorobenzene. A reaction solution containing a polyphenylene sulfide mixture and an alkali metal halide by heating a mixture containing a group compound, an alkali metal sulfide typified by sodium sulfide and an organic polar solvent typified by N-methyl-2-pyrrolidone Then, the reaction solution is treated with water or the like to obtain a polyphenylene sulfide mixture (polyphenylene sulfide and cyclic polyphenylene sulfide compound), or oxidative polymerization of diphenyl disulfides or thiophenols. Thus, a method for obtaining a polyphenylene sulfide mixture can be exemplified. However, since the cyclic polyphenylene sulfide compound generally contained in the polyphenylene sulfide mixture generally obtained by these methods is as low as less than 5% by weight, in order to obtain a polyphenylene sulfide mixture containing 5% by weight or more of the cyclic polyphenylene sulfide compound, for example, polyphenylene When polymerizing the sulfide mixture, a special method such as using a large amount of a polymerization solvent is required, and it is economically disadvantageous to obtain a large amount of polyphenylene sulfide mixture efficiently by such a method, and industrially. Is difficult to establish.

  As a method for producing a polyphenylene sulfide mixture other than the above, for example, at least a polyhalogenated aromatic compound typified by p-dichlorobenzene, an alkali metal sulfide typified by sodium sulfide, and N-methyl-2-pyrrolidone typified. The mixture containing an organic polar solvent is heated and polymerized, and then cooled to 220 ° C. or lower, and obtained by mixing at least granular polyphenylene sulfide and a polyphenylene sulfide mixture other than granular polyphenylene sulfide, an organic polar solvent, water, And a method of obtaining a polyphenylene sulfide mixture from the recovered slurry obtained when the granular polyphenylene sulfide is removed from the reaction solution containing the alkali metal halide and the alkali halide. Here, the granular polyphenylene sulfide refers to a polyphenylene sulfide component that can be recovered with a standard sieve (80 mesh sieve) having an average aperture of 0.175 mm. The polyphenylene sulfide mixture obtained by this method contains a large amount of low molecular weight polyphenylene sulfide having a weight average molecular weight of 5,000 or less. For example, the properties such as mechanical properties are significantly inferior to those of the granular polyphenylene sulfide. Conventionally, it has been recognized that it is difficult to apply to materials and has no industrial value. Therefore, the polyphenylene sulfide mixture obtained by this method is usually treated as industrial waste.

  As a result of detailed analysis of the polyphenylene sulfide mixture other than the granular polyphenylene sulfide, the present inventors have found that the polyphenylene sulfide contains 10% by weight of the cyclic polyphenylene sulfide (m = 4 to 20) represented by the formula (I). In particular, since these are obtained as a mixture of m = 4 to 20, it has been found preferable as a raw material for obtaining the cyclic polyphenylene sulfide compound of the present invention. This is significant from the viewpoint of recovering a compound having an extremely high industrial utility value from what was conventionally regarded as industrial waste by the method of the present invention.

  As a method for recovering polyphenylene sulfide from the recovered slurry, for example, at least 50% by weight or more of an organic polar solvent is removed from the recovered slurry, a residue is obtained, water is added thereto, and an acid is added as desired. In addition, at least the residual organic polar solvent and the alkali metal halide salt are removed and the polyphenylene sulfide mixture is separated and recovered, the polyphenylene sulfide mixture is precipitated from the recovered slurry, and the polyphenylene sulfide is recovered as a solid component, For example, after polyphenylene sulfide is precipitated by adding water to the recovered slurry, a method for obtaining polyphenylene sulfide as a solid component by a known solid-liquid separation method such as decantation, centrifugation, and filtration may be exemplified. it can.

(4) Preparation of Cyclic Polyphenylene Sulfide Compound-Containing Solution In the present invention, the polyphenylene sulfide compound is brought into contact with a solvent capable of dissolving the cyclic polyphenylene sulfide compound (m = 4 to 20) described in the formula (1) to form a cyclic polyphenylene sulfide compound. A solution containing is prepared.

  The solvent used here is not particularly limited as long as it is a solvent that can dissolve the cyclic polyphenylene sulfide compound. However, a solvent that dissolves the cyclic polyphenylene sulfide compound in the environment in which dissolution is performed but is difficult to dissolve the polyphenylene sulfide is preferable. A solvent that does not dissolve is more preferred. When the polyphenylene sulfide is brought into contact with the solvent, the reaction system pressure is preferably normal pressure or slight pressure, and particularly preferably normal pressure, and the reaction system of such pressure is inexpensive for the components of the reactor for constructing it. There are advantages. From this point of view, it is desirable that the reaction system pressure avoid pressurizing conditions that require an expensive pressure vessel. As the solvent to be used, those which do not substantially cause undesirable side reactions such as decomposition and crosslinking of polyphenylene sulfide and cyclic polyphenylene sulfide compounds are preferable. For example, when the operation of bringing the polyphenylene sulfide mixture into contact with the solvent is performed under atmospheric pressure reflux conditions Preferred solvents include hydrocarbon solvents such as pentane, hexane, heptane, octane, cyclohexane, cyclopentane, benzene, toluene, xylene, chloroform, bromoform, methylene chloride, 1,2-dichloroethane, 1,1,1- Halogen solvents such as trichloroethane, chlorobenzene, 2,6-dichlorotoluene, ketone solvents such as acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, methyl butyl ketone, acetophenone, Examples include ether solvents such as ethyl ether, tetrahydrofuran, and diisopropyl ether, and polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, trimethyl phosphoric acid, and N, N-dimethylimidazolidinone. Among them, benzene, toluene, xylene, chloroform, bromoform, methylene chloride, 1,2-dichloroethane, 1,1,1-trichloroethane, chlorobenzene, 2,6-dichlorotoluene, acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, methyl Butyl ketone, diethyl ether, tetrahydrofuran, diisopropyl ether, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, trimethyl phosphoric acid N, N-dimethylimidazolidinone are preferable, toluene, xylene, chloroform, methylene chloride, acetone, diethyl ketone, methyl ethyl ketone, tetrahydrofuran may be cited more preferably.

  There are no particular restrictions on the atmosphere in which polyphenylene sulfide is brought into contact with the solvent, but if polyphenylene sulfide or the solvent is subject to oxidative degradation due to conditions such as temperature or time at the time of contact, it should be performed in a non-oxidizing atmosphere. Is desirable. Note that the non-oxidizing atmosphere is an atmosphere having a gas phase oxygen concentration of 5% by volume or less, preferably 2% by volume or less, more preferably an oxygen-free atmosphere such as nitrogen, helium, argon, or the like. Among these, a nitrogen atmosphere is particularly preferable from the viewpoints of economy and ease of handling.

  The temperature at which the polyphenylene sulfide mixture is brought into contact with the solvent is not particularly limited, but generally, the higher the temperature, the more the cyclic polyphenylene sulfide compound tends to be dissolved in the solvent. As described above, since the contact of the polyphenylene sulfide mixture with the solvent is preferably performed under atmospheric pressure, the upper limit temperature is desirably set to the reflux condition temperature under the atmospheric pressure of the solvent used. When using a solvent, 20-150 degreeC can be illustrated as a specific temperature range, for example.

  The time for which the polyphenylene sulfide mixture is brought into contact with the solvent varies depending on the type of solvent used, the temperature, etc., and thus cannot be uniquely limited. For example, it can be exemplified by 1 minute to 50 hours. Even if it is too long, dissolution in the solvent reaches a saturated state, and no further effect can be obtained.

  The method of bringing polyphenylene sulfide into contact with the solvent is not particularly limited as long as a known general method is used. For example, a method of mixing the polyphenylene sulfide mixture and the solvent and stirring the solution as necessary, and then recovering the solution part, Any method such as a method of dissolving a cyclic polyphenylene sulfide in a solvent simultaneously with showering a solvent in a polyphenylene sulfide mixture on various filters and a method based on the principle of Soxhlet extraction can be used. Although there is no restriction | limiting in particular in the usage-amount of the solvent at the time of making a polyphenylene sulfide and a solvent contact, For example, the range of 0.5-100 can be illustrated by the bath ratio with respect to a polyphenylene sulfide weight. If the bath ratio is too small, not only the mixing of the polyphenylene sulfide mixture and the solvent becomes difficult, but the cyclic polyphenylene sulfide compound tends to be insufficiently dissolved in the solvent. A larger bath ratio is generally advantageous for dissolving a cyclic polyphenylene sulfide compound in a solvent, but if it is too large, no further effect can be expected, and conversely an economic disadvantage due to an increase in the amount of solvent used may occur. is there. When the contact between polyphenylene sulfide and the solvent is repeated, a sufficient effect is often obtained even with a small bath ratio. The Soxhlet extraction method, in principle, provides the same effect as when polyphenylene sulfide and a solvent are repeatedly contacted. In this case, a sufficient effect can often be obtained with a small bath ratio.

  After the polyphenylene sulfide is brought into contact with the solvent, the solution in which the cyclic polyphenylene sulfide compound is dissolved is obtained as a solid-liquid slurry containing the remaining solid polyphenylene sulfide. Recover. Examples of the solid-liquid separation method include separation by filtration, centrifugation, and decantation. For the solution thus separated, the solvent described later is removed. On the other hand, for the remaining solid component, when the cyclic polyphenylene sulfide compound still remains, specifically, when 0.05% by weight or more of the cyclic polyphenylene sulfide compound remains on the weight basis, the solvent is reused. The cyclic polyphenylene sulfide compound can be obtained in a higher yield by repeatedly performing contact with the catalyst and recovering the solution. Further, when the cyclic polyphenylene sulfide compound hardly remains, specifically, when the residual amount of the cyclic polyphenylene sulfide compound is less than 0.05% by weight, the residual solid is removed by removing the residual solvent. The polyphenylene sulfide can be suitably recycled as high-purity polyphenylene sulfide.

(5) Removal of solvent from cyclic polyphenylene sulfide compound solution In the present invention, the solvent is removed from the solution containing the cyclic polyphenylene sulfide compound (m = 4 to 20) represented by the formula (1) obtained as described above. Removal is performed to obtain a cyclic polyphenylene sulfide compound. Here, the removal of the solvent can be exemplified by, for example, a method of heating and treating at normal pressure or less, and removal of the solvent using a membrane, but in terms of obtaining a cyclic polyphenylene sulfide compound with higher yield and efficiency. A method of removing the solvent by heating at normal pressure or lower is preferred. The solution containing the cyclic polyphenylene sulfide compound obtained as described above may contain a solid depending on the temperature. In this case, since the solid belongs to the cyclic polyphenylene sulfide compound, the removal of the solvent. Sometimes it is desirable to recover together with a component soluble in a solvent, so that a cyclic polyphenylene sulfide compound can be obtained in a high yield.

  In removing the solvent, it is desirable to remove at least 50% by weight, preferably 70% by weight or more, more preferably 90% by weight or more, and still more preferably 95% by weight or more. Although the temperature at which the solvent is removed by heating depends on the characteristics of the solvent used, it cannot be limited uniquely. However, the temperature can usually be selected from 20 to 150 ° C, preferably from 40 to 120 ° C. In addition, the pressure for removing the solvent is preferably normal pressure or lower, which makes it possible to remove the solvent at a lower temperature.

(6) Other post-treatments The cyclic polyphenylene sulfide compound obtained by the method described in (3) to (5) has sufficiently high purity and can be suitably used as a cyclic polyphenylene sulfide compound of m = 4 to 20. However, it is possible to obtain a higher-purity cyclic polyphenylene sulfide compound or m = 6 cyclic polyphenylene sulfide alone by additionally performing post-treatment described below.

  The cyclic polyphenylene sulfide compound obtained by the operations (3) to (5) may contain an impurity component contained in the polyphenylene sulfide depending on the characteristics of the solvent used. Impurities are dissolved in cyclic polyphenylene sulfide compounds containing such a small amount of impurities, but cyclic polyphenylene sulfide compounds are not dissolved or contact with a second solvent in which cyclic polyphenylene sulfide compounds are difficult to dissolve to select impurity components. In many cases.

  The pressure of the reaction system when the cyclic polyphenylene sulfide compound is contacted with the second solvent is preferably normal pressure or slight pressure, and particularly preferably normal pressure, and the reaction system of such pressure is inexpensive to construct the members. There is an advantage of being. From this point of view, it is desirable that the reaction system pressure avoid pressurizing conditions that require an expensive pressure vessel. Preferred solvents as the second solvent are those that do not substantially cause undesirable side reactions such as decomposition and crosslinking of the target cyclic polyphenylene sulfide compound, such as methanol, ethanol, propanol, butanol, pentanol, ethylene glycol. , Alcohol / phenolic solvents such as propylene glycol, phenol, cresol, polyethylene glycol, and hydrocarbon solvents such as pentane, hexane, heptane, octane, cyclohexane, cyclopentane, etc., among which methanol, ethanol, propanol, butanol, Pentanol, ethylene glycol, propylene glycol, pentane, hexane, heptane, octane, cyclohexane, cyclopentane are preferred, methanol, ethanol , Propanol, ethylene glycol, pentane, hexane, heptane, octane, cyclohexane is particularly preferred. These solvents can be used as one kind or a mixture of two or more kinds.

  The temperature at which the cyclic polyphenylene sulfide compound is brought into contact with the second solvent is not particularly limited, but the upper limit temperature is preferably set to the reflux condition temperature under normal pressure of the second solvent to be used. In the case of using, for example, 20 to 100 ° C. can be exemplified as a preferable temperature range, and more preferably 25 to 80 ° C. can be exemplified.

  The time for which the cyclic polyphenylene sulfide compound is brought into contact with the second solvent cannot be uniquely limited because it varies depending on the type of solvent used, the temperature, etc., but for example, 1 minute to 50 hours can be exemplified. There is a tendency that the dissolution of the impurity in the second solvent tends to be insufficient, and if it is too long, the dissolution of the impurity in the second solvent reaches a saturated state, and no further effect is obtained.

  The cyclic polyphenylene sulfide compound is brought into contact with the second solvent by mixing the solid cyclic polyphenylene sulfide compound and the second solvent with stirring as necessary, or by adding the cyclic polyphenylene sulfide compound to the cyclic polyphenylene sulfide compound solid on various filters. A method of dissolving impurities in the second solvent at the same time as showering the second solvent, a method using Soxhlet extraction of the solid cyclic polyphenylene sulfide compound with the second solvent, a solution of the cyclic polyphenylene sulfide compound or solvent A method of bringing the cyclic polyphenylene sulfide compound slurry into contact with the second solvent and precipitating the cyclic polyphenylene sulfide compound in the presence of the second solvent can be used. Among them, the method of bringing the cyclic polyphenylene sulfide compound slurry containing the solvent into contact with the second solvent is an effective method because the cyclic polyphenylene sulfide compound obtained after the operation has high purity.

  After contacting the cyclic polyphenylene sulfide compound with the second solvent, a slurry in which the cyclic polyphenylene sulfide compound is precipitated in the second solvent is obtained, so that a solid cyclic polyphenylene sulfide is obtained using a known solid-liquid separation method. The compound is recovered. Examples of the solid-liquid separation method include separation by filtration, centrifugation, and decantation. If impurities still remain in the cyclic polyphenylene sulfide compound obtained after solid-liquid separation, it is also possible to contact the cyclic polyphenylene sulfide compound and the second solvent again to further remove the impurities.

(7) Characteristics of the cyclic polyphenylene sulfide compound of the present invention In the cyclic polyphenylene sulfide compound thus obtained, m in the formula (1) is 4 to 20, and m = 4 to 20 represented by the formula (1). The cyclic polyphenylene sulfide compounds having m different from each other are preferable, and the cyclic polyphenylene sulfide compound having a cyclic polyphenylene sulfide content of m = 6 in the cyclic polyphenylene sulfide compound is preferably less than 50% by weight.

  In addition, m of the cyclic polyphenylene sulfide compound of the present invention is m = 4 to 20 as described above, and m may be a mixture of 4 to 20, but as a cyclic polyphenylene sulfide compound, m = 4 as a cyclic polyphenylene sulfide compound as studied by the authors. When m is in this range, the fluidity-improving effect of the resin composition comprising the amorphous resin and the cyclic polyphenylene sulfide compound as described later, and the resin composition It has been found that processability and residence stability are improved when a product is melt processed.

  Although cyclic polyphenylene sulfide compounds having m of 12 or more are likely to exist, it is difficult to qualitatively or quantitatively determine them with the current analytical technique. This is because, as will be described later, it is difficult to distinguish between a linear polyphenylene sulfide oligomer contained in a cyclic polyphenylene sulfide compound and a cyclic polyphenylene sulfide having m = 13 or more with the latest analysis technique at present. However, in the present invention, the amorphous resin is blended with a cyclic polyphenylene sulfide compound of m = 4 to 20, and the content of the cyclic polyphenylene sulfide of m = 6 in the cyclic polyphenylene sulfide compound is a specific amount. Since the effect of the present invention is enhanced, a cyclic polyphenylene sulfide compound having m of 13 or more may be contained within a range not impairing the effect of the present invention.

Further, the cyclic polyphenylene sulfide compound obtained by the method described in (3) to (6) is sufficiently high in purity, but depending on conditions, a linear polyphenylene sulfide oligomer may be contained as an impurity. Further, as described above, it is difficult to distinguish between this linear polyphenylene sulfide oligomer and a cyclic polyphenylene sulfide compound having m = 13 or more with the latest analysis technique at present. The weight average molecular weight (Mw) of the oligomer component presumed to be this linear polyphenylene sulfide oligomer varies depending on the method for producing polyphenylene sulfide used as the raw material for the cyclic polyphenylene sulfide compound described in (3), but is usually 5000 or less. In some cases, it is 2000 or less.
The compounding amount of the cyclic polyphenylene sulfide compound of the present invention is a value including the cyclic polyphenylene sulfide compound and the linear polyphenylene sulfide oligomer and the cyclic polyphenylene sulfide compound having m of 13 or more, which are difficult to be separated and analyzed by the present analysis technique. Is defined as “cyclic polyphenylene sulfide compound”.

  The linear polyphenylene sulfide oligomer remaining as an impurity in the cyclic polyphenylene sulfide compound is poor in thermal stability as compared with the cyclic polyphenylene sulfide compound. If these are contained in a large amount as an impurity, the effect of the present invention can be obtained. In particular, there is a problem that the residence stability is lowered.

  Therefore, the amount of the linear polyphenylene sulfide oligomer in the cyclic polyphenylene sulfide compound obtained by the method described in (3) to (6) is preferably less than 50% by weight based on the total cyclic polyphenylene sulfide compound, and 40% by weight. % Is more preferred, and even more preferred is less than 30% by weight.

  The amount of linear polyphenylene sulfide oligomer in the cyclic polyphenylene sulfide compound at this time is determined by MALDI-TOF-MS as the total amount with the cyclic polyphenylene sulfide compound of m = 13 or more according to the present analysis technique. It is possible.

  In addition, as described in Patent Document 7, a method in which a cyclic polyphenylene sulfide compound is subjected to Soxhlet extraction from a crosslinked polyphenylene sulfide, the extract is cooled, and the precipitated white solid is recovered by a “recrystallization method”. When employed, it is disclosed that the obtained cyclic polyphenylene sulfide compound can be obtained with high purity of a cyclic polyphenylene sulfide having m = 6 (cyclohexa (p-phenylene sulfide). Although the amount recovered is small, cyclic polyphenylene sulfide alone of m = 6 can be obtained with high purity in the same manner from linear polyphenylene sulfide by the same extraction operation and “recrystallization”.

  Since the cyclic polyphenylene sulfide alone with m = 6 has a very stable needle-like crystal structure and is easily crystallized, it is a ring suitable for the method of “recrystallization”, but on the other hand, its stable needle-like crystal structure Reflecting this, the melting point becomes as high as 348 ° C., so the processing temperature must be increased. Even if the processing temperature is high, when melt-kneading into an amorphous resin, it will not melt and disperse sufficiently, and in applications where it is necessary to form aggregates in the resin or maintain transparency, molding There was a problem that the transparency of the product was lowered. Therefore, in the case where only m = 6 cyclic polyphenylene sulfide alone, in order to obtain the effects of the present invention, a method in which the cyclic polyphenylene sulfide compound is dissolved and supplied in a solvent for dissolving, and the crystallized cyclic polyphenylene sulfide alone is temporarily added. After melting above the melting point, quenching is performed to suppress crystallization and supply an amorphous powder, or the premelter is set above the melting point of the cyclic polyphenylene sulfide alone, and the cyclic polyphenylene sulfide alone in the premelter It is possible to employ a method in which only the resin is melted and supplied as a melt. When using cyclic polyphenylene sulfide alone as described above, the necessity of increasing the melt processing temperature or the necessity of melt-kneading the amorphous resin and the high-melting cyclic polyphenylene sulfide alone by the above method arises. From the viewpoint of melt processability and maintaining transparency, the content of the cyclic polyphenylene sulfide alone with m = 6 in the cyclic polyphenylene sulfide compound is preferably less than 50% by weight, more preferably less than 40% by weight, and more preferably 30% by weight. More preferably less than%.

  The reason for this is currently interpreted as follows. That is, when the content of the cyclic polyphenylene sulfide alone with m = 6 is reduced, there is an effect that the cyclic polyphenylene sulfide alone does not act as a crystal nucleus. As a result, the cyclic polyphenylene sulfide comprising a mixture of m = 4 or more. Crystallization of the sulfide compound is suppressed, and the melting point of the cyclic polyphenylene sulfide compound is lowered. As a result, both the amorphous resin as the matrix resin and the resin composition comprising the cyclic polyphenylene sulfide compound are melted, and the phase By dissolving, it is considered that the cyclic polyphenylene sulfide compound acts as a process plasticizer for the amorphous resin.

  In addition, since cyclic monomers other than m = 6 are difficult to crystallize compared to m = 6, it has been difficult to obtain a monomer by a method called “recrystallization” (isolated by a method called recrystallization). Only the cyclic polyphenylene sulfide of m = 6 is possible), the authors separated and recovered these monomers by a collection liquid chromatogram, and the cyclic polyphenylene sulfide of m = 4 (cyclotetra (p-phenylene sulfide), M = 5 cyclopenta (p-phenylene sulfide) (melting point 257 ° C.), m = 7 cyclohepta (p-phenylene sulfide) (melting point 328 ° C.), m = 8 cycloocta (p-phenylene sulfide) ) (Melting point 305 ° C.).

  That is, according to the methods described in (3) to (6), the obtained cyclic polyphenylene sulfide compound is a mixture having different m, and the content of the cyclic polyphenylene sulfide alone of m = 6 is less than 50% by weight. can get. Depending on the conditions, it is possible to obtain a cyclic polyphenylene sulfide having an m = 6 content of less than 30% by weight, or even less than 10% by weight. The obtained cyclic polyphenylene sulfide compound has a feature that its melting temperature is lower than that of a single cyclic polyphenylene sulfide composed of m, which means that, for example, a cyclic polyphenylene sulfide compound can be melt processed by a simple method. In addition, the fluidity at the time of melt processing is improved, and an excellent characteristic that good moldability is obtained at the time of melt processing of the amorphous resin composition containing the cyclic polyphenylene sulfide compound is expressed. Become.

  Furthermore, among the amorphous resins to be used, especially when using an amorphous transparent resin, by blending the cyclic polyphenylene sulfide compound of the present invention, not only good moldability but also the transparency of the amorphous transparent resin. Can be maintained.

(8) Amorphous Resin Composition The resin composition of the present invention has a cyclic polyphenylene sulfide compound represented by (B) the general formula (1) 0.1 to 100 parts by weight of the (A) amorphous resin. It is a resin composition formed by blending 50 parts by weight.

  When the amount of the cyclic polyphenylene sulfide compound is less than 0.1 part, the effect of improving the molding processability when the resin composition is melt processed, such as a sufficient effect of improving fluidity, is small. On the other hand, when the blending amount of the cyclic polyphenylene sulfide compound is 50% by weight or more, the characteristics of the amorphous resin itself may be lowered, or the viscosity may be drastically lowered, and the moldability may be lowered. Further, from the viewpoint of maintaining transparency, if it is 50% by weight or more, the transparency may be lowered.

Therefore, the addition amount of the cyclic polyphenylene sulfide compound is 0.1 to 50 parts by weight, preferably 0.5 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight.
The amorphous resin composition of the present invention can be obtained by blending (B) the cyclic polyphenylene sulfide compound obtained by the above-described method or the like with (A) the amorphous resin.

  The resin composition of the present invention may further contain a fibrous and / or non-fibrous filler as necessary. The blending amount is preferably 0.5 to 300 parts by weight with respect to 100 parts by weight of the amorphous resin (A) of the present invention. From the viewpoint of fluidity, the blending amount of the filler is 1 to 200 parts by weight. Part is preferable, and 1 to 100 parts by weight is more preferable. When the blending amount of the filler is less than 0.5 parts by weight, the mechanical strength improving effect tends to be insufficient, and when it exceeds 300 parts by weight, the fluidity may be lowered or the weight may be increased.

  As the kind of filler, any filler such as fibrous, plate-like, powdery, and granular can be used. As filler, glass fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, calcium carbonate whisker, wollastonite whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, stone koji fiber , Fibrous fillers such as metal fibers, or silicates such as talc, wollastonite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, bentonite, asbestos, alumina silicate, silicon oxide, magnesium oxide, alumina, Metal compounds such as zirconium oxide, titanium oxide and iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, glass beads, ceramic beads, boron nitride, silicon carbide, Hydroxides such as calcium oxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, glass flakes, glass powder, carbon black and silica, non-fibrous fillers such as graphite, and montmorillonite, beidellite, nontronite, saponite , Smectite clay minerals such as hectorite and soconite, and various clay minerals such as vermiculite, halloysite, kanemite, kenyanite, zirconium phosphate, titanium phosphate, Li type fluorine teniolite, Na type fluorine teniolite, Na type tetrasilicon fluorine mica, Li type Layered silicates typified by swelling mica such as tetrasilicon fluorine mica are used. The layered silicate may be a layered silicate in which exchangeable cations existing between layers are exchanged with organic onium ions, and examples of the organic onium ions include ammonium ions, phosphonium ions, and sulfonium ions. Of these, ammonium ions and phosphonium ions are preferred, and ammonium ions are particularly preferred. As the ammonium ion, any of primary ammonium, secondary ammonium, tertiary ammonium, and quaternary ammonium may be used. Primary ammonium ions include decyl ammonium, dodecyl ammonium, octadecyl ammonium, oleyl ammonium, benzyl ammonium and the like. Secondary ammonium ions include methyl dodecyl ammonium and methyl octadecyl ammonium. Examples of tertiary ammonium ions include dimethyl dodecyl ammonium and dimethyl octadecyl ammonium. Quaternary ammonium ions include benzyltrialkylammonium ions such as benzyltrimethylammonium, benzyltriethylammonium, benzyltributylammonium, benzyldimethyldodecylammonium, benzyldimethyloctadecylammonium, trioctylmethylammonium, trimethyloctylammonium, trimethyldodecylammonium, trimethyloctadecyl. Examples thereof include alkyltrimethylammonium ions such as ammonium, dimethyldialkylammonium ions such as dimethyldioctylammonium, dimethyldidodecylammonium, and dimethyldioctadecylammonium. Besides these, it is derived from aniline, p-phenylenediamine, α-naphthylamine, p-aminodimethylaniline, benzidine, pyridine, piperidine, 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and the like. And ammonium ions. Among these ammonium ions, trioctylmethylammonium, trimethyloctadecylammonium, benzyldimethyloctadecylammonium, ammonium ions derived from 12-aminododecanoic acid, and the like are preferable. Layered silicates in which exchangeable cations existing between layers are exchanged with organic onium ions can be produced by reacting layered silicates having exchangeable cations between layers and organic onium ions by a known method. it can. Specifically, a method by an ion exchange reaction in a polar solvent such as water, methanol, ethanol, or a method by directly reacting a layered silicate with a liquid or molten ammonium salt may be used. Among these fillers, preferred are glass fibers, talc, wollastonite, layered silicates such as montmorillonite and synthetic mica, and particularly preferred are glass fibers. The type of glass fiber is not particularly limited as long as it is generally used for reinforcing a resin, and can be selected from, for example, a long fiber type, a short fiber type chopped strand, a milled fiber, or the like. Moreover, said filler can also be used in combination of 2 or more types. The surface of the filler used in the present invention can be used by treating the surface with a known coupling agent (for example, silane coupling agent, titanate coupling agent, etc.) or other surface treatment agents. . Further, the glass fiber may be coated or bundled with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin.

  Furthermore, in the present invention, in order to maintain thermal stability, one or more kinds of heat-resistant agents selected from phenolic and phosphorus compounds can be contained. The blending amount of the heat-resistant agent is preferably 0.01 parts by weight or more, particularly preferably 0.02 parts by weight or more, with respect to 100 parts by weight of the amorphous resin (A) of the present invention, from the viewpoint of heat resistance improvement effect. From the viewpoint of gas components generated during molding, it is preferably 5 parts by weight or less, particularly preferably 1 part by weight or less. Moreover, it is particularly preferable to use a phenolic compound and a phosphorus compound in combination because of their large heat resistance, thermal stability, and fluidity retention effect.

  As the phenol compound, a hindered phenol compound is preferably used, and specific examples thereof include triethylene glycol-bis (3-t-butyl- (5-methyl-4-hydroxyphenyl) propionate), N, N ′. Hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), tetrakis (methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate) methane , Pentaerythrityltetrakis (3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate), 1,3,5-tris (3,5-di-t-butyl-4- Hydroxybenzyl) -s-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,1,3-tris (2-methyl-4-hydro) Loxy-5-tert-butylphenyl) butane, 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxy-) Phenyl) propionate, 3,9-bis (2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl) -2,4,8,10 -Tetraoxaspiro (5,5) undecane, 1,3,5-trimethyl-2,4,6-tris- (3,5-di-t-butyl-4-hydroxybenzyl) benzene and the like.

  Among them, N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), tetrakis (methylene-3- (3 ′, 5′-di-t-butyl-4′-) Hydroxyphenyl) propionate) methane and the like are preferably used.

  Next, as phosphorus compounds, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol di-phosphite, bis (2,4-di-t-butylphenyl) penta Erythritol di-phosphite, bis (2,4-di-cumylphenyl) pentaerythritol di-phosphite, tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2 , 4-Di-t-butylphenyl) -4,4′-bisphenylene phosphite, di-stearyl pentaerythritol di-phosphite, triphenyl phosphite, 3,5-dibutyl-4-hydroxybenzyl phosphonate Examples include diethyl ester. Among them, those having a high melting point are preferably used in order to reduce volatilization and decomposition of the heat-resistant material in the amorphous resin compound.

  Furthermore, the following compounds can be added to the amorphous resin composition of the present invention as long as the effects of the present invention are not impaired. Coupling agents such as organic titanate compounds and organic borane compounds, plasticizers such as polyalkylene oxide oligomer compounds, thioether compounds, ester compounds and organic phosphorus compounds, talc, kaolin, mica, sericite, basic Separation of inorganic fillers such as magnesium carbonate, aluminum hydroxide and glass flakes, montanic acid waxes, metal soaps such as lithium stearate and aluminum stearate, heavy compounds of ethylenediamine, stearic acid and sebacic acid, silicone compounds, etc. Ordinary additives such as a mold, an anti-coloring agent such as hypophosphite, and other additives such as a lubricant, an anti-ultraviolet agent, a coloring agent, a flame retardant, and a foaming agent can be blended. Any of the above compounds is not preferred because if the amount exceeds 20 parts by weight based on 100 parts by weight of the entire amorphous resin composition of the present invention, the original characteristics and fluidity of the amorphous resin composition of the present invention are impaired. Addition of not more than parts by weight, more preferably not more than 1 part by weight is preferable.

(9) Method for Producing Amorphous Resin Composition of the Present Invention The method for producing the amorphous resin composition of the present invention is not particularly limited. For example, amorphous resin (A), cyclic polyphenylene After previously blending the sulfide compound (B) and other additives as necessary, the mixture is uniformly melt-kneaded with a single-screw or twin-screw extruder above the melting point of the amorphous resin and the cyclic polyphenylene sulfide compound (B). The method, the method of removing a solvent after mixing in a solution, etc. are used. In particular, the cyclic polyphenylene sulfide compound (B) alone tends to have a high melting point. Therefore, when the cyclic polyphenylene sulfide simple substance is melt-kneaded, the cyclic polyphenylene sulfide compound is dissolved and supplied in a solvent that dissolves the cyclic polyphenylene sulfide compound. , A method in which the crystallized cyclic polyphenylene sulfide alone is once melted at a melting point or higher, and then quenched to suppress crystallization, and an amorphous powder is supplied. A method of setting the melting point or higher, melting only the cyclic polyphenylene sulfide alone in the premelter, and supplying it as a melt can be employed. In addition, the processing temperature here refers to the set temperature of a single screw or a twin screw extruder. Among these, from the viewpoint of productivity, a method of uniformly melting and kneading with a single-screw or twin-screw extruder is preferred, and in particular, using a twin-screw extruder, the glass transition temperature is higher than the amorphous resin, and a cyclic polyphenylene sulfide compound ( A method of uniformly kneading at a temperature equal to or higher than the melting point of B) is preferably used.

(10) Processing method of amorphous resin composition of the present invention The resin composition of the present invention can be molded by any known method such as injection molding, extrusion molding, blow molding, press molding, and spinning. It can be processed and used for various molded products. As molded products, they can be used as injection molded products, extrusion molded products, blow molded products, films, sheets, fibers, and the like. As a method for producing the film, a known melt film forming method can be employed. For example, after melting the resin composition in a single-screw or twin-screw extruder, the resin composition is extruded from a film die and cooled on a cooling drum. Examples include a method for producing an unstretched film, or a uniaxial stretching method, a biaxial stretching method, etc., in which a film thus produced is appropriately stretched in the longitudinal and transverse directions using a roller-type longitudinal stretching apparatus and a transverse stretching apparatus called a tenter. Although it is possible, it is not particularly limited to this.

  The feature of improving the fluidity of the resin composition of the present invention is that not only the effect of reducing the thickness unevenness of the film by suppressing the pressure fluctuation of the film die during the melt film formation, but also the melt film formation at a low pressure is possible. Therefore, the production discharge amount can be greatly increased. Usually, in order to reduce the melt viscosity, a technique of increasing the film forming temperature is general. However, due to the problem of generating bubble defects during film formation due to generation of decomposition gas and chemical deterioration due to long-term residence, Although there is a problem that the effect does not appear, the effect that the melt film-forming property is improved by using the resin composition of the present invention is recognized.

  As the fiber, it can be used as various fibers such as undrawn yarn, drawn yarn, and super-drawn yarn. As a method for producing a fiber using the resin composition of the present invention, a known melt spinning method can be applied. For example, chips made of a resin composition as a raw material are kneaded while being fed to a single-screw or twin-screw extruder, and then spun through a polymer streamline changer installed at the tip of the extruder, a filtration layer, etc. A method of extruding from the die, cooling, stretching, heat setting and the like can be employed, but is not particularly limited thereto.

  Furthermore, the fluidity of the resin composition is characterized by the fact that the pressure fluctuations of the filtration layer and the base during melt spinning can be suppressed, and not only the unevenness of the thickness of the yarn is small, but also melted yarn can be produced at a low pressure. Therefore, in addition to the effect that the production discharge amount can be greatly increased, melt spinning can be performed at a relatively low temperature, the generation of decomposition gas does not occur, and there is no problem such as yarn breakage.

  In particular, in the resin composition of the present invention, taking advantage of its excellent fluidity, it is processed into large injection molded products such as automobile parts and injection molded products having a thin part with a thickness of 0.01 to 1.0 mm. Is possible.

  Furthermore, the resin composition of the present invention can improve the above-described good fluidity and crystallization characteristics while maintaining high transparency, particularly when an amorphous transparent resin is selected among the amorphous resins. In addition, this feature is particularly suitable for resin applications, film applications, and optical applications that require transparency.

(11) Use of Amorphous Resin Composition of the Present Invention In the present invention, the various molded products are used for various applications such as automobile parts, electrical / electronic parts, building members, various containers, daily necessities, household goods and hygiene products. can do. Specific applications include air flow meters, air pumps, thermostat housings, engine mounts, ignition hobbins, ignition cases, clutch bobbins, sensor housings, idle speed control valves, vacuum switching valves, ECU housings, vacuum pump cases, inhibitor switches, rotations Sensor, Accelerometer, Distributor cap, Coil base, ABS actuator case, Radiator tank top and bottom, Cooling fan, Fan shroud, Engine cover, Cylinder head cover, Oil cap, Oil pan, Oil filter, Fuel cap, Fuel strainer , Distributor cap, vapor canister Automotive underhood parts such as uzing, air cleaner housing, timing belt cover, brake booster parts, various cases, various tubes, various tanks, various hoses, various clips, various valves, various pipes, torque control lever, safety belt parts, Car interior parts such as register blade, washer lever, window regulator handle, knob of window regulator handle, passing light lever, sun visor bracket, various motor housings, roof rail, fender, garnish, bumper, door mirror stay, spoiler, food louver, Wheel covers, wheel caps, grill apron cover frames, lamp reflectors, lamp bezels, door handles, etc. Car exterior parts, wire harness connectors, SMJ connectors, PCB connectors, door grommet connectors, various automotive connectors, relay cases, coil bobbins, optical pickup chassis, motor cases, laptop computer housings and internal parts, CRT display housings and internal parts, Printer housings and internal parts, mobile terminal housings and internal parts such as mobile phones, mobile PCs, handheld mobiles, recording medium (CD, DVD, PD, FDD, etc.) drive housings and internal parts, copier housings and internal parts And electrical / electronic parts such as facsimile housings and internal parts, parabolic antennas, and the like. In addition, VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, video cameras, projectors, lenses, viewfinders, filters, prisms, Fresnel lenses and other video equipment related parts, laser discs (registered) Trademark), compact disc (CD), CD-ROM, CD-R, CD-RW, DVD-ROM, DVD-R, DVD-RW, DVD-RAM, Blu-ray disc and other optical recording media substrates, various disc substrates Protective film, optical disc player pickup lens, optical recording / optical communication related parts such as optical fiber, optical switch, optical connector, liquid crystal display, flat panel display, plasma display light guide plate, Fresnel lens, polarizing plate, polarizing plate protective film, etc. Phase difference Film, light diffusing film, viewing angle widening film, reflective film, antireflection film, antiglare film, brightness enhancement film, prism sheet, pickup lens, light guide film for touch panel, cover and other information equipment related parts, lighting parts, refrigerator Examples include home and office electrical product parts such as parts, air conditioner parts, typewriter parts, word processor parts, and the like. Also, housings and internal parts of electronic musical instruments, home game machines, portable game machines, various gears, various cases, sensors, LEP lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, Optical pickups, oscillators, various terminal boards, transformers, plugs, printed wiring boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders , Electrical and electronic parts such as transformer members, coil bobbins, sash doors, blind curtain parts, piping joints, curtain liners, blind parts, gas meter parts, water meter parts, water heater parts, roof panels, Hot walls, adjusters, plastic bundles, ceiling fishing gear, staircases, doors, floors and other building materials, fishing lines, fishing nets, seaweed aquaculture nets, fishing bait bags and other marine products, vegetation nets, vegetation mats, weedproof bags, protection Grass net, curing sheet, slope protection sheet, fly ash holding sheet, drain sheet, water retention sheet, sludge / sludge dehydration bag, concrete formwork and other civil engineering related parts, gears, screws, springs, bearings, levers, key stems, cams , Ratchet, roller, water supply parts, toy parts, fans, gussets, pipes, cleaning jigs, motor parts, microscopes, binoculars, cameras, clocks, mechanical parts, multi-films, tunnel films, bird protection sheets, vegetation protection Non-woven fabric, seedling pots, vegetation piles, seed string tape, germination sheets, house lining sheets, farmhouse fasteners, slow-release fertilizers, root-proof sheets, garden nets Insect-proof nets, infant tree nets, printed laminates, fertilizer bags, sample bags, sandbags, animal damage prevention nets, incentive strings, windproof nets and other agricultural materials, paper diapers, sanitary products packaging materials, cotton swabs, towels, toilet seat wipes, etc. Supplies, medical non-woven fabric (stitching reinforcement, anti-adhesion film, prosthetic repair material), wound dressing, wound tape bandage, sticker base fabric, surgical suture, fracture reinforcement, medical film, spectacle lens, Glasses frames, contact lenses, endoscopes, medical supplies such as optical cells for analysis, medical equipment-related parts, calendars, stationery, clothing, food packaging films, trays, blisters, knives, forks, spoons, tubes, plastics Containers / tableware such as cans, pouches, containers, tanks, baskets, hot fill containers, microwave cooking containers, cosmetic containers, wraps, foam buffers, Paper lami, shampoo bottle, beverage bottle, cup, candy packaging, shrink label, lid material, envelope with window, fruit basket, hand cut tape, easy peel packaging, egg pack, HDD packaging, compost bag, recording media packaging, Containers and packaging such as shopping bags, wrapping films for electrical and electronic parts, natural fiber composites, polo shirts, T-shirts, innerwear, uniforms, sweaters, socks, ties, and other clothing, curtains, chairs, carpets, tablecloths , Interior goods such as futon, wallpaper, furoshiki, carrier tape, print lamination, heat sensitive stencil printing film, release film, porous film, container bag, credit card, cash card, ID card, IC card, paper, leather Hot melt buys such as nonwoven fabrics Binder, magnetic material, zinc sulfide, electrode material powder binder, optical element, conductive embossed tape, IC tray, golf tee, garbage bag, plastic bag, various nets, toothbrush, stationery, draining net, body towel, hand Towel, tea pack, drain filter, clear file, coating agent, adhesive, bag, chair, table, cooler box, kumade, hose reel, planter, hose nozzle, dining table, desk surface, furniture panel, kitchen cabinet, pen It is useful as a cap, a gas lighter and the like, and is particularly useful as a connector for various automobiles such as a wire harness connector, an SMJ connector, a PCB connector, and a door grommet connector.

  The amorphous resin composition of the present invention and a molded product comprising the same can be recycled. For example, a resin composition obtained by pulverizing a resin composition and a molded product comprising the resin composition, preferably powdered, and then adding additives as necessary, is used in the same manner as the resin composition of the present invention. It can also be a molded product.

  Hereinafter, the present invention will be specifically described with examples. The present invention is not limited to the following examples.

<Molecular weight measurement>
The molecular weight of the cyclic polyphenylene sulfide compound was calculated in terms of polystyrene by gel permeation chromatography (GPC), which is a type of size exclusion chromatography (SEC). The measurement conditions for GPC are shown below.
Apparatus: SSC-7100 (Senshu Science)
Column name: GPC3506 (Senshu Science)
Eluent: 1-chloronaphthalene detector: differential refractive index detector Column temperature: 210 ° C
Pre-constant temperature: 250 ° C
Pump bath temperature: 50 ° C
Detector temperature: 210 ° C
Flow rate: 1.0 mL / min
Sample injection amount: 300 μL (slurry: about 0.2% by weight)

The molecular weight of the poly (meth) acrylate copolymer was calculated in terms of polymethyl methacrylate by gel permeation chromatography (GPC) which is a kind of size exclusion chromatography (SEC). The measurement conditions for GPC are shown below.
Equipment: Shimadzu high performance liquid chromatograph (Shimadzu Corporation)
Column name: GPC KF-804L, GPC KF-806L (shodex)
Eluent: Tetrahydrofuran (for high performance liquid chromatography; Kanto Chemical)
Detector: Differential refractive index detector RID-10A
Column temperature: 30 ° C
Detector temperature: 35 ° C
Flow rate: 1.0 mL / min
Sample injection amount: 100 μL (sample concentration: 0.1 wt%).

<Fluidity>
In order to evaluate the fluidity, a capillary type melt viscosity measuring apparatus (CAPIROGRAPH-1C manufactured by Toyo Seiki Co., Ltd.) was used, and the pellets were put into the cylinder part for 3 minutes under the following conditions with a shear rate of 100 sec-1. The melt viscosity (Pa · s) measured after melting was used as a fluidity evaluation item. The melt viscosity at the time of residence was used as an indicator of residence stability by measuring the melt viscosity after retaining the pellets in the cylinder for 30 minutes.
Polyamide resin: 290 ° C., orifice L / D = 10 mm (inner diameter 1 mm)
Polycarbonate resin: 280 ° C., orifice L / D = 5 mm (inner diameter 1 mm)
Polyarylate resin: 340 ° C., orifice L / D = 1 mm (inner diameter 0.5 mm)
ABS resin: 280 ° C., orifice L / D = 5 mm (inner diameter 0.5 mm)
Polymethyl methacrylate: 230 ° C., orifice L / D = 5 mm (inner diameter 1 mm)
Poly (meth) acrylate copolymer: 280 ° C., orifice L / D = 5 mm (inner diameter 1 mm).

<Thermal characteristics>
Using a DSC RDC220 manufactured by Seiko Denshi Kogyo, the thermal characteristics of the obtained polymer were measured under a nitrogen atmosphere. The following measurement conditions were used, and the glass transition temperature Tg was 2nd Run.
First Run
・ 30 ℃ × 1 minute hold ・ Temperature increase from 30 ℃ to 250 ℃, temperature increase rate 20 ℃ / min ・ After temperature increase × 1 minute Hold ・ Temperature decrease to 0 ℃, temperature decrease rate 20 ℃ / min Second Run
• 0 ° C x 1 minute hold • Temperature rise from 0 ° C to 250 ° C, temperature rise rate 20 ° C / min (measure glass transition temperature at this time from DSC curve).

<Transparency (total light transmittance)>
Using a direct reading haze meter manufactured by Toyo Seiki Co., Ltd., the total light transmittance (%) was measured 5 times at 23 ° C. for a molded product having a thickness of 1 mm obtained by press molding under a predetermined temperature condition. The average value was used as an index of transparency.

(Reference Example 1) (Production Example of Polyphenylene Sulfide Mixture as Raw Material for Cyclic Polyphenylene Sulfide Compound)
A production example of polyphenylene sulfide as a raw material for the cyclic polyphenylene sulfide compound described in the text (3) will be described below.

<Preparation of polyphenylene sulfide mixture>
In a 1000 L autoclave with a stirrer, 42.7% sodium hydrosulfide 82.7 kg (700 mol), 96% sodium hydroxide 29.6 kg (710 mol), N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) In some cases, 114.4 kg (1160 mol), sodium acetate 17.2 kg (210 mol), and 100 kg of ion-exchanged water are charged and gradually heated to about 240 ° C. over about 3 hours while flowing nitrogen at normal pressure. After distilling 143 kg of water and 2.8 kg of NMP through the rectification tower, 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, 103 kg (703 mol) of p-dichlorobenzene and 90 kg (910 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 12.6 kg (700 mol) of water was injected over 15 minutes, it was cooled to 250 ° C. at a rate of 1.3 ° C./min. Thereafter, the slurry 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 (A). This slurry (A) was diluted with 200 kg of NMP to obtain a slurry (B).

  100 kg of the slurry (B) heated to 80 ° C. is filtered with a sieve (80 mesh, opening 0.175 mm) at a 25 kg / 1 batch scale, and a granular PPS resin containing the slurry as a mesh-on component is used as a filtrate component. About 75 kg of slurry (C) was obtained.

  Of the obtained slurry (C), 75 kg was charged in a devolatilizer at 25 kg / 1 batch and replaced with nitrogen, and then treated at 100 to 150 ° C. under reduced pressure for 1.5 hours, and then 150 wt. A solid was obtained by treatment at 1 ° C. for 1 hour. After adding 100 kg of ion-exchanged water (1.2 times the amount of slurry (C)) to this solid, it was stirred at 70 ° C. for 30 minutes to make a slurry again. This slurry was subjected to vacuum suction filtration with a filter having an opening of 10 to 16 μm. 100 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 form a slurry again. Similarly, after suction filtration, vacuum drying was performed at 70 ° C. for 5 hours to obtain 0.9 kg of a polyphenylene sulfide mixture.

  Next, production examples of cyclic polyphenylene sulfide compounds by the methods described in the texts (4) to (6) will be described below.

Reference Example 2 Production of Cyclic Polyphenylene Sulfide Compound (cPPS-1) 500 g of the polyphenylene sulfide mixture obtained by the method of Reference Example 1 was collected, and Soxhlet extraction was performed at a bath temperature of about 80 ° C. using 12 kg of chloroform as a solvent. By the method, the polyphenylene sulfide mixture and the solvent were contacted for 3 hours to obtain an extract. The obtained extract was in the form of a slurry partially containing solid components at room temperature. Chloroform was distilled off from this extract slurry using an evaporator and then treated at 70 ° C. for 3 hours in a vacuum dryer to obtain 210 g of a solid (yield 42% with respect to the polyphenylene sulfide mixture).

  The solid thus obtained was confirmed to be a compound having a phenylene sulfide skeleton from an absorption spectrum in infrared spectroscopic analysis (apparatus; FTIR-8100A manufactured by Shimadzu Corporation). In addition, mass spectrum analysis (device: Hitachi M-1200H) of components separated from high performance liquid chromatography (device; Shimadzu LC-10, column; C18, detector; photodiode array), MALDI-TOF -Based on molecular weight information by MS and GPC, this solid is a mixture mainly composed of cyclic polyphenylene sulfide having 4 to 12 repeating units. The weight fraction of cyclic polyphenylene sulfide is about 87% and 13% is linear. It was found to be a polyphenylene sulfide oligomer and a cyclic polyphenylene sulfide compound (Mw = 2000) having m = 13 or more.

  A series of results are shown in Table 1.

  According to the present invention, it was found that a high-purity cyclic polyphenylene sulfide mixture containing about 87% by weight of cyclic polyphenylene sulfide can be obtained in high yield.

Reference Example 3 Production of Cyclic Polyphenylene Sulfide Compound (cPPS-2) After obtaining a solid in the same manner as in Reference Example 2, 2 kg of chloroform was added to the obtained solid, and ultrasonic waves were applied at room temperature to form a slurry. A mixture was obtained. In order to bring this into contact with methanol as the second solvent, the slurry mixture was slowly added dropwise to 25 kg 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 180 g of a white powder. The yield of white powder was 35% based on the polyphenylene sulfide mixture used.

  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. Further, white powder of cyclic polyphenylene sulfide having 4 to 12 repeating units as a main component is obtained from mass spectral analysis of components separated by high performance liquid chromatography, molecular weight information by MALDI-TOF-MS and molecular weight information by GPC. It was found that the weight fraction of the cyclic polyphenylene sulfide was about 94%, and 6% was a linear polyphenylene sulfide oligomer and a cyclic polyphenylene sulfide compound (Mw = 2000) of m = 13 or more.

Reference Example 4 Production of Cyclic Polyphenylene Sulfide Compound (cPPS-3) After obtaining a solid in the same manner as Reference Example 3, the following operation was further added. That is, 3 kg of chloroform was again added to the obtained solid, and ultrasonic mixture was applied at room temperature to obtain a slurry mixture. In order to bring this into contact with methanol as the second solvent, the slurry mixture was slowly added dropwise to 25 kg of methanol over about 10 minutes while stirring. After completion of dropping, stirring was continued for about 15 minutes. 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 140 g of a white powder. The yield of white powder was 28% based on the polyphenylene sulfide mixture used.

  From the absorption spectrum in the infrared spectroscopic analysis of this white powder, it was confirmed that the white powder was a polymer compound composed of phenylene sulfide units. Moreover, from the mass spectrum analysis of the component divided into components by high performance liquid chromatography, and further from the molecular weight information by MALDI-TOF-MS, this white powder is a mixture mainly composed of cyclic polyphenylene sulfide having 4 to 12 repeating units, It was found that the weight fraction of the cyclic polyphenylene sulfide was about 97%, and 3% was a linear polyphenylene sulfide oligomer and a cyclic polyphenylene sulfide compound (Mw = 2000) of m = 13 or more.

Reference Example 5 Production of polyphenylene sulfide mixture using diphenyl disulfide and production of cyclic polyphenylene sulfide compound (cPPS-4) 22.4 g (0.1 mol) of palladium acetate was dissolved in 20 L of 1,2-dichloroethane, 30.02 g (0.2 mol) of trifluoromethanesulfonic acid and 840.12 g (4 mol) of trifluoroacetic anhydride were added. Thereto, 436.69 g (2 mol) of diphenyl disulfide was added, the inside of the reaction system was replaced with oxygen, heated to 40 ° C., and reacted at 40 ° C. for 5 hours. In addition, disappearance of diphenyl disulfide was confirmed 2 hours after the start of the reaction by gas chromatography analysis of the reaction solution. After completion of the reaction, the reaction solution was poured into 20 kg of 10% by weight hydrochloric acid methanol solution to obtain a precipitate. The precipitate was filtered, washed with 10 kg of water and 10 kg of methanol, and then dried at 80 ° C. under reduced pressure to obtain a polyphenylene sulfide mixture (280 g) in a yield of 64%. The following operations were performed in the same manner as in Reference Example 2. That is, 280 g of the obtained polyphenylene sulfide mixture was fractioned, and 12 kg of chloroform was used as a solvent, and the polyphenylene sulfide mixture and the solvent were contacted by a Soxhlet extraction method at a bath temperature of about 80 ° C. for 3 hours to obtain an extract. The obtained extract was in the form of a slurry partially containing solid components at room temperature. Chloroform was distilled off from this extract slurry using an evaporator, and the mixture was then treated at 70 ° C. for 3 hours to obtain 50 g of a solid. The yield of white powder was 18% based on the polyphenylene sulfide mixture used.
The solid thus obtained was confirmed to be a compound having a phenylene sulfide skeleton from an absorption spectrum in infrared spectroscopic analysis (apparatus; FTIR-8100A manufactured by Shimadzu Corporation). In addition, mass spectrum analysis (device: Hitachi M-1200H) of components separated from high performance liquid chromatography (device; Shimadzu LC-10, column; C18, detector; photodiode array), MALDI-TOF From the molecular weight information by -MS, this solid is a mixture mainly composed of cyclic polyphenylene sulfide having 5 to 12 repeating units. The weight fraction of cyclic polyphenylene sulfide is about 80%, and 20% is linear polyphenylene sulfide. It was found to be an oligomer and a cyclic polyphenylene sulfide compound (Mw = 3000) having m = 13 or more.

Reference Example 6 Production of simple cyclic polyphenylene sulfide having m = 6 (cPPS-5)
By a method similar to that described in JP-A-11-315206, 1000 L of chloroform was extracted from 10 kg of a commercially available cross-linked PPS resin (“Torelina” M2100). Thereafter, the extract was cooled to room temperature, and the precipitated white solid and the solvent were separated by filtration. The obtained white solid was naturally dried overnight and then dried at 160 ° C. for 2 hours. Mass spectral analysis of the components separated from the obtained white solid (50 g) by high performance liquid chromatography (apparatus; Shimadzu LC-10, column; C18, detector; photodiode array) (apparatus; Hitachi M- 1200H), and further from molecular weight information by MALDI-TOF-MS, cyclohexa (p-phenylene sulfide) having a purity of 99.9%, linear polyphenylene sulfide oligomer having a purity of 0.1%, and cyclic polyphenylene sulfide compound having m = 13 or more ( Mw = 2000).

Reference Example 7 Production of cyclic polyphenylene sulfide alone with m = 6 (cPPS-6)
500 g of the polyphenylene sulfide mixture obtained by the method of Reference Example 1 was collected, 12 kg 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 3 hours. Obtained. The obtained extract was in the form of a slurry partially containing solid components at room temperature. Chloroform was distilled off from this extract slurry using an evaporator and then treated at 70 ° C. for 3 hours in a vacuum dryer to obtain 210 g of a solid (yield 42% with respect to the polyphenylene sulfide mixture).

  210 g of the solid thus obtained was again subjected to Soxhlet extraction with 12 kg of chloroform for 8 hours. The extract was filtered while hot, then the filtrate was gradually cooled to room temperature and left for 24 hours. The precipitated white solid and the solvent were separated by filtration and treated at a vacuum dryer at 70 ° C. for 3 hours to recover 100 g of a solid. Mass spectral analysis of the components separated from the obtained white solid (100 g) by high performance liquid chromatography (apparatus; Shimadzu LC-10, column; C18, detector; photodiode array) (apparatus; Hitachi M- 1200H), and further from molecular weight information by MALDI-TOF-MS, cyclohexa (p-phenylene sulfide) having a purity of 99.9%, linear polyphenylene sulfide oligomer having a purity of 0.1%, and cyclic polyphenylene sulfide compound having m = 13 or more ( Mw = 2000).

(Reference Example 8) Isolation of Cyclic Polyphenylene Sulfide Unit A 97% pure cyclic polyphenylene sulfide compound (cPPS-3) produced in Reference Example 4 was separated into each component using preparative high performance liquid chromatography, and m = 4 The components of ˜12 were separated and collected, and the melting point was measured. The melting point is shown in Table 2 for reference.

  From Table 2, it can be seen that the melting point of the simple substance of cyclic polyphenylene sulfide is very high, and a decrease in the melting point is observed as m increases. Further, from comparison between Table 1 and Table 2, it can be seen that the melting point of the cyclic polyphenylene sulfide compound comprising a mixture of m = 4 to 12 specifically decreases to around 225 ° C. as compared with the cyclic polyphenylene sulfide alone.

(Reference Examples 9 to 11) Preparation of cyclic polyphenylene sulfide simple substance and cyclic polyphenylene sulfide compound blended with c = 6 (cPPS-7, 8, 9) and their thermal properties cPPS-3 (purity 97%) prepared in Reference Example 4 ) (Cyclic polyphenylene sulfide compound) and Patent Document 5, cPPS-5 (m = 6 cyclic polyphenylene sulfide alone) prepared in Reference Example 6 was dry blended using a Henschel mixer at the following blending ratio.
cPPS-7: cPPS-3 / cPPS-5 = 80/20 (% by weight) (Reference Example 9)
cPPS-8: cPPS-3 / cPPS-5 = 70/30 (wt%) (Reference Example 10)
cPPS-9: cPPS-3 / cPPS-5 = 50/50 (% by weight) (Reference Example 11)
The melting points of the obtained blended products are shown in Table 1.

  The melting point of the cyclic polyphenylene sulfide compound (cPPS-7) containing 32% by weight of cyclic polyphenylene sulfide (m = 6) was 250 ° C., and cPPS-5 containing 99.9% of cyclic polyphenylene sulfide (m = 6). It turns out that melting | fusing point is low compared with (reference example 6) and cPPS-6 (reference example 7). As the amount of the cyclic polyphenylene sulfide alone with m = 6 increases, the melting point tends to increase. The melting point of cPPS-8 (containing 33.5% by weight of the cyclic polyphenylene sulfide alone with m = 6) is 270 ° C. It can be seen that cPPS-9 (containing 41% by weight of cyclic polyphenylene sulfide alone with m = 6) has a melting point almost the same as the melting point 282 ° C. of polyphenylene sulfide.

  The results of Reference Examples 1 to 11 are summarized as follows.

  A cyclic polyphenylene sulfide compound is obtained by the methods described in the texts (3) to (6), and the content of the cyclic polyphenylene sulfide alone with m = 6 is less than 50% by weight. The amount of linear PPS oligomer contained as an impurity is 20% by weight or less.

  The melting point of the cyclic polyphenylene sulfide compound composed of a mixture of m = 4 to 12 is specifically around 226 ° C., whereas the melting point of the cyclic polyphenylene sulfide alone of m = 6 is extremely high as 348 ° C. Recognize. Further, it can be seen that not only m = 6 but also any of the cyclic polyphenylene sulfides of m = 4, 5, and 7 to 12 isolated by preparative high performance liquid chromatography have a higher melting point than the cyclic polyphenylene sulfide compound. In the cyclic polyphenylene sulfide compound, when the content of the cyclic polyphenylene sulfide alone with m = 6 is less than 50% by weight, the melting point is around 280 ° C.

  Next, the glutaric anhydride-containing copolymer used in the examples of the present invention will be described.

(Reference Example 12) Method for Producing Resin Containing Mainly Copolymer Composed of Unsaturated Carboxylic Acid Alkyl Ester Unit, Glutaric Anhydride Unit and Other Monomer Units The copolymer polymerization method was described below. Although it does not restrict to a method, the synthesis method by the precipitation polymerization method using the solvent of the poly (meth) acrylate copolymer is shown as an example.

(A-1): Precipitation polymerization method The following mixed substances are supplied to a stainless steel autoclave having a capacity of 20 liters and equipped with a baffle and a foudra-type stirring blade, and nitrogen is added to the system while stirring at 250 rpm. Gas was bubbled for 15 minutes. Next, nitrogen gas was flowed at a flow rate of 5 L / min, and the reaction system was heated to 80 ° C. while stirring. When the internal temperature reached 80 ° C., the polymerization was started. The internal temperature was maintained at 80 ° C. for 90 minutes, and after raising the temperature to 95 ° C., the polymerization was further continued for 90 minutes to complete the polymerization. The reaction system was cooled to room temperature, and the resulting slurry was treated with a centrifuge “LAC-21” (product of Matsumoto Machine Sales Co., Ltd.) for 2 hours while flowing nitrogen gas, and copolymer (A-1) And the organic solvent were separated. The polymer recovery rate by the centrifuge processing was almost 100%. The reslurry washing with the polymerization solvent was repeated three times, followed by drying at 80 ° C. for 12 hours to obtain a powdery copolymer (A-1). The copolymer (A-1) had a polymerization rate of 76% and a weight average molecular weight of 120,000.
Methacrylic acid 25 parts by weight Methyl methacrylate 75 parts by weight n-Heptane 225 parts by weight Butyl acetate 675 parts by weight 2,2′-azobis-2,4-dimethylvaleronitrile 0.5 parts by weight

  Next, a method for obtaining a glutaric anhydride-containing copolymer by subjecting the copolymer (A-1) obtained above to a heat treatment will be described. Although heat processing is not restricted to the following method, it shows about the melt-kneading method using an extruder as an example.

(B-1): Extruder melt kneading method 100 parts by weight of copolymer (A-1) was mixed with 0.2 parts by weight of lithium acetate, and this was mixed with a 44 mmφ twin screw extruder (TEX-44 (Japan). L / D = 28.0, vent part: 3 places), while purging nitrogen at a rate of 10 L / min from the hopper part, screw rotation speed 75 rpm, raw material supply rate 5 kg / h, An intramolecular cyclization reaction was performed at a cylinder temperature of 280 ° C. to obtain a pellet-shaped thermoplastic copolymer (B-1).

(Reference Example 13)
A fluidity improver was prepared according to Patent Document 1 (Japanese Patent Laid-Open No. 2006-236557, method described in Production Example 1).

  In a separable flask equipped with a condenser and a stirrer, anionic emulsifier ("Latemul ASK", manufactured by Kao Corporation) (solid content 28%) 1.0 part (solid content) and 290 parts of distilled water were charged. Heated to 80 ° C. in a water bath under nitrogen atmosphere. Next, 0.0001 part of ferrous sulfate, 0.0003 part of ethylenediaminetetraacetic acid disodium salt and 0.3 part of Rongalite were dissolved in 5 parts of distilled water and then added, followed by 87.5 parts of styrene and 12.5 parts of phenyl methacrylate. A mixture of 0.2 part of t-butyl hydroperoxide and 0.5 part of n-octyl mercaptan was added dropwise over 180 minutes. Thereafter, the mixture was stirred for 60 minutes to complete the polymerization. Next, 300 parts by weight of an aqueous solution in which sulfuric acid was dissolved at a rate of 0.7% was heated to 70 ° C. and stirred. In this, the obtained polymer emulsion was gradually dripped and coagulated. The precipitate was separated and washed and then dried at 75 ° C. for 24 hours to obtain a polymer. The polymerization yield was 96%, which is almost equivalent to that described in Patent Document 1. Weight average molecular weight of this polymer (method described in the above <Molecular Weight Measurement> section; Shimadzu High Performance Liquid Chromatograph (Shimadzu Corporation) Column name: GPC KF-804L, GPC KF-806L (shodex), eluent: tetrahydrofuran ( Adopted for high performance liquid chromatography; Kanto Chemical Co., Ltd.) had Mw = 50000 and a molecular weight almost equivalent to the result described in Patent Document 1.

[Examples 1 to 12, Comparative Examples 1 and 2]
Tg = 160 ° C., 20% of 98% sulfuric acid 1.0 g / dl 98% sulfuric acid relative viscosity 1.95 grill amide resin (TR55 manufactured by EMS) (hereinafter abbreviated as TR55) Blend, set to an extrusion temperature of 290 ° C, have two kneading zones, and supply to a twin screw extruder (PCM-30 manufactured by Ikegai Kogyo Co., Ltd.) rotated at a high rotational speed of 200 rpm. Then, after pelletizing, vacuum drying was performed at a temperature of 80 ° C. for 3 hours, and then a melt viscosity was measured at 290 ° C. and a shear rate of 100 sec ⁻¹ . In addition, in the case of TR55 simple substance of the comparative example 1, TR55 simple substance was melt-kneaded similarly in order to remove the difference in heat history with other resin compositions. In Examples 11 and 12, the same method except that m = 6 cyclic polyphenylene sulfide alone (m = 6 is 99.9%) was dissolved and blended in advance as a 10 wt% N-methylpyrrolidone (NMP) solution. I went there.

  Moreover, in the comparative example 2, it carried out similarly to Examples 1-12 except having used the fluidity improver adjusted by the reference example 13. FIG.

  In Examples 1 to 12 and Comparative Examples 1 and 2, the molded product used for the transparency evaluation (total light transmittance (%)) of the resin composition was melted at a temperature of 290 ° C. for 5 minutes using a press die. After the heating, the press mold was cooled at 80 ° C. for 5 minutes to prepare a molded product having a thickness of 1 mm.

  In Comparative Example 2, a slight foaming behavior due to thermal decomposition of the fluidity improver itself was observed during melt kneading and pressing. A series of results are shown in Table 3.

From Examples 1 to 10, the TR55 resin composition containing a cyclic polyphenylene sulfide compound (mixture of m = 4 to 20) has a remarkable melt viscosity at 290 ° C. as compared with the melt-kneaded TR55 of Comparative Example 1 alone. It can be seen that it has dropped. Moreover, it shows that melt viscosity performance is almost the same after the residence test, and that the resin composition is excellent in residence stability and exhibits good fluidity after residence.
Moreover, the fluidity improvement effect is recognized also in Examples 11 and 12 in which a cyclic substance having m = 6 as a cyclic polyphenylene sulfide compound is blended as an NMP solution. In addition, compared with the case where the cyclic polyphenylene sulfide compound of Examples 1-10 is mix | blended, the tendency for a fluid improvement effect to be slightly low is recognized. Further, from the results of Examples 1 to 7 and Examples 8 to 12, a higher fluidity improving effect can be obtained when the content of the cyclic polyphenylene sulfide alone with m = 6 in the cyclic polyphenylene sulfide compound is less than 50% by weight. I understand.

  From these results, it can be seen that by adding a cyclic polyphenylene sulfide compound to TR55, the fluidity is increased and the retention stability is also excellent.

  Furthermore, the resin composition which mix | blended the fluidity improver (reference example 13) prepared by the method of patent document 1 from the comparison of Examples 1-12 and Comparative Example 2 has little fluidity improvement effect, and also fluidity | liquidity. It turns out that transparency (light transmittance) falls remarkably by the mixing | blending of an improver.

  From the above results, the resin composition containing the cyclic polyphenylene sulfide compound has not only a fluidity improving effect, but also a transparent composition almost equivalent to that obtained by melt kneading only TR55 of Comparative Example 1, that is, nothing blended. It was found to maintain sex. In general, when an additive is added to a resin, not only the problem of poor dispersion but also the transparency is significantly lowered due to the difference in refractive index between the resin and the additive. However, in Examples 1-12, it turns out that transparency has hardly fallen.

[Examples 12 to 24, Comparative Examples 3 and 4]
Tg = 151 ° C., 0.7 g dissolved in 100 ml of methylene chloride and measured at 20 ° C. Polycarbonate resin having a specific viscosity of 1.14 (“Iupilon” S3000 manufactured by Mitsubishi Engineering Plastics Co., Ltd.) Examples 1-12 and Comparative Example 1 except that the raw material consisting of the above was dry blended, the extrusion temperature was set to 270 ° C., the screw rotation speed was set to 200 rpm, and the hot air dryer was used to dry at 120 ° C. for 5 hours. The melt viscosity was measured at 280 ° C. and a shear rate of 100 sec ⁻¹ . In Examples 23 and 24, the same procedure was followed except that m = 6 cyclic polyphenylene sulfide alone (m = 6 was 99.9%) was dissolved and blended in advance as a 10 wt% NMP solution.

  In Examples 12 to 24 and Comparative Examples 3 and 4, the molded product used for the transparency evaluation (total light transmittance (%)) of the resin composition was melted at a temperature of 270 ° C. for 5 minutes using a press mold. After the heating, the press mold was cooled at 80 ° C. for 5 minutes to prepare a molded product having a thickness of 1 mm.

  From Examples 13 to 22, the melt viscosity at 280 ° C. of the polycarbonate resin composition containing the cyclic polyphenylene sulfide compound is significantly lower than that obtained by melt-kneading only the polycarbonate resin. In addition, since the polycarbonate resin undergoes a decrease in molecular weight due to long-term residence, the melt viscosity after residence tends to decrease overall. From the comparison of melt viscosity after residence in Examples 13 to 22 and Comparative Example 2, It can be seen that the resin composition containing the polyphenylene sulfide compound maintains good fluidity and further maintains transparency as compared with the polycarbonate resin alone.

  Moreover, although the fluidity improvement effect is recognized also in Example 23 and 24 which mix | blended the cyclic | annular substance of m = 6 as an NMP solution as a cyclic polyphenylene sulfide compound, compared with the cyclic polyphenylene sulfide compound of Examples 13-22, fluidity improvement There is a tendency to be slightly less effective.

  In addition, from the results of Examples 13 to 19 and Examples 20 to 24, the higher fluidity improvement effect can be obtained when the content of the cyclic polyphenylene sulfide of m = 6 in the cyclic polyphenylene sulfide compound is less than 50% by weight. I understand.

  Furthermore, from the comparison between Examples 13 to 24 and Comparative Example 4, the resin composition containing the fluidity improver (Reference Example 13) prepared by the method described in Patent Document 1 has a small fluidity improvement effect, and further fluidity. It can be seen that the light transmittance is significantly reduced by the incorporation of the improver.

  From these results, it can be seen that even when a cyclic polyphenylene sulfide compound is added to the polycarbonate resin, the fluidity is increased and the effect is maintained even after the residence stability.

  Furthermore, from the results of Examples 13 to 24, not only the fluidity improving effect but also the transparency almost equivalent to that obtained by melt-kneading only the polycarbonate resin of Comparative Example 3, that is, nothing blended is maintained. I understood.

[Examples 25 to 36, Comparative Example 5]
Tg = 193 ° C. polyarylate resin (U-100 manufactured by Unitika Ltd.) is dry blended with the raw materials having the composition shown in Table 5, the extrusion temperature is set to 360 ° C., the screw speed is set to 100 rpm, and hot air drying is performed. The melt viscosity was measured at 340 ° C. and a shear rate of 100 sec ⁻¹ by performing the same operations as in Examples 1 to 12 and Comparative Example 1 except that the film was dried at 140 ° C. for 12 hours. In Examples 35 and 36, the same procedure was followed except that m = 6 cyclic polyphenylene sulfide alone (m = 6 was 99.9%) was dissolved and blended in advance as a 10 wt% NMP solution.

  The polyarylate resin has a high Tg, and it is necessary to set the extrusion temperature to a high temperature of 360 ° C. However, at this extrusion temperature, the fluidity improver prepared in Reference Example 13 is poor in thermal stability, It has been difficult to blend fluidity improvers.

In Examples 25 to 36 and Comparative Example 5, the molded product used for the transparency evaluation (total light transmittance (%)) of the resin composition was melt-heated at a temperature of 270 ° C. for 5 minutes using a press mold. The press mold was cooled at 80 ° C. for 5 minutes to produce a molded product having a thickness of 1 mm.

  From Examples 25 to 34, the polyarylate resin composition containing a cyclic polyphenylene sulfide compound has a markedly lower melt viscosity at 340 ° C. than that obtained by melt-kneading only the polyarylate resin. Further, from the comparison of the melt viscosity after residence in Examples 25 to 34 and Comparative Example 3, it can be seen that the resin composition containing the cyclic polyphenylene sulfide compound maintains good fluidity as compared with the polyarylate resin alone. .

  In addition, the fluidity improvement effect is also observed in Examples 35 and 36 in which m = 6 cyclic substance alone as a cyclic polyphenylene sulfide compound is blended as an NMP solution. There is a tendency to be slightly less effective.

  Further, from the results of Examples 25-31 and Examples 32-36, a higher fluidity-improving effect is obtained when the content of the cyclic polyphenylene sulfide of m = 6 in the cyclic polyphenylene sulfide compound is less than 50% by weight. I understand.

  From these results, it can be seen that even when a cyclic polyphenylene sulfide compound is added to the polyarylate resin, the fluidity is increased and the effect is maintained even after the residence stability.

  Further, from the results of Examples 25 to 36, it was found that not only the fluidity improving effect but also the characteristic of maintaining substantially the same transparency as that obtained by melt kneading only the polyarylate resin of Comparative Example 5 was obtained.

[Examples 37 to 48, Comparative Examples 6 and 7]
The raw materials having the composition shown in Table 6 were dry blended with ABS resin (Toyolac "1050B" manufactured by Toray Industries, Inc.) having an intrinsic viscosity of 0.39 dl / g of soluble methyl etol ketone, and the extrusion temperature was 250 ° C. The same procedure as in Examples 1 to 12 and Comparative Example 1 was performed except that the screw rotation speed was set to 200 rpm, and drying was performed at 70 ° C. for 6 hours with a hot air dryer, at 250 ° C. and a shear rate of 100 sec ⁻¹ . The melt viscosity was measured. In Examples 47 and 48, the same procedure was followed except that m = 6 cyclic polyphenylene sulfide alone (m = 6 was 99.9%) was dissolved and blended in advance as a 10 wt% NMP solution.

  Moreover, in the comparative example 7, it carried out similarly to Examples 1-12 except having used the fluidity improver adjusted by the reference example 13. FIG. The ABS resin is an amorphous resin in which butadiene rubber is blended as an impact modifier, and the ABS resin itself is a resin that does not have transparency. Therefore, in Examples 37 to 48 and Comparative Examples 6 and 7, the ABS resin is transparent. It was difficult to evaluate (total light transmittance (%)).

  From Examples 37 to 46, the melt viscosity at 250 ° C. of the ABS resin composition containing the cyclic polyphenylene sulfide compound is significantly lower than that obtained by melt-kneading only the ABS resin. Moreover, it turns out that the resin composition which mix | blended the cyclic polyphenylene sulfide compound maintains the good fluidity compared with the ABS resin single-piece | unit from the comparison of the melt viscosity after residence of Examples 37-46 and the comparative example 6. FIG. Moreover, although the fluidity improvement effect is recognized also in Example 47 and 48 which mix | blended the cyclic | annular substance of m = 6 as an NMP solution as a cyclic polyphenylene sulfide compound, compared with the cyclic polyphenylene sulfide compound of Examples 37-46, fluidity improvement There is a tendency to be slightly less effective.

  Further, from the results of Examples 37 to 43 and Examples 44 to 48, a higher fluidity improving effect is obtained when the content of the cyclic polyphenylene sulfide of m = 6 in the cyclic polyphenylene sulfide compound is less than 50% by weight. I understand.

  Furthermore, from comparison between Examples 37 to 48 and Comparative Example 7, it can be seen that the resin composition containing the fluidity improver (Reference Example 13) prepared by the method described in Patent Document 1 has a small fluidity improvement effect. From these results, it can be seen that by adding the cyclic polyphenylene sulfide compound to the ABS resin, the fluidity is increased and the effect is maintained even after the residence stability.

[Examples 49 to 60, Comparative Examples 8 and 9]
A raw material having the composition shown in Table 7 was dry blended with a polymethyl methacrylate resin having a Tg of 118 ° C. and a weight average molecular weight of 100,000, the extrusion temperature was set to 230 ° C., and 100 ° C. for 3 hours with a hot air dryer. Except for drying, the same operations as in Examples 1 to 12 and Comparative Example 1 were performed, and melt viscosity measurement and DSC measurement were performed at 230 ° C. and a shear rate of 100 sec ⁻¹ . In Examples 59 and 60, the same procedure was followed except that m = 6 cyclic polyphenylene sulfide alone (m = 6 was 99.9%) was dissolved and mixed in advance as a 10 wt% NMP solution.

In Comparative Example 9, the same procedure as in Examples 1 to 12 was performed except that the fluidity improver prepared in Reference Example 13 was used. In Examples 49 to 60 and Comparative Examples 8 and 9, the molded product used for the transparency evaluation (total light transmittance (%)) of the resin composition was melted at a temperature of 230 ° C. for 5 minutes using a press mold. After the heating, the press mold was cooled at 80 ° C. for 5 minutes to prepare a molded product having a thickness of 1 mm.

  From Examples 49 to 58, the polymethyl methacrylate resin composition containing a cyclic polyphenylene sulfide compound has a significantly reduced melt viscosity at 230 ° C. compared to a melt-kneaded polymethyl methacrylate resin alone, It can be seen that the melt viscosity after residence also shows almost the same melt viscosity.

  There was almost no change in the overall melt viscosity after residence. From the comparison of the melt viscosity after residence in Examples 49 to 58 and Comparative Example 8, the resin composition containing the cyclic polyphenylene sulfide compound was polymethyl methacrylate resin. It is understood that it maintains good fluidity compared to a single substance, and maintains substantially the same transparency as that obtained by melt-kneading only polymethyl methacrylate resin, that is, nothing blended (Comparative Example 8). It was.

  In addition, the fluidity improvement effect is also observed in Examples 59 and 60 in which a simple substance of m = 6 as a cyclic polyphenylene sulfide compound is blended as an NMP solution, but the fluidity is improved as compared with the cyclic polyphenylene sulfide compounds of Examples 49 to 58. There is a tendency to be slightly less effective.

  Further, from the results of Examples 49 to 55 and Examples 56 to 60, a higher fluidity improving effect can be obtained when the content of the cyclic polyphenylene sulfide alone of m = 6 in the cyclic polyphenylene sulfide compound is less than 50% by weight. I understand.

  From these results, it can be seen that even when a cyclic polyphenylene sulfide compound is added to the polymethyl methacrylate resin, the fluidity is increased and the retention stability is also excellent.

  Moreover, from the comparison of Examples 49-60 and Comparative Example 9, the resin composition containing the fluidity improver (Reference Example 13) prepared by the method described in Patent Document 1 has a small fluidity improvement effect and further transparency. It turns out that it falls remarkably.

[Examples 61 to 72, Comparative Examples 10 and 11]
The poly (meth) acrylate copolymer obtained in B-1 of Reference Example 12 having a Tg of 137 ° C. and a weight average molecular weight of 120,000 was dry-blended with the raw material having the composition shown in Table 8, and the extrusion temperature was adjusted. The melt viscosity was measured at 280 ° C. and a shear rate of 100 sec ⁻¹ by performing the same operations as in Examples 1 to 12 and Comparative Example 1 except that the temperature was set at 280 ° C. and dried at 110 ° C. for 3 hours with a hot air dryer. DSC measurement was performed. In Examples 71 and 72, the same procedure was followed except that m = 6 cyclic polyphenylene sulfide alone (m = 6 was 99.9%) was dissolved and blended in advance as a 10 wt% NMP solution.

Moreover, in the comparative example 10, it carried out similarly to Examples 1-12 except having used the fluidity improver adjusted by the reference example 13. FIG. In Examples 61 to 72 and Comparative Examples 10 and 11, the molded product used for the transparency evaluation (total light transmittance (%)) of the resin composition was melted at a temperature of 280 ° C. for 5 minutes using a press mold. After the heating, the press mold was cooled at 80 ° C. for 5 minutes to prepare a molded product having a thickness of 1 mm.

  From Examples 61 to 70, the resin composition of the poly (meth) acrylate copolymer containing the cyclic polyphenylene sulfide compound is melt viscosity at 280 ° C. as compared with the one obtained by melt kneading only the poly (meth) acrylate copolymer. Is significantly reduced, and the melt viscosity after residence is almost the same, or a poly (meth) acrylate copolymer only melt-kneaded, that is, nothing blended ( It can be seen that the same transparency as in Comparative Example 10) is maintained.

There is almost no change in the overall melt viscosity after residence. From the comparison of the melt viscosity after residence in Examples 61 to 70 and Comparative Example 10, the resin composition containing the cyclic polyphenylene sulfide compound was poly (meth) acrylate. It can be seen that good fluidity and transparency are maintained as compared with the copolymer alone.

  Moreover, although the fluidity improvement effect is recognized also in Example 71,72 which mix | blended the cyclic | annular substance of m = 6 as an NMP solution as a cyclic polyphenylene sulfide compound, compared with the cyclic polyphenylene sulfide compound of Examples 61-70, fluidity improvement There is a tendency to be slightly less effective.

  Further, from the results of Examples 61 to 67 and Examples 68 to 72, a higher fluidity improving effect can be obtained when the content of the cyclic polyphenylene sulfide alone with m = 6 in the cyclic polyphenylene sulfide compound is less than 50% by weight. I understand.

  Further, from the comparison between Examples 61 to 70 and Comparative Example 11, the resin composition containing the fluidity improver (Reference Example 13) prepared by the method described in Patent Document 1 has a small fluidity improvement effect and further transparency. It turns out that it falls remarkably.

  From these results, it can be seen that even when a cyclic polyphenylene sulfide compound is added to the poly (meth) acrylate copolymer, the fluidity is increased and the retention stability and transparency are also excellent.

  As described above, regarding an amorphous resin composition, by blending a cyclic polyphenylene sulfide compound having a specific ring structure, the resin has excellent fluidity without impairing the characteristics of the amorphous resin, and the resin. It has become possible to provide an amorphous resin composition having excellent processability during melt processing of molded products, sheets, films, fibers, pipes, and the like.

Claims (7)

(A) A resin composition obtained by blending 0.1 to 50 parts by weight of a cyclic polyphenylene sulfide compound represented by the general formula (1) with respect to 100 parts by weight of an amorphous resin.

(M may be an integer of 4 to 20, m may be a mixture of 4 to 20) (A) The amorphous resin is at least one selected from amorphous nylon resin, polycarbonate (PC) resin, polyarylate resin, ABS resin, poly (meth) acrylate resin, and poly (meth) acrylate copolymer The resin composition according to claim 1. The resin composition according to any one of claims 1 and 2, wherein in the cyclic polyphenylene sulfide compound, the content of a single cyclic polyphenylene sulfide of m = 6 is less than 50% by weight. 4. The resin composition according to claim 1, wherein in the cyclic polyphenylene sulfide compound, the content of the cyclic polyphenylene sulfide alone of m = 6 is less than 30% by weight. The resin composition according to any one of claims 1 to 4, wherein m of the cyclic polyphenylene sulfide compound represented by the general formula (1) is 4 to 12. The method for producing a resin composition according to any one of claims 1 to 5, wherein the resin composition is melt-kneaded. A molded product obtained by melt-molding the resin composition according to any one of claims 1 to 6.