Resin composition for fiber-reinforced composite molded articles

Abstract

To provide a resin composition for a fiber-reinforced composite body which is excellent in mechanical characteristics such as flexural strength and shear strength, and long-term durability of the mechanical characteristics, and flame retardancy.SOLUTION: A resin composition for a fiber-reinforced composite body contains 70-99 pts.wt. of (A) a polycarbonate resin (component A), and 30-1 pts.wt. of (B) phosphazene (component B) containing 98.5 mol% or more of a phosphazene cyclic trimer.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to a resin composition for fiber-reinforced composite molded articles. More specifically, it relates to a resin composition for fiber-reinforced composite molded articles that is excellent in long-term strength durability and flame retardancy, and is suitable for electrical and electronic components, home appliances, automotive parts, infrastructure parts, housing equipment parts, and the like. [Background technology]

[0002] Polycarbonates and carbonate unit-containing copolymers are used as matrix layers in laminates containing fiber-containing structures. Laminates based on polycarbonates and fiber structures can be molded into various structures by thermoforming, net-shape stretching, deep drawing, etc. Such laminated structures can be used in a wide range of applications, including automotive parts, general industrial materials, electronic equipment, and medical devices. From a safety perspective, flame retardancy, and from the perspective of reducing environmental impact by extending product life, the ability to maintain performance over long-term use is becoming extremely important for these laminated structures.

[0003] A method of imparting flame retardancy to fiber-reinforced composite molded articles using polycarbonate resin as the matrix resin is known, which involves adding phosphazene compounds (Patent Documents 1 and 2).

[0004] However, when phosphazene compounds are added, there is a problem of reduced strength under high temperature and high humidity conditions. Therefore, there is a need for a resin composition for fiber-reinforced composite molded articles that can achieve both flame retardancy and long-term durability. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Special Publication No. 2021-506616 [Patent Document 2] Japanese Patent Publication No. 2016-008295 [Overview of the project] [Problems that the invention aims to solve]

[0006] In view of the above, the object of the present invention is to provide a resin composition for fiber-reinforced composite molded articles that is excellent in mechanical properties such as bending strength and shear strength, as well as in their long-term durability and flame retardancy. [Means for solving the problem]

[0007] As a result of diligent research to solve the above problems, the inventors of the present invention have found that by compounding a polycarbonate resin and a thermoplastic resin containing phosphazene with a phosphazene cyclic trimer of 98.5 mol% or more with reinforcing fibers, a fiber-reinforced composite molded article with excellent long-term durability of mechanical strength and flame retardancy can be obtained, thus completing the present invention. According to the present invention, the above problems are solved by the following items 1 to 7.

[0008] 1. A resin composition for fiber-reinforced composite molded articles characterized by containing (A) 70 to 99 parts by weight of polycarbonate resin (component A) and (B) 30 to 1 part by weight of phosphazene (component B) containing 98.5 mol% or more of a phosphazene cyclic trimer. 2. The resin composition for fiber-reinforced composite molded articles described in item 1 above, which contains 0.1 to 20 parts by weight of (C) adhesion improver (component C) per 100 parts by weight of the total amount of component A and component B. 3. The fiber-reinforced composite molded article according to item 1 or 2 above, wherein component C is an organic compound having at least one functional group selected from the group consisting of epoxy groups, carboxylic acid groups, and acid anhydride groups in one molecule. 4. A resin composition for fiber-reinforced composite molded articles according to any one of items 1 to 3 above, wherein component C is at least one organic compound selected from the group consisting of glycidyl methacrylate, bisphenol A type epoxy resin, polybutylene terephthalate, polyethylene terephthalate, polyarylate, and styrene-maleic acid resin. 5. A fiber-reinforced composite molded article which is a composite of the resin composition according to any one of claims 1 to 4 and reinforcing fibers. 6. The fiber reinforced composite body according to paragraph 5 above, wherein the fiber constituting the reinforcing fiber is at least one fiber selected from carbon fiber, glass fiber, and aramid fiber. 7. The fiber reinforced composite body according to paragraph 5 or 6 above, wherein the reinforcing fiber is in the form of a reinforcing fiber sheet, the resin composition is in the form of a resin composition sheet, and it is a laminate of the reinforcing fiber sheet and the resin composition sheet.

Advantages of the Invention

[0009] The fiber reinforced composite containing the resin composition for the fiber reinforced composite body of the present invention is excellent in long-term durability of mechanical strength and flame retardancy, and is useful for electric and electronic parts, household electrical appliances, automobile-related parts, infrastructure-related parts, housing-related parts, etc., and the industrial effects achieved are particularly remarkable.

Brief Description of the Drawings

[0010] [Figure 1] It is a schematic diagram of a cross-sectional view of the laminate in the present invention. [Figure 2] It is a schematic diagram of a cross-sectional view of the fiber reinforced composite body in the present invention. [Figure 3] It is a schematic diagram of an LFT-D apparatus.

Embodiments for Carrying Out the Invention

[0011] Hereinafter, the present invention will be specifically described.

[0012] <Laminate> <Component A: Polycarbonate Resin> The polycarbonate resin used in the present invention is obtained by reacting a divalent phenol with a carbonate precursor. Examples of the reaction method include interfacial polymerization method, melt transesterification method, solid-phase transesterification method of carbonate prepolymer, and ring-opening polymerization method of cyclic carbonate compound, etc.

[0013] Typical examples of divalent phenols used here include hydroquinone, resorcinol, 4,4'-biphenol, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane (commonly known as bisphenol A), 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxyphenyl)pentane, and 4,4'-(p-phenyl Examples include bis(4-hydroxyphenyl)diphenol, 4,4'-(m-phenylenediisopropylidene)diphenol, 1,1-bis(4-hydroxyphenyl)-4-isopropylcyclohexane, bis(4-hydroxyphenyl)oxide, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)ketone, bis(4-hydroxyphenyl)ester, bis(4-hydroxy-3-methylphenyl)sulfide, 9,9-bis(4-hydroxyphenyl)fluorene, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene. Preferred divalent phenols are bis(4-hydroxyphenyl)alkanes, among which bisphenol A is particularly preferred and widely used in terms of impact resistance.

[0014] In this invention, in addition to bisphenol A-based polycarbonate resins, which are general-purpose polycarbonate resins, it is also possible to use special polycarbonate resins manufactured using other divalent phenols as component A.

[0015] For example, polycarbonate resins (homopolymers or copolymers) using 4,4'-(m-phenylenediisopropylidene)diphenol (sometimes abbreviated as "BPM"), 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (sometimes abbreviated as "Bis-TMC"), 9,9-bis(4-hydroxyphenyl)fluorene, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (sometimes abbreviated as "BCF") as some or all of the divalent phenol components are suitable for applications where dimensional changes due to water absorption and morphological stability are particularly demanding. It is preferable to use these divalent phenols other than BPA in an amount of 5 mol% or more, particularly 10 mol% or more, of the total divalent phenol components constituting the polycarbonate resin.

[0016] In particular, when high rigidity and better hydrolysis resistance are required, it is especially preferable that component A constituting the resin composition is one of the copolymer polycarbonate resins (1) to (3) below. (1) A copolymer polycarbonate resin in which, of 100 mol% of the divalent phenol component constituting the polycarbonate resin, BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, even more preferably 45 to 65 mol%) and BCF is 20 to 80 mol% (more preferably 25 to 60 mol%, even more preferably 35 to 55 mol%). (2) A copolymer polycarbonate resin in which, of 100 mol% of the divalent phenol component constituting the polycarbonate resin, BPA is 10 to 95 mol% (more preferably 50 to 90 mol%, even more preferably 60 to 85 mol%) and BCF is 5 to 90 mol% (more preferably 10 to 50 mol%, even more preferably 15 to 40 mol%). (3) A copolymer polycarbonate resin in which, of 100 mol% of the divalent phenol component constituting the polycarbonate resin, BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, even more preferably 45 to 65 mol%) and Bis-TMC is 20 to 80 mol% (more preferably 25 to 60 mol%, even more preferably 35 to 55 mol%).

[0017] These special polycarbonate resins may be used individually or mixed in appropriate combinations of two or more types. They can also be mixed with commonly used bisphenol A type polycarbonate resins. The manufacturing methods and properties of these special polycarbonate resins are described in detail in, for example, Japanese Patent Publication No. 6-172508, Japanese Patent Publication No. 8-27370, Japanese Patent Publication No. 2001-55435, and Japanese Patent Publication No. 2002-117580.

[0018] Furthermore, among the various polycarbonate resins mentioned above, those whose copolymerization composition and other properties have been adjusted to bring the water absorption rate and Tg (glass transition temperature) within the following ranges exhibit excellent hydrolysis resistance of the polymer itself, as well as significantly superior low warping after molding. Therefore, they are particularly suitable for fields requiring morphological stability. (i) A polycarbonate resin having a water absorption rate of 0.05 to 0.15%, preferably 0.06 to 0.13%, and a Tg of 120 to 180°C, or (ii) A polycarbonate resin having a Tg of 160 to 250°C, preferably 170 to 230°C, and a water absorption rate of 0.10 to 0.30%, preferably 0.13 to 0.30%, more preferably 0.14 to 0.27%.

[0019] Here, the water absorption rate of the polycarbonate resin was measured using a disc-shaped test piece with a diameter of 45 mm and a thickness of 3.0 mm, after immersion in water at 23°C for 24 hours in accordance with ISO 62-1980. The glass transition temperature (Tg) was determined by differential scanning calorimeter (DSC) measurement in accordance with JIS K7121.

[0020] Carbonyl halides, diester carbonates, or haloformates are used as carbonate precursors, specifically including phosgene, diphenyl carbonate, or dihaloformates of divalent phenols.

[0021] When producing a polycarbonate resin by interfacial polymerization of the divalent phenol and the carbonate precursor, a catalyst, an end-terminating agent, an antioxidant to prevent oxidation of the divalent phenol, etc., may be used as needed. The polycarbonate resin of the present invention also includes a branched polycarbonate resin copolymerized with a trifunctional or polyfunctional aromatic compound, a polyester carbonate resin copolymerized with an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid, a copolymerized polycarbonate resin copolymerized with a bifunctional alcohol (including alicyclic), and a polyester carbonate resin copolymerized with both such bifunctional carboxylic acid and bifunctional alcohol. Furthermore, a mixture of two or more of the obtained polycarbonate resins may also be used.

[0022] Branched polycarbonate resins can impart properties such as drip prevention to the resin composition of the present invention. Examples of trifunctional or polyfunctional aromatic compounds used in such branched polycarbonate resins include phloroglucin, phloroglucides, or 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-2, 2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 4-{4-[1,1-bis(4- Examples include trisphenols such as hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acid chlorides, among which 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred.

[0023] In branched polycarbonate resins, the structural units derived from polyfunctional aromatic compounds are preferably 0.01 to 1 mol%, more preferably 0.05 to 0.9 mol%, and even more preferably 0.05 to 0.8 mol%, of the total 100 mol% of structural units derived from divalent phenols and those derived from such polyfunctional aromatic compounds. Furthermore, especially in the case of melt transesterification, branched structural units may be generated as a side reaction, but the amount of such branched structural units is also preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9 mol%, and even more preferably 0.01 to 0.8 mol%, of the total 100 mol% of structural units derived from divalent phenols. 1 It can be calculated by 1H-NMR measurement.

[0024] Among aliphatic difunctional carboxylic acids, α,ω-dicarboxylic acids are preferred. Examples of aliphatic difunctional carboxylic acids include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanediic acid), dodecanediic acid, tetradecanediic acid, octadecanediic acid, and eicosanedioic acid, as well as alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. As for difunctional alcohols, alicyclic diols are more preferred, with examples including cyclohexanedimethanol, cyclohexanediol, and tricyclodecanedimethanol.

[0025] The reaction methods used in the present invention for producing polycarbonate resin, such as interfacial polymerization, molten transesterification, solid-phase transesterification of carbonate prepolymers, and ring-opening polymerization of cyclic carbonate compounds, are well-known methods described in various literatures and patent publications.

[0026] In producing the thermoplastic resin composition of the present invention, the viscosity-average molecular weight (M) of the polycarbonate resin is not particularly limited, but is preferably 1.8 × 10⁻⁶. 4 ~4.0×10 4 And more preferably 2.0 × 10 4 ~3.5×10 4, more preferably 2.2×10 4 ~3.0×10 4 . When the polycarbonate resin has a viscosity average molecular weight of less than 1.8×10 4 , good mechanical properties may not be obtained. On the other hand, a resin composition obtained from a polycarbonate resin having a viscosity average molecular weight exceeding 4.0×10 4 is inferior in versatility in terms of poor fluidity during injection molding.

[0027] Incidentally, the polycarbonate resin may be obtained by mixing those having a viscosity average molecular weight outside the above range. In particular, a polycarbonate resin having a viscosity average molecular weight exceeding the above range (5×10 4 ) has improved entropy elasticity of the resin. As a result, good molding processability is exhibited in gas-assisted molding and foam molding, which may be used when molding a reinforced resin material into a structural member. Such improvement in molding processability is even better than that of the branched polycarbonate resin. As a more preferred embodiment, component A is a polycarbonate resin A-1-1 component having a viscosity average molecular weight of 7×10 4 ~3×10 5 , and an aromatic polycarbonate resin (A-1-2 component) having a viscosity average molecular weight of 1×10 4 ~3×10 4 , and a polycarbonate resin (A-1 component) having a viscosity average molecular weight of 1.6×10 4 ~3.5×10 4 (hereinafter, may be referred to as "high molecular weight component-containing polycarbonate resin") can also be used.

[0028] In such a high molecular weight component-containing polycarbonate resin (A-1 component), the molecular weight of the A-1-1 component is preferably 7×10 4 ~2×10 5 , more preferably 8×10 4 ~2×10 5 , still more preferably 1×10 5 ~2×10 5 , particularly preferably 1×10 5 ~1.6×10 5The molecular weight of component A-1-1-2 is 1 × 10⁻⁶. 4 ~2.5×10 4 Preferably, and more preferably, 1.1 × 10 4 ~2.4×10 4 More preferably 1.2 × 10 4 ~2.4×10 4 Particularly preferred is 1.2 × 10 4 ~2.3×10 4 That is the case.

[0029] A polycarbonate resin containing high molecular weight components (component A-1) can be obtained by mixing component A-1-1 and component A-1-2 in various proportions and adjusting them to satisfy a predetermined molecular weight range. Preferably, component A-1-1 is 2 to 40% by weight of component A-1 out of 100% by weight of component A-1, more preferably 3 to 30% by weight of component A-1-1, even more preferably 4 to 20% by weight of component A-1-1, and particularly preferably 5 to 20% by weight of component A-1-1.

[0030] Furthermore, methods for preparing component A-1 include (1) a method of independently polymerizing component A-1-1 and component A-1-2 and mixing them; (2) a method of producing an aromatic polycarbonate resin that exhibits multiple polymer peaks in a molecular weight distribution chart by GPC method within the same system, as exemplified by the method shown in Japanese Patent Application Publication No. 5-306336, and producing such an aromatic polycarbonate resin to satisfy the conditions for component A-1 of the present invention; and (3) a method of mixing the aromatic polycarbonate resin obtained by such a production method (production method of (2)) with separately produced component A-1-1 and / or component A-1-2.

[0031] In this invention, the viscosity-average molecular weight is first calculated using the following formula: the specific viscosity (η SP The viscosity of the solution was determined using an Ostwald viscometer from a solution prepared by dissolving 0.7 g of polycarbonate resin in 100 ml of methylene chloride at 20°C. Specific viscosity (η SP ) = (t-t0) / t0 [t0 is the number of seconds for the methylene chloride to fall, and t is the number of seconds for the sample solution to fall.] The specific viscosity (η) SP The viscosity-average molecular weight M is calculated from the following formula. η SP / c=[η]+0.45×[η] 2 c (where [η] is the intrinsic viscosity) [η] = 1.23 × 10 -4 M 0.83 c = 0.7 Furthermore, the viscosity-average molecular weight of the polycarbonate resin in the thermoplastic resin composition of the present invention is calculated in the following manner. Specifically, the composition is mixed with methylene chloride in an amount 20 to 30 times its weight to dissolve the soluble components in the composition. These soluble components are collected by Celite filtration. The solvent is then removed from the resulting solution. The solid after solvent removal is thoroughly dried to obtain a solid of the components that dissolve in methylene chloride. The specific viscosity at 20°C is determined from a solution obtained by dissolving 0.7 g of this solid in 100 ml of methylene chloride in the same manner as above, and the viscosity-average molecular weight M is calculated from this specific viscosity in the same manner as above.

[0032] A polycarbonate-polydiorganosiloxane copolymer resin can also be used as the polycarbonate resin of the present invention. Preferably, the polycarbonate-polydiorganosiloxane copolymer resin is a copolymer resin containing a divalent phenol unit represented by the following general formula (1) and a hydroxyaryl-terminated polydiorganosiloxane unit represented by the following general formula (3).

[0033] [ka]

[0034] [In the above general formula (1), R 1 and R 2Each of the following groups independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. If there are multiple groups, they may be the same or different. a and b are integers from 1 to 4, and W is at least one group selected from the group consisting of a single bond or a group represented by the general formula (2) below.

[0035] [ka]

[0036] (In the above general formula (2), R 11 ,R 12 ,R 13 ,R 14 ,R 15 ,R 16 ,R 17 and R 18 Each of these independently represents a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms, R 19 and R 20 Each of these independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group with 1 to 18 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, a cycloalkyl group with 6 to 20 carbon atoms, a cycloalkoxy group with 6 to 20 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, an aryl group with 6 to 14 carbon atoms, an aryloxy group with 6 to 10 carbon atoms, an aralkyl group with 7 to 20 carbon atoms, an aralkyloxy group with 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. If there are multiple groups, they may be the same or different. c is an integer from 1 to 10, and d is an integer from 4 to 7.

[0037] [ka]

[0038] [In the above general formula (3), R 3 , R 4 , R 5 , R 6 , R 7 and R 8 Each of these is independently a hydrogen atom, a C1-C12 alkyl group, or a C6-C12 substituted or unsubstituted aryl group, R 9 and R 10 Each of the following is independently a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, and an alkoxy group with 1 to 10 carbon atoms; e and f are integers from 1 to 4; p is a natural number; q is 0 or a natural number; and p+q is a natural number between 4 and 150. X is a divalent aliphatic group with 2 to 8 carbon atoms.

[0039] Examples of divalent phenols (I) that derive the carbonate constituent units represented by general formula (1) include 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, and 2,2-bis(4-hydroxy-3 ,3'-biphenyl)propane, 2,2-bis(4-hydroxy-3-isopropylphenyl)propane, 2,2-bis(3-t-butyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, 2,2-bis(3-bromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 1,1-bis(3-cyclohexyl-4- Hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)diphenylmethane, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenyl sulfoxide , 4,4'-dihydroxydiphenyl sulfide, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 2,2'-diphenyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfide, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,Examples include 4-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis(4-hydroxyphenyl)cyclohexane, 1,3-bis(4-hydroxyphenyl)cyclohexane, 4,8-bis(4-hydroxyphenyl)tricyclo[5.2.1.02,6]decane, 4,4'-(1,3-adamantanediyl)diphenol, and 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane.

[0040] Among these, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-sulfonyldiphenol, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, and 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene are preferred, with 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane (BPZ), 4,4'-sulfonyldiphenol, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene being particularly preferred. Among these, 2,2-bis(4-hydroxyphenyl)propane, which has excellent strength and good durability, is the most suitable. These may be used individually or in combination of two or more.

[0041] In the carbonate constituent unit represented by the above general formula (3), R 3 , R 4 , R 5 , R 6 , R 7 and R 8 Each of these is preferably independently a hydrogen atom, a C1-C6 alkyl group, or a C6-C12 substituted or unsubstituted aryl group, with a hydrogen atom, a C1-C6 alkyl group, or a phenyl group being particularly preferred. 9 and R 10Each of these is preferably independently a hydrogen atom and an alkyl group having 1 to 10 carbon atoms, with a hydrogen atom and an alkyl group having 1 to 4 carbon atoms being particularly preferred. As the dihydroxyaryl-terminated polydiorganosiloxane (II) that derives the carbonate structural unit represented by the above general formula (3), for example, compounds such as those shown in the following general formula (I) are preferably used.

[0042] [ka]

[0043] p+q is preferably 4 to 120, more preferably 30 to 120, even more preferably 30 to 100, and most preferably 30 to 60.

[0044] Next, a method for producing the preferred polycarbonate-polydiorganosiloxane copolymer resin described above will be explained below. In advance, a mixed solution of chloroformate compounds containing chloroformate of divalent phenol(I) and / or a divalent phenol(I) carbonate oligomer having terminal chloroformate groups is prepared by reacting divalent phenol(I) with a chloroformate-forming compound such as phosgene or chloroformate of divalent phenol(I) in a mixture of an organic solvent insoluble in water and an alkaline aqueous solution. Phosgene is preferred as the chloroformate-forming compound.

[0045] In producing chloroformate compounds from divalent phenol(I), the entire amount of divalent phenol(I) that derives the carbonate structural unit represented by the above general formula (1) may be used to form the chloroformate compound at once, or a portion of it may be added as a post-added monomer to the subsequent interfacial polycondensation reaction as a reaction material. The post-added monomer is added to expedite the subsequent polycondensation reaction, and does not need to be added if unnecessary. The method of this chloroformate compound production reaction is not particularly limited, but it is generally preferable to carry it out in a solvent in the presence of an acid binder. Furthermore, if desired, small amounts of antioxidants such as sodium sulfite and hydrosulfide may be added, and it is preferable to add them. The proportion of chloroformate-forming compounds used should be adjusted appropriately considering the stoichiometric ratio (equivalent) of the reaction. When using phosgene, which is a suitable chloroformate-forming compound, a method of blowing gasified phosgene into the reaction system can be suitably employed.

[0046] Examples of acid binders include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, or mixtures thereof. The proportion of acid binder used should be determined appropriately, taking into account the stoichiometric ratio (equivalents) of the reaction, as described above. Specifically, it is preferable to use 2 equivalents or a slightly excess amount of acid binder per mole of divalent phenol(I) used to form the chloroformate compound of divalent phenol(I) (usually 1 mole corresponds to 2 equivalents).

[0047] As the aforementioned solvent, various reaction-inert solvents, such as those used in the production of known polycarbonates, can be used individually or as a mixture of solvents. Typical examples include hydrocarbon solvents such as xylene, and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. Halogenated hydrocarbon solvents such as methylene chloride are particularly preferred.

[0048] There are no particular restrictions on the pressure used in the reaction to produce chloroformate compounds; it can be carried out at atmospheric pressure, under pressure, or under reduced pressure, although it is usually advantageous to carry out the reaction at atmospheric pressure. The reaction temperature is selected from the range of -20 to 50°C, and since the reaction is often exothermic, it is desirable to cool the reaction with water or ice. The reaction time depends on other conditions and cannot be specified in general, but it is usually carried out in 0.2 to 10 hours. The pH range for the reaction to produce chloroformate compounds can be determined using known interfacial reaction conditions, and the pH is usually adjusted to 10 or higher.

[0049] In the production of the polycarbonate-polydiorganosiloxane copolymer resin of the present invention, a mixed solution of a chloroformate compound containing a chloroformate of divalent phenol (I) and a carbonate oligomer of divalent phenol (I) having terminal chloroformate groups is prepared in this manner. Then, while stirring the mixed solution, a dihydroxyaryl-terminated polydiorganosiloxane (II), which derives a carbonate structural unit represented by general formula (3), is added at a rate of 0.01 moles / min or less per mole of divalent phenol (I) added during the preparation of the mixed solution, and the dihydroxyaryl-terminated polydiorganosiloxane (II) and the chloroformate compound are interfacially polycondensed to obtain the polycarbonate-polydiorganosiloxane copolymer resin.

[0050] Polycarbonate-polydiorganosiloxane copolymer resins can be made into branched polycarbonate-polydiorganosiloxane copolymer resins by using a branching agent in combination with a divalent phenolic compound. Examples of trifunctional or polyfunctional aromatic compounds used in such branched polycarbonate resins include phloroglucin, phloroglucides, or 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-2, 2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 4-{4-[1,1-bis(4- Examples include trisphenols such as hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acid chlorides, among which 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred.

[0051] The method for producing such branched polycarbonate-polydiorganosiloxane copolymer resin may be either a method in which the branching agent is included in the mixed solution during the chloroformate compound formation reaction, or a method in which the branching agent is added during the interfacial polycondensation reaction after the formation reaction is completed. The proportion of carbonate constituent units derived from the branching agent is preferably 0.005 to 1.5 mol%, more preferably 0.01 to 1.2 mol%, and particularly preferably 0.05 to 1.0 mol%, of the total amount of carbonate constituent units constituting the copolymer resin. 1 It can be calculated by 1H-NMR measurement.

[0052] The pressure in the system in the polycondensation reaction can be any of reduced pressure, normal pressure, or increased pressure, but usually, it can be preferably carried out at normal pressure or at about the self-pressure of the reaction system. The reaction temperature is selected from the range of -20 to 50 °C. Since heat is usually generated during polymerization, it is desirable to carry out water cooling or ice cooling. The reaction time varies depending on other conditions such as the reaction temperature and cannot be generally specified, but usually, it is carried out for 0.5 to 10 hours. In some cases, appropriate physical treatments (such as mixing and fractionation) and / or chemical treatments (such as polymer reactions, crosslinking treatments, and partial decomposition treatments) are applied to the obtained polycarbonate-polydiorganosiloxane copolymer resin to obtain a polycarbonate-polydiorganosiloxane copolymer resin with a desired reduced viscosity [η SP / c]. The obtained reaction product (crude product) can be recovered as a polycarbonate-polydiorganosiloxane copolymer resin with a desired purity (degree of purification) by performing various post-treatments such as known separation and purification methods.

[0053] The content of the polydiorganosiloxane block represented by the following general formula (4) contained in the above general formula (3) is preferably 1.0 to 10.0% by weight, more preferably 1.0 to 8.0% by weight, still more preferably 1.0 to 5.0% by weight, and most preferably 1.0 to 3.0% by weight based on the total weight of the polycarbonate resin composition.

[0054] [Chemical formula]

[0055] (In the above general formula (4), R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, p is a natural number, q is 0 or a natural number, and p + q is a natural number of 4 or more and 150 or less.)

[0056] <Component B: Phosphazene> In the present invention, the thermoplastic resin contains a phosphazene comprising 98.5 mol% or more of a phosphazene cyclic trimer as a constituent component. The phosphazene is not particularly limited as long as it does not contain halogen atoms and has a phosphazene structure in its molecule. The phosphazene structure referred to here is the structure represented by the formula: -P(R2)=N-[wherein R2 is an organic group]. The phosphazene is represented by the general formulas (5) and (6).

[0057] [ka]

[0058] (In the formula, X1, X2, X3, and X4 represent organic groups that do not contain hydrogen, hydroxyl, amino, or halogen atoms. Also, n represents an integer between 3 and 10.) Examples of organic groups that do not contain halogen atoms, as represented by X1, X2, X3, and X4 in formulas (5) and (6) above, include alkoxy groups, phenyl groups, amino groups, and allyl groups.

[0059] The phosphazene component B must contain 98.5 mol% or more of phosphazene cyclic trimers. The content is preferably in the range of 99 mol% to 100 mol%, and more preferably in the range of 99.5 mol% to 100 mol%. If the phosphazene cyclic trimer content is less than 98.5 mol%, the strength retention rate after high-temperature and high-humidity testing decreases. General methods for producing phosphazenes are described in European Patent Publication No. 728811 and International Publication No. 97 / 40092, among others.

[0060] During the manufacturing process, phosphazene produces cyclic tetramers and higher-grade oligomers as by-products in addition to cyclic trimers. However, the content of phosphazene cyclic trimers can be increased by purification using methods such as column chromatography.

[0061] Furthermore, the content of phosphazene cyclic trimers in phosphazene is 31It can be quantified by PNMR (chemical shift, δ trimer 6.5 to 10.0 ppm, δ tetramer -10 to -13.5 ppm, δ higher oligomers -16.5 to -25.0 ppm).

[0062] The content of component B is 1 to 30 parts by weight, preferably 3 to 25 parts by weight, and more preferably 5 to 20 parts by weight in 100 parts by weight of the total amount of component A and component B. If the content of component B is less than 1 part by weight, the flame retardant effect cannot be obtained, and if it exceeds 30 parts by weight, the strength retention rate after the high temperature and high humidity test decreases.

[0063] <Component C: Adhesion improver> The adhesion improver preferably used as component C of the present invention is a compound that improves the adhesion between component A and component B. Among them, an organic compound having at least one functional group selected from the group consisting of an epoxy group, a carboxylic acid group, and an acid anhydride group in one molecule is preferably used.

[0064] In the present invention, in order to significantly exhibit the bending strength, interlaminar shear strength, and long-term durability improvement effects, which are the effects of the present invention, it is preferable to contain the above organic compound. By blending the above organic compound in the resin composition, the adhesion between component A and component B can be strengthened, and thereby the bending strength, interlaminar shear strength, and long-term durability improvement effects are significantly exhibited. The epoxy group-containing compound is not particularly limited as long as it is an organic compound containing an epoxy group, and examples thereof include phenoxy resin and epoxy resin. Examples of the phenoxy resin include, for example, the phenoxy resin represented by the following general formula (7).

[0065] [Chemical formula]

[0066] (In the formula, X is at least one group selected from the group consisting of the groups represented by the following general formula (8), Y is a hydrogen atom or a residue of a compound that reacts with a hydroxyl group, and n is an integer of 0 or more.)

[0067] [ka]

[0068] (In the formula, Ph represents a phenyl group.) In the above general formula (7), examples of compounds that react with the hydroxyl group include compounds having esters, carbonates, epoxy groups, carboxylic acid anhydrides, acid halides, isocyanate groups, etc. Among esters, intramolecular esters are particularly preferred, such as caprolactone. In the phenoxy resin represented by the above general formula (7), the compound in which Y is a hydrogen atom can be easily produced from divalent phenols and epichlorohydrin. Furthermore, the compound in which Y is a residue of the compound that reacts with the hydroxyl group can be easily produced by mixing the phenoxy resin produced from divalent phenols and epichlorohydrin with the compound that reacts with the hydroxyl group under heating. In particular, bisphenol A type phenoxy resin using bisphenol A as the divalent phenol is preferred. Furthermore, examples of epoxy resins include epoxy resins represented by the following general formula (9).

[0069] [ka]

[0070] (In the equation, X and n are the same as in equation (7).) The epoxy resin represented by the above general formula (9) can be easily produced from divalent phenols and epichlorohydrin. Suitable divalent phenols include bisphenol A type epoxy resins such as 2,2-bis(4-hydroxyphenyl)propane [bisphenol A], 1,1-bis(4-hydroxyphenyl)ethane, or 4,4'-dihydroxybiphenyl. Bisphenol A type epoxy resins are particularly preferred.

[0071] Commercially available phenoxy resins and epoxy resins can also be used. Examples of commercially available phenoxy resins (bisphenol A type) include PKHB (manufactured by Gabriel Phenoxies, Mw=32,000), PKHH (manufactured by Gabriel Phenoxies, Mw=52,000), and PKFE (manufactured by Gabriel Phenoxies, Mw=60,000). Examples of commercially available epoxy resins (bisphenol A type) include jER1256 (manufactured by Mitsubishi Chemical Corporation, Mw=50,000).

[0072] The weight-average molecular weight of phenoxy resins and epoxy resins is not particularly limited, but is usually 5,000 to 100,000, preferably 8,000 to 80,000, and more preferably 10,000 to 50,000. When the weight-average molecular weight is in the range of 5,000 to 100,000, the mechanical properties are particularly good.

[0073] As for the carboxylic acid group-containing compound, there are no particular restrictions as long as it is an organic compound containing a carboxylic acid group. However, from the viewpoint of resistance to flame retardants, heat resistance, and compatibility with component A, aromatic polyester resins such as polybutylene terephthalate, polyethylene terephthalate, and polyarylate are preferred, and polybutylene terephthalate is most preferably used due to its excellent impregnation properties into component B.

[0074] The aromatic polybutylene terephthalate resin and aromatic polyethylene terephthalate resin that are suitably used in the present invention are preferably aromatic polyester resins in which, of the dicarboxylic acid and diol components forming the polyester, 70 mol% or more of the dicarboxylic acid component (100 mol%) is aromatic dicarboxylic acid, more preferably 90 mol% or more, and most preferably 99 mol% or more is aromatic dicarboxylic acid. Examples of these dicarboxylic acids include terephthalic acid, isophthalic acid, adipic acid, 2-chloroterephthalic acid, 2,5-dichloroterephthalic acid, 2-methylterephthalic acid, 4,4-stilbenidicarboxylic acid, 4,4-biphenyldicarboxylic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, bisbenzoic acid, bis(p-carboxyphenyl)methane, anthracenedicarboxylic acid, 4,4-diphenyletherdicarboxylic acid, 4,4-diphenoxyethanedicarboxylic acid, 5-Na sulfisoisophthalic acid, ethylene-bis-p-benzoic acid, and the like. These dicarboxylic acids can be used individually or in combination of two or more. In addition to the aromatic dicarboxylic acids mentioned above, the aromatic polyester resin of the present invention can be copolymerized with less than 30 mol% of aliphatic dicarboxylic acid components. Specific examples include adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid. Examples of the diol components of the present invention include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, trans- or cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, decamethylene glycol, cyclohexanediol, p-xylenediol, bisphenol A, tetrabromobisphenol A, and tetrabromobisphenol A-bis(2-hydroxyethyl ether). These can be used individually or in combination of two or more.Furthermore, it is preferable that the divalent phenol content in the diol component be 30 mol% or less.

[0075] The method for producing the aromatic polybutylene terephthalate resin and aromatic polyethylene terephthalate resin used in the present invention is carried out by conventional methods, in which the dicarboxylic acid component and the diol component are polymerized while heating in the presence of a polycondensation catalyst containing titanium, germanium, antimony, etc., and the by-product water or lower alcohol is discharged from the system. For example, germanium-based polymerization catalysts include germanium oxides, hydroxides, halides, alcoholates, phenolates, etc., and more specifically, germanium oxide, germanium hydroxide, germanium tetrachloride, tetramethoxygermanium, etc. In addition, the present invention can also use compounds such as manganese, zinc, calcium, and magnesium, which are used in the transesterification reaction that is a known precursor to polycondensation, and it is also possible to deactivate such catalysts with a phosphoric acid or phosphorous acid compound, etc. after the completion of the transesterification reaction and then perform polycondensation. Furthermore, the method for producing the aromatic polybutylene terephthalate resin and aromatic polyethylene terephthalate resin can be either a batch method or a continuous polymerization method.

[0076] The molecular weight of the aromatic polybutylene terephthalate resin and aromatic polyethylene terephthalate resin of the present invention is not particularly limited, but it is preferably 0.4 to 1.5, and particularly preferably 0.5 to 1.2, intrinsic viscosity measured at 25°C with o-chlorophenol as the solvent.

[0077] Furthermore, the amount of terminal carboxyl groups in the aromatic polybutylene terephthalate resin and aromatic polyethylene terephthalate resin used in the present invention is preferably 5 to 75 eq / ton, more preferably 5 to 70 eq / ton, and even more preferably 7 to 65 eq / ton.

[0078] The aromatic polyarylate resins preferably used in the present invention are those obtained from aromatic dicarboxylic acids or their derivatives and divalent phenols or their derivatives. The aromatic dicarboxylic acids used in the preparation of the polyarylate can be any that react with divalent phenols to give a satisfactory polymer, and one or more types can be used in combination.

[0079] Preferred aromatic dicarboxylic acid components include terephthalic acid and isophthalic acid. Mixtures thereof may also be used.

[0080] Specific examples of divalent phenol components include 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenylmethane, 2,2'-bis(4-hydroxy-3,5-dimethylphenyl)propane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 4,4'-dihydroxydiphenyl, and hydroquinone. These divalent phenol components are para-substituted compounds, but other isomers may also be used, and ethylene glycol, propylene glycol, neopentyl glycol, etc. may be used in combination with the divalent phenol components.

[0081] Among the above, a preferred polyarylate resin is one in which the aromatic dicarboxylic acid component consists of terephthalic acid and isophthalic acid, and the divalent phenol component consists of 2,2-bis(4-hydroxyphenyl)propane (bisphenol A). The ratio of terephthalic acid to isophthalic acid is preferably terephthalic acid / isophthalic acid = 9 / 1 to 1 / 9 (molar ratio), and in particular, 7 / 3 to 3 / 7 is desirable in terms of melt processability and performance balance.

[0082] Other representative polyarylate resins include those in which the aromatic dicarboxylic acid component is terephthalic acid and the divalent phenol component is bisphenol A and hydroquinone. The ratio of bisphenol A to hydroquinone is preferably bisphenol A / hydroquinone = 50 / 50 to 70 / 30 (molar ratio), more preferably 55 / 45 to 70 / 30, and even more preferably 60 / 40 to 70 / 30.

[0083] In this invention, the viscosity-average molecular weight of the polyarylate resin is preferably in the range of approximately 7,000 to 100,000, considering its physical properties and extrusion processability. Furthermore, the polyarylate resin can be polymerized using either the interfacial polycondensation method or the transesterification reaction method.

[0084] Examples of acid anhydride group-containing compounds include maleic acid resins such as the Marquid series (maleic acid resin, manufactured by Arakawa Chemical Co., Ltd.), the Alastor series (styrene-maleic acid resin, manufactured by Arakawa Chemical Co., Ltd.), and the Isoban series (isobutylene-maleic anhydride block copolymer, manufactured by Kuraray Co., Ltd.). From the viewpoint of heat resistance and compatibility with component A, styrene-maleic acid resin is most preferably used.

[0085] The content of component C is preferably 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight, and even more preferably 1 to 5 parts by weight, based on 100 parts by weight of the total amount of components A and B. If the content of component C is less than 1 part by weight, excellent bending strength, interlaminar shear strength, and long-term durability may not be obtained. If it exceeds 20 parts by weight, heat resistance will be impaired, which may reduce flame retardancy and long-term durability.

[0086] (Other ingredients) Various additives can be incorporated into the resin composition of the present invention, provided that they do not impair the effects of the present invention. Examples of such additives include phosphorus-based heat stabilizers, phenol-based heat stabilizers, sulfur-containing antioxidants, mold release agents, ultraviolet absorbers, hindered amine-based light stabilizers, flame retardants other than the phosphazenes mentioned above, and dyes and pigments. These additives will be described in detail below.

[0087] (Phosphorus-based heat stabilizer) As phosphorus-based stabilizers, phosphite compounds, phosphonite compounds, and phosphate compounds can all be used.

[0088] Various phosphite compounds can be used. Specifically, examples include the phosphite compound represented by the following general formula

[10] , the phosphite compound represented by the following general formula

[11] , and the phosphite compound represented by the following general formula

[12] .

[0089] [ka]

[0090] [R in the formula 31 This represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkaryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a halo, alkylthio (alkyl groups having 1 to 30 carbon atoms) or hydroxy substituent, and three R 31 These can be selected as either identical or different from each other, and a cyclic structure can also be selected by derivation from divalent phenols.

[0091] [ka]

[0092] [R in the formula 32 , R 33 Each of these represents a hydrogen atom, a C1-C20 alkyl group, a C6-C20 aryl group, a C6-C20 alkylaryl group, a C7-C30 aralkyl group, a C4-C20 cycloalkyl group, and a C15-C25 2-(4-oxyphenyl)propyl-substituted aryl group. Note that the cycloalkyl group and aryl group can be either unsubstituted with an alkyl group or substituted with an alkyl group.

[0093] [ka]

[0094] [R in the formula 34 , R 35 R is an alkyl group having 12 to 15 carbon atoms. 34 and R 35 They can be either identical or different to each other. Examples of phosphonite compounds include those represented by the following general formula

[13] and those represented by the following general formula

[14] .

[0095] [ka]

[0096] [In the formula, Ar 1 Ar 2 This represents an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 6 to 20 carbon atoms, or a 2-(4-oxyphenyl)propyl-substituted aryl group having 15 to 25 carbon atoms, and four Ar 1 They can be either identical or different from each other. Or two Ar 2 They can be either identical or different from each other.

[0097] Preferred specific examples of the phosphite compound represented by the above general formula

[10] include diphenylisooctyl phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, diphenyl mono(tridecyl) phosphite, phenyldiisodecyl phosphite, and phenyldi(tridecyl) phosphite.

[0098] Preferred specific examples of the phosphite compound represented by the above general formula

[11] include distearyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, and dicyclohexyl pentaerythritol diphosphite. Preferably, distearyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, and bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite can be used. One or more of these phosphite compounds can be used in combination.

[0099] A preferred specific example of the phosphite compound represented by the above general formula

[12] is 4,4'-isopropylidenediphenoltetratridecylphosphite.

[0100] Preferred specific examples of the phosphonite compound represented by the above general formula

[13] include tetrakis(2,4-di-iso-propylphenyl)-4,4'-biphenylenediphosphonite, tetrakis(2,4-di-n-butylphenyl)-4,4'-biphenylenediphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylenediphosphonite, and tetrakis(2,4-di-tert-butylphenyl)-3,3' Examples include biphenylenediphosphonite, tetrakis(2,6-di-iso-propylphenyl)-4,4'-biphenylenediphosphonite, tetrakis(2,6-di-n-butylphenyl)-4,4'-biphenylenediphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,3'-biphenylenediphosphonite, and tetrakis(2,6-di-tert-butylphenyl)-3,3'-biphenylenediphosphonite. Among these, tetrakis(di-tert-butylphenyl)-biphenylenediphosphonite is preferred, and tetrakis(2,4-di-tert-butylphenyl)-biphenylenediphosphonite is more preferred. A mixture of two or more of these tetrakis(2,4-di-tert-butylphenyl)-biphenylenediphosphonites is preferred. Specifically, one or more of tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylenediphosphonite, and tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylenediphosphonite can be used in combination, but a mixture of these three is preferred.

[0101] Preferred specific examples of the phosphonite compound represented by the above general formula

[14] include bis(2,4-di-iso-propylphenyl)-4-phenyl-phenylphosphonite, bis(2,4-di-n-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,4-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, bis(2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6-di-iso-propylphenyl)-4-phenyl-phenylphosphonite, bis(2,6-di-n-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, and bis(2,6-di-tert-butylphenyl)-3-phenyl-phenylphosphonite. Bis(di-tert-butylphenyl)-phenyl-phenylphosphonite is preferred, and bis(2,4-di-tert-butylphenyl)-phenyl-phenylphosphonite is more preferred.

[0102] This bis(2,4-di-tert-butylphenyl)-phenyl-phenylphosphonite is preferably a mixture of two or more types. Specifically, one or two types of bis(2,4-di-tert-butylphenyl)-4-phenyl-phenylphosphonite and bis(2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonite can be used in combination. A mixture of such two types is preferred. In the case of a mixture of two types, the mixing ratio is preferably in the range of 5:1 to 4 by weight, and more preferably in the range of 5:2 to 3.

[0103] On the other hand, examples of phosphate compounds include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, and diisopropyl phosphate. Trimethyl phosphate is preferred.

[0104] Among the above phosphorus-containing heat stabilizers, more preferable compounds include compounds represented by the following general formulas

[15] and

[16] .

[0105] [Chemical formula]

[0106] [In formula

[15] , R 36 and R 37 each independently represent an alkyl group, cycloalkyl group, aryl group or aralkyl group having 1 to 12 carbon atoms.]

[0107] [Chemical formula]

[0108] [In formula

[16] , R 41 , R 42 , R 43 , R 44 , R 47 , R 48 and R 49 each independently represent a hydrogen atom, an alkyl group, cycloalkyl group, aryl group or aralkyl group having 1 to 12 carbon atoms, R 45 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 46 represents a hydrogen atom or a methyl group.]

[0109] In formula

[15] , R 36 and R 37 are preferably alkyl groups having 1 to 12 carbon atoms, more preferably alkyl groups having 1 to 8 carbon atoms. Examples of compounds represented by formula

[15] include tris(dimethylphenyl) phosphite, tris(diethylphenyl) phosphite, tris(di-iso-propylphenyl) phosphite, tris(di-n-butylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris(2,6-di-tert-butylphenyl) phosphite, and tris(2,6-di-tert-butylphenyl) phosphite. Tris(2,6-di-tert-butylphenyl) phosphite is particularly preferred.

[0110] Specific examples of compounds represented by formula

[16] include phosphites derived from 2,2'-methylenebis(4,6-di-tert-butylphenol) and 2,6-di-tert-butylphenol, and phosphites derived from 2,2'-methylenebis(4,6-di-tert-butylphenol) and phenol. Phosphates derived from 2,2'-methylenebis(4,6-di-tert-butylphenol) and phenol are particularly preferred.

[0111] The content of the phosphorus-based heat stabilizer is preferably 0.001 to 3.0 parts by weight, more preferably 0.01 to 2.0 parts by weight, and even more preferably 0.05 to 1.0 parts by weight, based on 100 parts by weight of the total of components A and B. If the content of the phosphorus-based heat stabilizer is less than 0.001 parts by weight, the mechanical properties will not be sufficiently expressed, and even if it exceeds 3.0 parts by weight, the mechanical properties may not be sufficiently expressed.

[0112] (Phenol-based heat stabilizer) Examples of phenolic stabilizers include hindered phenols, semi-hindered phenols, and less-hindered phenol compounds. Hindered phenol compounds are particularly preferred for providing heat-stable formulations for polycarbonate resins.

[0113] Examples of such hindered phenol compounds include, for example, vitamin E, n-octadecyl-β-(4'-hydroxy-3',5'-di-tert-butylphenyl)propionate, 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, 2,6-di-tert-butyl-4-(N,N-dimethylaminomethyl)phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, and 2,2'-methylenebis(4-methylphenylmethyl)phenol. 4,4'-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-dimethylenebis(6-α-methyl-benzyl-p-cresol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 2,2'-butylidenebis(4-methyl-6-tert-butylphenol), 4,4'-butylidenebis(3-methyl (Tyl-6-tert-butylphenol), triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, bis[2-tert-butyl-4-methyl6-(3-tert-butyl-5-methyl-2-hydroxybenzyl)phenyl]terephthalate, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyl oxy ]-1,1,-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, 4,4'-thiobis(6-tert-butyl-m-cresol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-thiobis(4-methyl-6-tert-butylphenol), bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4'-di-thiobis(2,6-di-tert-butylphenol), 4,4'-tri-thiobis(2,6-di-tert-butylphenol), 2,4-Bis(n-octylthio)-6-(4-hydroxy-3',5'-di-tert-butylanilino)-1,3,5-triazine, N,N'-Hexamethylenebis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N,N'-Bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, 1,1,3-Tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-Trimethyl-2,4,6-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, Tri Examples include (3,5-di-tert-butyl-4-hydroxyphenyl) isocyanurate, tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris-2[3(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl isocyanurate, and tetrakis[methylene-3-(3',5'-di-tert-butyl-4-hydroxyphenyl)propionate]methane. These can be preferably used.

[0114] More preferably, n-octadecyl-β-(4'-hydroxy-3',5'-di-tert-butylphenyl)propionate, 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1,-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, and tetrakis[methylene-3-(3',5'-di-tert-butyl-4-hydroxyphenyl)propionate]methane. Furthermore, n-octadecyl-β-(4'-hydroxy-3',5'-di-tert-butylphenyl)propionate is preferred.

[0115] (Sulfur-containing antioxidant) Sulfur-containing antioxidants can also be used as antioxidants in polycarbonate resin compositions. This is particularly suitable when the resin composition is used for rotational molding or compression molding. Specific examples of such sulfur-containing antioxidants include dilauryl-3,3'-thiodipropionate, ditridecyl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, laurylstearyl-3,3'-thiodipropionate, pentaerythritol tetra(β-laurylthiopropionate) ester, bis[2-methyl-4-(3-laurylthiopropionyloxy)-5-tert-butylphenyl] sulfide, octadecyl disulfide, mercaptobenzimidazole, 2-mercapto-6-methylbenzimidazole, and 1,1'-thiobis(2-naphthol). More preferably, pentaerythritol tetra(β-laurylthiopropionate) ester can be used.

[0116] The phosphorus-based stabilizers, phenol-based stabilizers, and sulfur-containing antioxidants listed above can each be used individually or in combination of two or more. The content of the phenol-based stabilizer and sulfur-containing antioxidant is preferably 0.0001 to 1 part by weight, more preferably 0.0005 to 0.5 parts by weight, and even more preferably 0.001 to 0.2 parts by weight, per 100 parts by weight of the total of components A and B.

[0117] (Flame retardant: Flame retardants other than phosphazene) The resin composition of the present invention can be given flame retardancy by incorporating a flame retardant. Various compounds conventionally known as flame retardants for thermoplastic resins can be used as such flame retardants, but more preferably, (i) halogen-based flame retardants (e.g., brominated polycarbonate compounds), (ii) phosphorus-based flame retardants (e.g., monophosphate compounds, phosphate oligomer compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, phosphonic acid amide compounds, and phosphazene compounds), (iii) metal salt-based flame retardants (e.g., alkali (earth) metal salts of organic sulfonic acid, metal salt-based flame retardants of borate, and metal salt-based flame retardants of stainate), and (iv) silicone-based flame retardants consisting of silicone compounds. Furthermore, the incorporation of compounds used as flame retardants not only improves flame retardancy but also brings about improvements in properties such as antistatic properties, fluidity, rigidity, and thermal stability, depending on the properties of each compound.

[0118] The flame retardant content is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 25 parts by weight, and even more preferably 0.08 to 20 parts by weight, based on 100 parts by weight of the total of components A and B. If the flame retardant content is less than 0.01 parts by weight, sufficient flame retardancy may not be obtained, and if it exceeds 30 parts by weight, there may be a significant decrease in interlaminar shear strength and strength retention rate after high temperature and high humidity tests.

[0119] (Drip prevention agent) The resin composition of the present invention can be given flame retardancy by incorporating a drip inhibitor. By including this drip inhibitor, good flame retardancy can be achieved without impairing the physical properties of the molded product.

[0120] Examples of drip inhibitors include fluorine-containing polymers having fibril-forming ability, such as polytetrafluoroethylene, tetrafluoroethylene copolymers (e.g., tetrafluoroethylene / hexafluoropropylene copolymer, etc.), partially fluorinated polymers as described in U.S. Patent No. 4,379,910, and polycarbonate resins produced from fluorinated diphenols. Among these, polytetrafluoroethylene (hereinafter sometimes referred to as PTFE) is preferred.

[0121] PTFE with fibril-forming ability has an extremely high molecular weight and tends to bond with other PTFE materials to form fibers under external forces such as shear force. Its molecular weight, calculated from the standard specific gravity, is 1 million to 10 million, preferably 2 million to 9 million. Such PTFE can be used in solid form as well as aqueous dispersion form. Furthermore, to improve dispersibility in resins and to obtain even better flame retardancy and mechanical properties, it is also possible to use PTFE mixtures in mixed form with other resins.

[0122] Examples of commercially available PTFE products with such fibril-forming ability include Teflon® 6J from Mitsui DuPont Fluorochemicals Co., Ltd., and Polyflon MPA FA500 and F-201L from Daikin Industries, Ltd. Representative examples of commercially available aqueous dispersions of PTFE include Fluon AD-1 and AD-936 from Asahi ICI Fluoropolymers Co., Ltd., Fluon D-1 and D-2 from Daikin Industries, Ltd., and Teflon® 30J from Mitsui DuPont Fluorochemicals Co., Ltd.

[0123] As for PTFE in mixed form, (1) a method of mixing an aqueous dispersion of PTFE with an aqueous dispersion or solution of an organic polymer and co-precipitating to obtain a co-aggregated mixture (methods described in Japanese Patent Publication No. 60-258263, Japanese Patent Publication No. 63-154744, etc.), (2) a method of mixing an aqueous dispersion of PTFE with dried organic polymer particles (method described in Japanese Patent Publication No. 4-272957), (3) a method of uniformly mixing an aqueous dispersion of PTFE with an organic polymer particle solution and separating each medium from the mixture. (1) A method of removing the organic polymer (as described in Japanese Patent Publication No. 06-220210, Japanese Patent Publication No. 08-188653, etc.), (2) a method of polymerizing monomers that form an organic polymer in an aqueous dispersion of PTFE (as described in Japanese Patent Publication No. 9-95583), and (3) a method of uniformly mixing an aqueous dispersion of PTFE and an organic polymer dispersion, further polymerizing vinyl monomers in the mixed dispersion, and then obtaining a mixture (as described in Japanese Patent Publication No. 11-29679, etc.) can be used. Examples of commercially available PTFE in these mixed forms include "Metablen A3800" (product name) from Mitsubishi Chemical Corporation and "BLENDEX B449" (product name) from GE Specialty Chemicals.

[0124] In the mixed form, the proportion of PTFE is preferably 1 to 60% by weight, and more preferably 5 to 55% by weight, of 100% by weight of the PTFE mixture. When the proportion of PTFE is within this range, good dispersibility of PTFE can sometimes be achieved. Note that the proportion of component F above indicates the net amount of drip inhibitor, and in the case of PTFE in mixed form, it indicates the net amount of PTFE.

[0125] The amount of drip inhibitor is preferably 0.05 to 2 parts by weight, more preferably 0.1 to 1.5 parts by weight, and even more preferably 0.2 to 1 part by weight, based on 100 parts by weight of the total of components A and B. If the amount of drip inhibitor is less than 0.05 parts by weight, sufficient flame retardancy cannot be obtained, and if it exceeds 2 parts by weight, the interlaminar shear strength may decrease.

[0126] Furthermore, examples of styrene monomers used in organic polymers used in polytetrafluoroethylene mixtures include, but are not limited to, styrenes that may be substituted with one or more groups selected from the group consisting of C1-C6 alkyl groups, C1-C6 alkoxy groups, and halogens, such as ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, dimethylstyrene, ethylstyrene, para-tert-butylstyrene, methoxystyrene, fluorostyrene, monobromostyrene, dibromostyrene, and tribromostyrene, vinylxylene, and vinylnaphthalene. The styrene monomers can be used individually or in mixtures of two or more types.

[0127] The acrylic monomers used in organic polymers used in polytetrafluoroethylene mixtures include substituted (meth)acrylate derivatives. Specifically, the acrylic monomers include (meth)acrylate derivatives that may be substituted with one or more groups selected from the group consisting of C1-C20 alkyl groups, C3-C8 cycloalkyl groups, aryl groups, and glycidyl groups, for example, (meth)acrylonitrile, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl ( Examples of acrylic monomers include, but are not limited to, meth)acrylate, cyclohexyl(meth)acrylate, octyl(meth)acrylate, dodecyl(meth)acrylate, phenyl(meth)acrylate, benzyl(meth)acrylate, and glycidyl(meth)acrylate, maleimides which may be substituted with C1-C6 alkyl groups or aryl groups, such as maleimide, N-methyl-maleimide, and N-phenyl-maleimide, maleic acid, phthalic acid, and itaconic acid. The acrylic monomers can be used individually or in combination of two or more types. Among these, (meth)acrylonitrile is preferred.

[0128] The amount of acrylic monomer-derived units in the organic polymer used in the coating layer is preferably 8 to 11 parts by weight, more preferably 8 to 10 parts by weight, and even more preferably 8 to 9 parts by weight, per 100 parts by weight of styrene monomer-derived units. If the amount of acrylic monomer-derived units is less than 8 parts by weight, the coating strength may decrease, and if it is more than 11 parts by weight, the surface appearance of the molded product may deteriorate.

[0129] The polytetrafluoroethylene mixture preferably has a residual moisture content of 0.5% by weight or less, more preferably 0.2 to 0.4% by weight, and even more preferably 0.1 to 0.3% by weight. A residual moisture content greater than 0.5% by weight may adversely affect flame retardancy.

[0130] The manufacturing process for polytetrafluoroethylene-based mixtures includes a step of forming a coating layer on the outside of branched polytetrafluoroethylene containing one or more monomers selected from the group consisting of styrene monomers and acrylic monomers, in the presence of an initiator. Furthermore, it is preferable to include a step of drying after the coating layer formation step so that the residual moisture content is 0.5% by weight or less, preferably 0.2 to 0.4% by weight, and more preferably 0.1 to 0.3% by weight. The drying step can be carried out using, for example, an art-known method such as hot air drying or vacuum drying.

[0131] The initiator used in the polytetrafluoroethylene mixture can be any initiator used in polymerization reactions of styrene and / or acrylic monomers, without limitation. Examples of such initiators include, but are not limited to, cumyl hydroperoxide, di-tert-butyl peroxide, benzoyl peroxide, hydrogen peroxide, and potassium peroxide. One or more of the above initiators can be used in the polytetrafluoroethylene mixture of the present invention, depending on the reaction conditions. The amount of the initiator can be freely selected within a range that takes into account the amount of polytetrafluoroethylene and the type / amount of monomers, and it is preferable to use 0.15 to 0.25 parts by weight based on the total amount of the composition.

[0132] The polytetrafluoroethylene mixture was manufactured by suspension polymerization using the following procedure. First, water and branched polytetrafluoroethylene dispersion (solid concentration: 60%, polytetrafluoroethylene particle size: 0.15-0.3 μm) were added to a reactor. Acrylic monomer, styrene monomer, and cumene hydroperoxide as a water-soluble initiator were added while stirring, and the reaction was carried out at 80-90°C for 9 hours. After the reaction was complete, water was removed by centrifugation for 30 minutes to obtain a paste-like product. The paste was then dried in a hot air dryer at 80-100°C for 8 hours. The dried product was then pulverized to obtain the polytetrafluoroethylene-based mixture of the present invention.

[0133] This suspension polymerization method does not require the emulsion dispersion polymerization step exemplified in emulsion polymerization methods such as Patent No. 3469391, and therefore does not require emulsifiers or electrolyte salts for coagulating and precipitating the polymerized latex. Furthermore, in polytetrafluoroethylene mixtures produced by emulsion polymerization, emulsifiers and electrolyte salts tend to be mixed in the mixture and are difficult to remove, making it difficult to reduce the sodium and potassium ions derived from such emulsifiers and electrolyte salts. Since the polytetrafluoroethylene mixture used in the present invention is produced by suspension polymerization, such emulsifiers and electrolyte salts are not used, thus reducing the sodium and potassium ion content in the mixture and improving thermal stability and hydrolysis resistance.

[0134] Furthermore, coated branched PTFE can be used as a drip-preventing agent. Coated branched PTFE is a polytetrafluoroethylene mixture consisting of branched polytetrafluoroethylene particles and an organic polymer, and has a coating layer on the outside of the branched polytetrafluoroethylene consisting of an organic polymer, preferably a polymer containing styrene monomer-derived units and / or acrylic monomer-derived units. The coating layer is formed on the surface of the branched polytetrafluoroethylene. It is also preferable that the coating layer contains a copolymer of styrene monomers and acrylic monomers.

[0135] The polytetrafluoroethylene contained in coated branched PTFE is branched polytetrafluoroethylene. If the contained polytetrafluoroethylene is not branched polytetrafluoroethylene, the anti-dropping effect will be insufficient when the amount of polytetrafluoroethylene added is small. Branched polytetrafluoroethylene is particulate and preferably has a particle size of 0.1 to 0.6 μm, more preferably 0.3 to 0.5 μm, and even more preferably 0.3 to 0.4 μm. When the particle size is smaller than 0.1 μm, the surface appearance of the molded product is excellent, but it is difficult to commercially obtain polytetrafluoroethylene with a particle size smaller than 0.1 μm. Also, when the particle size is larger than 0.6 μm, the surface appearance of the molded product may be poor. The number average molecular weight of polytetrafluoroethylene is 1 × 10⁻⁶ 4 ~1 × 10 7 Preferably, 2 × 10 6 ~9×10 6 Generally, polytetrafluoroethylenes with higher molecular weights are more preferable in terms of stability. They can be used in either powder or dispersion form. The branched polytetrafluoroethylene content in coated branched PTFE is preferably 20 to 60 parts by weight, more preferably 40 to 55 parts by weight, even more preferably 47 to 53 parts by weight, particularly preferably 48 to 52 parts by weight, and most preferably 49 to 51 parts by weight, per 100 parts by weight of the total weight of coated branched PTFE. When the proportion of branched polytetrafluoroethylene is within this range, good dispersibility of the branched polytetrafluoroethylene can sometimes be achieved.

[0136] (Release agent) The resin composition of the present invention may further contain a mold release agent for the purpose of improving productivity during molding and reducing distortion of molded products. Known mold release agents can be used.

[0137] Examples include saturated fatty acid esters, unsaturated fatty acid esters, polyolefin waxes (such as polyethylene wax and 1-alkene polymers; those modified with functional group-containing compounds such as acid modification can also be used), silicone compounds, fluorine compounds (such as fluorine oils represented by polyfluoroalkyl ethers), paraffin wax, and beeswax.

[0138] Among preferred release agents are fatty acid esters. Such fatty acid esters are esters of aliphatic alcohols and aliphatic carboxylic acids. Such aliphatic alcohols may be monohydric alcohols or polyhydric alcohols of two or more hydric values. The number of carbon atoms in the alcohol is preferably in the range of 3 to 32, and more preferably in the range of 5 to 30.

[0139] Examples of such monohydric alcohols include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, ceryl alcohol, and triacontanol.

[0140] Examples of such polyhydric alcohols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerols (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol. Polyhydric alcohols are more preferred in fatty acid esters. On the other hand, aliphatic carboxylic acids are preferably those having 3 to 32 carbon atoms, and particularly preferably those having 10 to 22 carbon atoms.

[0141] Examples of the aliphatic carboxylic acid include saturated aliphatic carboxylic acids such as decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, behenic acid, eicosanic acid, and docosanic acid, as well as unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and cetoleic acid. Among the above, aliphatic carboxylic acids having 14 to 20 carbon atoms are preferred. Saturated aliphatic carboxylic acids are particularly preferred. Stearic acid and palmitic acid are especially preferred.

[0142] The above-mentioned aliphatic carboxylic acids, such as stearic acid and palmitic acid, are usually produced from natural oils and fats, such as animal fats and fats, represented by beef tallow and lard, and vegetable oils, represented by palm oil and sunflower oil. Therefore, these aliphatic carboxylic acids are usually mixtures containing other carboxylic acid components with different numbers of carbon atoms. Accordingly, in the production of fatty acid esters of the present invention, aliphatic carboxylic acids produced from such natural oils and fats, and in the form of mixtures containing other carboxylic acid components, particularly stearic acid and palmitic acid, are preferably used.

[0143] The fatty acid ester may be either a partial ester or a full ester. However, since partial esters usually have a high hydroxyl value and tend to induce resin decomposition at high temperatures, full esters are more preferable. The acid value of the fatty acid ester is preferably 20 or less, more preferably in the range of 4 to 20, and even more preferably in the range of 4 to 12, from the viewpoint of thermal stability. The acid value can be substantially 0. Furthermore, the hydroxyl value of the fatty acid ester is more preferably in the range of 0.1 to 30. Furthermore, the iodine value is preferably 10 or less. The iodine value can be substantially 0. These properties can be determined by the method specified in JIS K 0070.

[0144] The amount of release agent is preferably 0.005 to 2 parts by weight, more preferably 0.01 to 1 part by weight, and even more preferably 0.05 to 0.5 parts by weight, based on 100 parts by weight of the total of components A and B.

[0145] (UV absorber) The resin composition of the present invention may contain an ultraviolet absorber. Examples of benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-bendyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydridebenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium sulfoxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

[0146] Benzotriazole derivatives include, for example, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazole-2-yl)phenol], 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, and 2-(2-hydroxy-3,5-di-tert-butylphenyl) Examples include phenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-4-octoxyphenyl)benzotriazole, 2,2'-methylenebis(4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis(1,3-benzoxazin-4-one), and 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole. Examples include polymers having a 2-hydroxyphenyl-2H-benzotriazole skeleton, such as copolymers of 2-(2'-hydroxy-5-methacryloxyethylphenyl)-2H-benzotriazole with a vinyl monomer copolymerizable with the monomer, or copolymers of 2-(2'-hydroxy-5-acryloxyethylphenyl)-2H-benzotriazole with a vinyl monomer copolymerizable with the monomer.

[0147] Examples of hydroxyphenyltriazine compounds include 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-hexyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-methyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-ethyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-propyloxyphenol, and 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-butyloxyphenol. Furthermore, examples include compounds in which the phenyl group of the above example compounds has been replaced with a 2,4-dimethylphenyl group, such as 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl)-5-hexyloxyphenol.

[0148] Examples of cyclic iminoesters include 2,2'-p-phenylenebis(3,1-benzoxazine-4-one), 2,2'-(4,4'-diphenylene)bis(3,1-benzoxazine-4-one), and 2,2'-(2,6-naphthalene)bis(3,1-benzoxazine-4-one).

[0149] Examples of cyanoacrylate compounds include 1,3-bis-[(2'-cyano-3',3'-diphenylacryloyl)oxy]-2,2-bis[(2-cyano-3,3-diphenylacryloyl)oxy]methyl)propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene.

[0150] Furthermore, the above-mentioned ultraviolet absorber may be a polymer-type ultraviolet absorber obtained by copolymerizing such ultraviolet-absorbing monomer and / or a photostable monomer having a hindered amine structure with a monomer such as an alkyl (meth)acrylate, by adopting the structure of a monomer compound that can be radically polymerized. Suitable examples of the above-mentioned ultraviolet-absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic iminoester skeleton, and a cyanoacrylate skeleton in the ester substituent of a (meth)acrylic acid ester.

[0151] Among the above, benzotriazole and hydroxyphenyltriazine types are preferred in terms of ultraviolet absorption capacity, while cyclic iminoester and cyanoacrylate types are preferred in terms of heat resistance and hue (transparency). The above ultraviolet absorbers may be used individually or as a mixture of two or more.

[0152] The amount of ultraviolet absorber is preferably 0.01 to 2 parts by weight, more preferably 0.02 to 2 parts by weight, even more preferably 0.03 to 1 part by weight, and even more preferably 0.05 to 0.5 parts by weight, based on 100 parts by weight of the total of components A and B.

[0153] (Hindered amine-based light stabilizers) The resin composition of the present invention may contain a hindered amine light stabilizer. Hindered amine light stabilizers are generally called HALS (Hindered Amine Light Stabilizer) and are compounds having a 2,2,6,6-tetramethylpiperidine skeleton in their structure.

[0154] For example, 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(phenylacetoxy)-2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetramethylpiperidine Peridine, 4-benzyloxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine, 4-(ethylcarbamoyloxy)-2,2,6,6-tetramethylpiperidine, 4-(cyclohexylcarbamoyloxy)-2,2,6,6-tetramethylpiperidine, 4-(phenylcarbamoyloxy)-2,2,6,6-tetramethylpiperidine, bis(2,2,6,6-tetramethyl-4-piperidyl) carbonate, bis(2,2,6,6-tetramethyl-4-piperidyl) oxalate, bis( 2,2,6,6-tetramethyl-4-piperidyl)malonate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)adipate, bis(2,2,6,6-tetramethyl-4-piperidyl)terephthalate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)carbonate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)oxalate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)malonate, bis(1,2,2,6,6-pentamethyl (Tyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) adipate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) terephthalate, N,N'-bis-2,2,6,6-tetramethyl-4-piperidinyl-1,3-benzenedicarboxyamide, 1,2-bis(2,2,6,6-tetramethyl-4-piperidyloxy)ethane, α,α'-bis(2,2,6,6-tetramethyl-4-piperidyloxy)-p-xylene, bis(2,2,6,6-tetramethyl-4-piperidyltrylene-2,4-Dicarbamate, bis(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylene-1,6-dicarbamate, tris(2,2,6,6-tetramethyl-4-piperidyl)-benzene-1,3,5-tricarboxylate, N,N',N'',N'''-tetrakis-(4,6-bis-(butyl-(N-methyl-2,2,6,6-tetramethylpiperidine-4-yl)amino)-triazine-2-yl)-4,7-diazadecane-1,10- Diamine, dibutylamine·1,3,5-triazine·N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine polycondensate, poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethylene{(2,2,6, 6-tetramethyl-4-piperidyl)imino}], tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tris(2,2,6,6-tetramethyl-4-piperidyl)benzene-1,3,4-tricarboxylate, 1-[2-{3-(3,5-di-t-butyl-4-hi Examples include droxyphenyl)propionyloxy}butyl]-4-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]2,2,6,6-tetramethylpiperidine, and condensates of 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol, and β,β,β',β'-tetramethyl-3,9-[2,4,8,10-tetraoxaspiro(5,5)undecane]diethanol.

[0155] Hindered amine light stabilizers are broadly classified into three types based on the bonding partner of the nitrogen atom in the piperidine skeleton: NH type (hydrogen bonded to the nitrogen atom), NR type (alkyl group (R) bonded to the nitrogen atom), and N-OR type (alkoxy group (OR) bonded to the nitrogen atom). When applied to polycarbonate resins, it is more preferable to use the low-basic NR type or N-OR type from the viewpoint of the basicity of the hindered amine light stabilizer. The above hindered amine light stabilizers can be used individually or in combination of two or more types.

[0156] The content of the hindered amine light stabilizer is preferably 0 to 1 part by weight, more preferably 0.05 to 1 part by weight, even more preferably 0.08 to 0.7 parts by weight, and particularly preferably 0.1 to 0.5 parts by weight, per 100 parts by weight of the total of components A and B. If the content of the hindered amine light stabilizer is greater than 1 part by weight, appearance defects due to gas generation and deterioration of physical properties due to decomposition of the polycarbonate resin may occur. Also, if it is less than 0.05 parts by weight, sufficient light resistance may not be achieved.

[0157] (Dyes and pigments) The resin composition of the present invention can further contain various dyes and pigments to provide molded articles exhibiting diverse design properties. By incorporating fluorescent whitening agents or other fluorescent dyes that emit light, even better design effects can be achieved by utilizing the luminescent color. Furthermore, a fiber-reinforced polycarbonate resin composition that can be colored with minute amounts of dyes and pigments and exhibits vivid color development can also be provided.

[0158] Examples of fluorescent dyes (including fluorescent whitening agents) include coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, perylene-based fluorescent dyes, anthraquinone-based fluorescent dyes, thioindigo-based fluorescent dyes, xanthene-based fluorescent dyes, xanthone-based fluorescent dyes, thioxanthene-based fluorescent dyes, thioxanthone-based fluorescent dyes, thiaidine-based fluorescent dyes, and diaminostilbene-based fluorescent dyes. Among these, coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, and perylene-based fluorescent dyes are preferred because they have good heat resistance and do not degrade much during the molding process of polycarbonate resin.

[0159] Other dyes besides the bluing agents and fluorescent dyes mentioned above include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as Prussian blue, perinone dyes, quinoline dyes, quinacridone dyes, dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Furthermore, the resin composition of the present invention can be further enhanced by incorporating metallic pigments to obtain better metallic colors. Suitable metallic pigments include those having a metal coating or metal oxide coating on various plate-shaped fillers. The content of the above-mentioned dye pigment is preferably 0.00001 to 1 part by weight, and more preferably 0.00005 to 0.5 parts by weight, per 100 parts by weight of the total of components A and B.

[0160] (Other resins) The resin composition of the present invention may also contain other resins in small proportions, as long as they do not exert the effects of the present invention. Other resins include, for example, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polyolefin resins other than polycarbonate resins, polymethacrylate resins, phenolic resins, epoxy resins, and others.

[0161] (Other fillers) The resin composition of the present invention may also contain other fillers in small proportions, as long as they do not exert the effects of the present invention. Other fillers include fibrous fillers such as potassium titanate whiskers, zinc oxide whiskers, alumina fibers, silicon carbide fibers, ceramic fibers, asbestos fibers, gypsum fibers, and metal fibers; and silicates such as wollastonite, sericite, kaolin, mica, clay, bentonite, asbestos, talc, and alumina silicate. Also included are swellable layered silicates such as montmorillonite and synthetic mica; metal compounds such as alumina, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, and iron oxide; carbonates such as calcium carbonate, magnesium carbonate, and dolomite; sulfates such as calcium sulfate and barium sulfate; and non-fibrous fillers such as glass beads, ceramic beads, boron nitride, silicon carbide, calcium phosphate, and silica.

[0162] (Other additives) The resin composition of the present invention may contain small amounts of well-known additives to impart various functions or improve the properties of molded articles. These additives are used in normal amounts, as long as they do not impair the objectives of the present invention. Examples of such additives include lubricants (e.g., PTFE particles), fluorescent dyes, inorganic phosphors (e.g., phosphors with aluminate as the matrix crystal), antistatic agents, nucleating agents, inorganic and organic antimicrobial agents, photocatalytic antifouling agents (e.g., fine-particle titanium dioxide, fine-particle zinc oxide), radical generators, infrared absorbers (heat absorbers), and photochromic agents.

[0163] (Method for manufacturing resin compositions) There are no particular limitations on the method for producing the resin composition of the present invention, and well-known methods can be used. For example, one method is to mix each component in a solution state and then evaporate the solvent or precipitate the components in the solvent. From an industrial standpoint, a method of kneading each component in a molten state is preferred. For molten kneading, kneading equipment such as single-screw or twin-screw extruders and various types of kneaders that are commonly used can be used. A twin-screw high-pressure kneader is particularly preferred. When molten kneading, the cylinder setting temperature of the kneading equipment is preferably in the range of 200 to 360°C, more preferably in the range of 200 to 300°C, and even more preferably in the range of 230 to 280°C. When kneading, each component may be uniformly mixed beforehand in an apparatus such as a tumbler or Henschel mixer, or if necessary, mixing can be omitted and each component can be supplied separately in a quantitative amount to the kneading equipment.

[0164] The resin composition of the present invention can be pelletized or formed into sheets by melt-kneading using an extruder such as a single-screw extruder or a twin-screw extruder. Various reinforcing fillers and additives can also be incorporated into the preparation of these pellets and sheets.

[0165] (Reinforcement fibers) The content of the reinforcing fibers used in the present invention is preferably 15 to 400 parts by weight, more preferably 80 to 300 parts by weight, and even more preferably 100 to 250 parts by weight, based on 100 parts by weight of the total amount of components A and B. If the content of reinforcing fibers is less than 15 parts by weight, the long-term durability of the strength may decrease, and if the content of reinforcing fibers exceeds 400 parts by weight, the flame retardancy may deteriorate.

[0166] The reinforcing fibers used in the present invention are preferably reinforcing fibers with a heat resistance of 350°C or higher. Specifically, inorganic fibers such as high-strength carbon fibers, glass fibers, and metal fibers, as well as organic synthetic fibers such as aromatic polyamide fibers, can be used. Furthermore, these may be used individually or in combination of two or more types. Examples of metal fibers include stainless steel fibers, which are preferred for their conductivity and mechanical properties. In addition, the surface of the reinforcing fibers may be coated or vapor-deposited with metal or the like. For example, nickel-coated carbon fibers are preferred for their conductivity. Carbon fibers and glass fibers with high strength and high modulus are particularly preferred, and in order to obtain a highly rigid laminate, carbon fibers, more specifically carbon fibers such as polyacrylonitrile (PAN)-based, petroleum / coal pitch-based, rayon-based, and lignin-based carbon fibers, can be used. In particular, PAN-based carbon fibers made from PAN are preferred because they have excellent productivity and mechanical properties on an industrial scale.

[0167] Furthermore, the reinforcing fibers used in this invention are preferably long in one direction, and the concept includes not only general fibers and filaments, but also so-called whiskers and the like.

[0168] More specifically, examples of reinforcing fibers suitably used in the present invention include fibrous materials made of inorganic fillers such as glass fiber, flat-section glass fiber, carbon fiber, metal fiber, asbestos, rock wool, ceramic fiber, slag fiber, potassium titanate whisker, boron whisker, aluminum borate whisker, calcium carbonate whisker, titanium oxide whisker, wollastonite, xonotlite, palygorskite (atapulgite), and sepiolite; heat-resistant organic fibers such as aramid fiber, polyimide fiber, PBO (poly-p-phenylene benzoxazole) fiber, and polybenzthiazole fiber; and fibers in which dissimilar materials such as metals or metal oxides are surface-coated.

[0169] The fibers coated with dissimilar materials only need to be in a fibrous form, and examples include metal-coated glass fibers, metal-coated glass flakes, titanium oxide-coated glass flakes, and metal-coated carbon fibers. The method for coating the surface of the dissimilar materials is not particularly limited and can be described as various known plating methods (e.g., electrolytic plating, electroless plating, hot-dip plating, etc.), vacuum deposition, ion plating, CVD (e.g., thermal CVD, MOCVD, plasma CVD, etc.), PVD, and sputtering.

[0170] Among these reinforcing fibers, it is particularly preferable to use one selected from carbon fiber, glass fiber, and aramid fiber. Furthermore, one type of reinforcing fiber may be used, or multiple types may be used.

[0171] The reinforcing fibers should preferably have an average diameter of 3 to 20 μm, and more preferably 5 to 15 μm. Within this range, not only are the physical properties of the fibers high, but their dispersibility in the thermoplastic resin that ultimately forms the matrix is ​​also excellent. Furthermore, from a productivity standpoint, it is also preferable that these reinforcing fibers are bundles of 1,000 to 50,000 single fibers.

[0172] Furthermore, the reinforcing fibers used in the laminate of the present invention should preferably have high strength in order to ultimately reinforce the resin. The tensile strength of the fibers should preferably be 3500 MPa to 7000 MPa, and the modulus should preferably be 220 GPa to 900 GPa. From the viewpoint of obtaining a high-strength molded product in the end, carbon fibers are particularly preferred as reinforcing fibers, and PAN-based carbon fibers are more preferred.

[0173] The surface of the carbon fibers is preferably oxidized to improve compatibility with the matrix resin and to enhance the dispersibility of the polycarbonate resin. Although the mechanism is not yet clear, oxidizing the surface of the carbon fibers improves the surface polarity, further reducing the adhesion between the nonpolar propylene resin and the carbon fibers. As a result, it is thought that the adhesion with the relatively more polar polycarbonate resin improves.

[0174] The degree of oxidation treatment can be quantified by the surface oxygen concentration (O / C) on the carbon fibers. The surface oxygen concentration (O / C), which is the ratio of the number of oxygen (O) atoms to carbon (C) atoms on the fiber surface measured by X-ray photoelectron spectroscopy, is preferably 0.15 or higher, more preferably 0.18 or higher, and even more preferably 0.2 or higher. If the surface oxygen concentration is less than 0.15, the adhesion between the carbon fibers and the polycarbonate resin may be insufficient, which is undesirable. There is no particular upper limit to the surface oxygen concentration, but it is generally preferable to have it at 0.5 or lower from the perspective of balancing the handling and productivity of the carbon fibers.

[0175] The oxidation treatment method is not particularly limited, but preferred examples include (1) a method of treating carbon fibers with an acid or alkali or a salt thereof, or an oxidizing gas; (2) a method of firing carbon fiber-compatible fibers or fibrous carbon filler at a temperature of 700°C or higher in the presence of an inert gas containing an oxygen-containing compound; and (3) a method of oxidizing carbon fibers and then heat-treating them in the presence of an inert gas.

[0176] These reinforcing fibers can be used in either the form of long fibers or short fibers in the fiber-reinforced composite molded body. However, from the viewpoint of reinforcing the resin, the long fiber form is preferable, and conversely, from the viewpoint of making the physical properties of the resulting composite isotropic, a composition mainly of short fibers is preferable. Here, short fibers refer to discontinuous fibers that are not long fibers. When used as short fibers, a reinforcing fiber sheet is preferable, and the reinforcing fiber sheet is preferably a fiber aggregate or nonwoven fabric in which the fiber orientation has been randomized in advance. The reinforcing fiber sheet is preferably a woven or knitted fabric, a nonwoven fabric, or a unidirectional sheet.

[0177] Furthermore, when reinforcing fibers are used as short fibers (discontinuous fibers), their length is preferably 300 μm or more, more preferably 3 mm or more, even more preferably 6 mm or more, and most preferably 20 mm or more. When used as short fibers, their length is preferably 100 mm or less, even more preferably 80 mm or less, and particularly preferably 60 mm or less. When such fibers are used in the form of a nonwoven fabric, the anisotropy with respect to strength and dimensions is improved.

[0178] On the other hand, when reinforcing fibers are used as long fibers, they can be used in various forms such as unidirectional sheets, woven fabrics, knitted fabrics, and braids. However, from the standpoint of strengthening the final composite, it is preferable to use them as unidirectional sheets (so-called UD sheets). Alternatively, it is preferable that some or all of the reinforcing fibers are unidirectional fiber sheets or unidirectional tapes, and that these be used partially. When used as long fibers, particularly preferred forms include woven fabrics such as biaxial or triaxial fibers. Furthermore, it is also possible to use one or more of these fiber forms in combination.

[0179] The amount of reinforcing fibers used in the present invention is 15 to 400 parts by weight, preferably 40 to 300 parts by weight, more preferably 100 to 250 parts by weight, and even more preferably 120 to 200 parts by weight, based on 100 parts by weight of the total of components A and B of the thermoplastic resin. If the amount of reinforcing fibers is less than 15 parts by weight, the strength of the fiber-reinforced composite molded article will not be sufficiently exhibited, and if it exceeds 400 parts by weight, a large number of reinforcing fibers will slip off, resulting in a poor appearance.

[0180] (Fiber-reinforced composite molded body) In the present invention, it is preferable that the reinforcing fibers are in the form of a reinforcing fiber sheet, the resin composition is in the form of a resin composition sheet, and the fiber-reinforced composite molded article is a laminate of the reinforcing fiber sheet and the resin composition sheet.

[0181] A fiber-reinforced composite molded article can be produced by pressurizing a laminate of a reinforcing fiber sheet and a resin composition sheet at a temperature above the melting temperature of the thermoplastic resin constituting the resin composition sheet and below the heat resistance temperature of the reinforcing fibers constituting the reinforcing fiber sheet.

[0182] The weight ratio of the resin composition sheet to the reinforcing fiber sheet is preferably in the range of 90:10 to 20:80, and more preferably in the range of 30:70 to 50:50. Furthermore, for the resin composition sheet, a peacock probe with a diameter of 8 mm was used to measure a load of 1.25 N / cm. 2 Under these conditions, the thickness measured is preferably 0.05 to 0.5 mm, more preferably 0.1 to 0.3 mm, and the basis weight is 2 to 100 g / m². 2 It is preferable that the thickness be within this range. For the reinforcing fiber sheet, the thickness should be 0.05 to 1.0 mm and the basis weight should be 100 to 2000 g / m². 2 It is preferable that it be within the range.

[0183] The laminate is made by stacking multiple thin resin composition sheets and reinforcing fiber sheets, preferably in an alternating arrangement, and more preferably with resin composition sheets on the outermost surfaces of both the front and back. The number of reinforcing fiber sheets is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 to 2. Figure 1 shows a schematic cross-sectional view of the laminate of the present invention.

[0184] The form of the resin composition sheet used in the present invention is not particularly limited, but in order to achieve the above objective, it is preferable that at least one dimension of the three dimensions of length, width, and thickness is in the range of 1 to 300 μm, more preferably 1 to 100 μm, even more preferably 1 to 50 μm, and most preferably 1 to 30 μm. Examples of such forms include films, nonwoven fabrics, and mesh-like fiber sheets, and among these, films are preferred from the viewpoint of quality stability of the resin composition sheet.

[0185] (Method for manufacturing fiber-reinforced composite molded articles) The fiber-reinforced composite molded articles of the present invention are formed by known molding methods such as injection molding, blow molding, extrusion molding, press molding, compression molding, and insert molding. More preferred methods include a molding method in which the aforementioned laminate, formed by layering a resin composition sheet and a reinforcing fiber sheet, is press-molded, and a molding method in which it is molded using an LFT-D (Long-Fiber Thermoplastics Direct) apparatus.

[0186] Fiber-reinforced composites obtained by press molding of laminates are obtained by pressurizing the aforementioned laminates. Specifically, the aforementioned laminates can be manufactured by pressurizing them at a temperature above the melting temperature of the polycarbonate resin constituting the resin composition sheet, and below the heat resistance temperature of the reinforcing fibers constituting the reinforcing fiber sheet.

[0187] In this method, the reinforcing fibers are surrounded by polycarbonate resin, and it is preferable that there are no voids in order to improve the physical properties of the composite. The temperature for pressurization is preferably in the range of 200 to 340°C, and more preferably in the range of 240 to 330°C, although this depends on the polycarbonate resin used. The processing time is preferably about 1 to 30 minutes, more preferably about 1 to 10 minutes, and particularly preferably in the range of 3 to 10 minutes. The press pressure during processing is preferably in the range of 2 to 30 MPa, and more preferably in the range of 5 to 20 MPa.

[0188] A fiber-reinforced composite molded article obtained by press molding of a laminate has a structure in which reinforcing fiber sheets are layered on top of each other via resin composition sheets. Although a portion of the resin composition sheets of the laminate are impregnated into the reinforcing fiber sheets, it basically has a cross-sectional shape similar to that of the laminate. Figure 2 shows a schematic cross-sectional view of a fiber-reinforced composite manufactured by a molding method that press-moldes a laminate.

[0189] The basic configuration of the LFT-D molding system consists of a twin-screw extruder, a rotary valve / injection plunger, and a press molding machine. Specifically, first, the aforementioned resin composition pellets are fed into the twin-screw extruder via a feeder, and the reinforcing fibers are supplied directly to the twin-screw extruder cylinder, where they are mixed with the molten resin to produce a composite material. Next, the composite material flows into the injection plunger through a rotary valve installed at the front of the twin-screw extruder. During the flow, the injection plunger is retracted to fill the injection plunger with a predetermined amount of composite material (metering operation). After that, the injection plunger is advanced to inject the composite material into the mold, and a fiber-reinforced composite molded body is obtained by press molding. The two injection plungers perform a metering operation on one side while the injection operation is in progress on the other, and the injection and metering operations are repeated alternately, thus enabling the continuous production of composite materials by the twin-screw extruder.

[0190] This molding method supplies reinforcing fibers to the molten resin portion within the twin-screw extruder cylinder, thereby suppressing fiber breakage compared to conventional injection molding and enabling the production of high-strength molded products. A schematic diagram of the LFT-D apparatus is shown in Figure 3.

[0191] The present inventors consider the best possible form of the present invention to be a combination of the preferred ranges of the above-mentioned requirements, and a representative example is described in the following examples. Of course, the present invention is not limited to these forms. [Examples]

[0192] The following describes examples and comparative examples of the present invention in detail, but the present invention is not limited thereto. The manufacturing methods and evaluation methods in the production examples, examples, and comparative examples were carried out as follows.

[0193] [Examples A1-A5 and Comparative Examples A1-A4 (Manufacturing Examples 1-9)] (I) Resin composition sheet (I-1) Manufacturing of sheets composed of resin compositions The polycarbonate resin compositions listed in Table 1 were dried in a hot air circulating dryer at 90°C for 5 hours. Then, they were extruded from a twin-screw extruder at the extrusion temperatures listed in the table, and rapidly cooled at the die exit to produce film-like resin composition sheets of the thicknesses listed in Table 1. The evaluation of these film-like sheets is shown in Table 1. (I-2) Average thickness (film-like sheet) Using a peacock probe with a diameter of 8 mm, the load was 1.25 N / cm. 2 The thickness was measured under the specified conditions. Measurements were taken at three points: both ends and the center of the film. The average of these measurements was taken as the average thickness.

[0194] [Example A6 (Manufacturing Example 10)] A mixture (resin composition) with the composition shown in Table 1 was supplied from the first feed port of the extruder. This mixture was obtained by mixing in a V-type blender. The twin-screw extruder used was a Japan Steel Works "TEX30αIII" co-rotating twin-screw extruder with a diameter of 30 mmφ, a total of 10 barrels (referred to as cylinders C1 to C10 from upstream) with feed ports at the uppermost C1 and C5 downstream, and one vent. The extrusion conditions were a temperature of C1: 260°C, C2 to C10: 270°C, a screw rotation speed of 200 rpm, a discharge rate of 25 kg / h, and a vent vacuum of 3 kPa, and the mixture was melt-kneaded to obtain pellets.

[0195] [Examples B1-B11, Comparative Examples B1-B4] (II) Fiber-reinforced composite (II-1) Fabrication of fiber-reinforced composites (II-1-1) Press molding of laminated bodies The resin composition sheets and reinforcing fiber sheets obtained in Production Examples 1 to 9 were laminated in the proportions shown in Tables 2 and 3 to form a laminate. The laminate was inserted into a preheated hot press, and fiber-reinforced composites (FRP molded articles) were obtained under the pressing conditions (temperature, pressing time, and pressing pressure) shown in Tables 2 and 3. Care was taken to ensure that the reinforcing fibers were evenly distributed during lamination, and the amount of thermoplastic fiber sheets and reinforcing fibers was adjusted so that the desired thickness of the fiber-reinforced composite article was achieved after preheating and pressing. The evaluation of the final obtained fiber-reinforced composite articles is shown in Tables 2 and 3. Laminates using reinforcing fibers FI-1 and FI-3 were fabricated with the fiber directions aligned.

[0196] (II-1-2) Press forming using LFT-D equipment Resin composition pellets obtained in Production Example 10 were supplied from the first feed port (C1) of a twin-screw extruder in the proportions shown in Table 2, and reinforcing fibers were supplied to the fifth feed port (C5) for melt-mixing. The resulting composite material was then injected into a press mold using an injection plunger, and a fiber-reinforced composite molded body was obtained under the press conditions (temperature, press time, press pressure) shown in Table 2.

[0197] The twin-screw extruder used was a Japan Steel Works "TEX30αIII" co-rotating twin-screw extruder with a diameter of 30 mmφ, consisting of 10 barrels in total (referred to as cylinders C1 to C10 from upstream) with supply ports at the uppermost C1 and C5 downstream, and equipped with one vent. The extrusion conditions were 260°C for C1 and 270°C for C2 to C10, with a screw rotation speed of 200 rpm, a discharge rate of 25 kg / h, and a vent vacuum of 3 kPa, during which melting and mixing took place.

[0198] (II-2) Bending strength Sample pieces were cut from the fiber-reinforced composite molded body obtained from (II-1), and their bending strength was measured in accordance with ISO 178 (measurement conditions: test speed 2 mm / min, test temperature 23°C). For laminates using reinforcing fibers FI-1 and FI-3, sample pieces were cut so that the longer side was in the direction of the fibers, and the bending strength was measured. For laminates using reinforcing fibers FI-2, 4, 5, and 6, samples were cut in two directions perpendicular to each other, and the bending strength was evaluated as the average of the bending strengths in those two directions.

[0199] (II-3) Interstory shear strength Sample pieces were cut from the fiber-reinforced composite molded body obtained from (II-1), and the interlaminar shear strength was measured in accordance with ASTM D2324 (measurement conditions: test temperature 23°C). For laminates using reinforcing fibers FI-1 and FI-3, sample pieces were cut so that the longer side was in the fiber direction, and the interlaminar shear strength was measured.

[0200] (II-4) High temperature and high humidity test (long-term durability evaluation) (a) Bending strength retention rate Sample pieces were cut from the fiber-reinforced composite molded body obtained from (II-1), heat-treated for 1000 hours at 60°C and 55% humidity, and the bending strength was measured in accordance with ISO 178 (measurement conditions: test speed 2 mm / min, test temperature 23°C). From these results, the bending strength retention rate was calculated using the following formula. A bending strength retention rate of 60% or more is preferable. Bending strength retention rate (%) = (Bending strength after high temperature and high humidity test / Initial bending strength) × 100 (b) Inter-lay shear strength retention rate Sample pieces were cut from the fiber-reinforced composite molded body obtained from (II-1), heat-treated for 1000 hours at 60°C and 55% humidity, and the interlaminar shear strength was measured in accordance with ASTM D2324 (measurement conditions: test temperature 23°C). From these results, the retention rate of bending strength was calculated using the following formula. It is preferable that the interlaminar shear strength retention rate is 60% or higher. Interlaminar shear strength retention rate (%) = (Interlaminar shear strength after high temperature and high humidity test / Initial interlaminar shear strength) × 100

[0201] (II-5 Flame retardant) Combustion tests were conducted using 1.0 mm thick UL test specimens obtained by the following method, in accordance with the UL94 vertical combustion test defined by Underwriter Laboratory, Inc., USA. The results were evaluated and classified as V-0, V-1, V-2, and not V. A flame retardancy of V-0 is preferable.

[0202] [Composition used] The following components were used in the examples. (Component A) (Polycarbonate resin) A-1: Polycarbonate resin consisting of 2,2-bis(4-hydroxyphenyl)propane as the monomer component [MVR (300℃, 1.2kg load) = 8.5cm 3 [10 min]

[0203] (Component B) (Phosphazene) B-1: Cyclic phenoxyphosphazene in which the content of the k=1 trimer in the following formula (18) is 100 mol% B-2; A cyclic phenoxyphosphazene in which the content of the k=1 trimer in formula (18) below is 98.5 mol%, the content of the k=2 tetramer is 1 mol%, and the content of the k=3 or higher polymer is 0.5 mol. B-3: A cyclic phenoxyphosphazene in which the content of the k=1 trimer in formula (18) below is 98 mol%, the content of the k=2 tetramer is 1.5 mol%, and the content of the k=3 or higher polymer is 0.5 mol. B-4: Cyclic phenoxyphosphazene with the content of the trimer with k = 1 in the following formula (18) being 70 mol%, the content of the tetramer with k = 2 being 20 mol%, and the content of the polymer with k ≥ 3 being 10 mol%

[0204]

Chemical formula

[0205] (Component C) (Bisphenol A type epoxy resin) C-1: Bisphenol A type epoxy resin, epoxy equivalent 7500 - 8500 g / eq, JER1256 (product name) manufactured by Mitsubishi Chemical Corporation

[0206] (Component D) D-1: Octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, AO-50 (product name) manufactured by Adeka Corporation D-2: 3,9-Bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane, Adeka Stab PEP36 (product name) manufactured by Adeka Corporation

[0207] (Reinforcing fiber) FI-1: Carbon fiber unidirectional tape ["F-22" manufactured by Toray Tenax Co., Ltd., fiber diameter = 7 μm] FI-2: Carbon fiber woven fabric ["W3101" manufactured by Toray Tenax Co., Ltd., basis weight = 200 g / m 2 , thickness 0.25 mm, fiber diameter = 7 μm] FI-3: Nickel-coated carbon fiber tape ["HTS40 MC" manufactured by Toray Tenax Co., Ltd., fiber diameter = 7.5 μm, width 10 mm] FI-4: Glass fiber woven fabric ["WF150" manufactured by Nitto Boseki Co., Ltd.], basis weight = 144 g / m 2 , thickness 0.22 mm, fiber diameter = 13 μm] FI-5: Aramid fiber non-woven fabric ["Technora EF200" manufactured by Teijin Fibers Limited], basis weight = 200 g / m 2 , fiber diameter = 12 μm] FI-6: Carbon fiber sheet [Manufactured by Toho Tenax Co., Ltd.: HT C422, 6mm in diameter, 7μm in length, cut length 6mm carbon fiber, compressed to form a sheet 300mm wide and 300mm long]

[0208] [Table 1]

[0209] [Table 2]

[0210] [Table 3] [Industrial applicability]

[0211] The fiber-reinforced composite molded articles obtained by compounding the resin composition for fiber-reinforced composite molded articles of the present invention with reinforcing fibers exhibit excellent mechanical properties such as bending strength and shear strength, as well as their long-term durability and flame retardancy, making them useful for electrical and electronic components, home appliances, automotive parts, infrastructure parts, housing equipment parts, and the like. [Explanation of Symbols]

[0212] 1. Thermoplastic resin sheet layer 2. Reinforcement fiber sheet layer 3. Thermoplastic resin pellets 4. Reinforced fiber 5. Raw material feeder 6. Twin-screw extruder 7. Rotary valve 8. Injection plunger 9. Press molding machine

Claims

1. A resin composition for fiber-reinforced composite molded articles, characterized by containing (A) 70 to 99 parts by weight of polycarbonate resin (component A), (B) 30 to 1 part by weight of phosphazene (component B) containing 98.5 mol% or more of a phosphazene cyclic trimer, and (C) 0.1 to 20 parts by weight of an adhesion improver (component C), which is at least one organic compound selected from the group consisting of glycidyl methacrylate, bisphenol A type epoxy resin, polyarylate, and styrene-maleic acid resin, per 100 parts by weight of the total amount of components A and B.

2. A fiber-reinforced composite molded article which is a composite of the resin composition described in claim 1 and reinforcing fibers.

3. The fiber-reinforced composite molded article according to claim 2, wherein the fibers constituting the reinforcing fibers are at least one fiber selected from carbon fibers, glass fibers, and aramid fibers.

4. The fiber-reinforced composite molded article according to claim 2 or 3, wherein the reinforcing fibers are in the form of a reinforcing fiber sheet, and the resin composition is in the form of a resin composition sheet, and the composite is a laminate of the reinforcing fiber sheet and the resin composition sheet.

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