JP2018193522A - Heat-caulking joint - Google Patents

Abstract

To provide a heat-caulking joint that prevents its components from being loosened after heat-caulking.SOLUTION: A heat-caulking joint is obtained by fixing a plastic component and another component by heat-caulking. The plastic component is a molding composed of a glass reinforced polycarbonate resin composition containing 100 pts.wt. of a resin component comprising (A) a polycarbonate resin (component A) 0-90 wt.% and (B) a polycarbonate-polydiorganosiloxane copolymer resin (component B) 10-100 wt.%, as well as (C) 10-100 pts.wt. of glass flake with an average thickness of 0.2-0.7 μm.SELECTED DRAWING: None

Description

  The present invention relates to a thermal caulking joined body in which a plastic part and another part are fixed by thermal caulking. More specifically, the present invention relates to a heat caulking joined body in which the plastic part is a specific glass-reinforced polycarbonate resin composition and the part after the heat caulking is less shaky.

  As a method of joining a plastic part and another part, there are methods such as 1) mechanical joining (press-fit, screw, snap fit, heat caulking, etc.), 2) adhesion, 3) welding or welding. Each coupling method has its advantages and disadvantages. When actually designing the coupling part, material characteristics, number of parts, cost, performance such as strength and durability, dimension and shape are selected from the above methods. In consideration of the configuration of internal parts, etc., a method desirable in design is selected. The fastening method using heat caulking is not suitable for fastening parts that are scheduled to be replaced because once the caulking is done, the caulking part cannot be removed unless it is damaged. However, since the structure is simple and the cost of the caulking device is relatively low, and the time required for caulking is as short as several seconds, it is used in various fields. Further, glass reinforced polycarbonate resin compositions containing glass flakes and other plate-like glass fillers are also widely used as metal substitutes from the viewpoints of weight reduction, moldability, and low warpage. Injection molding is mainly used as the molding process, but for product design, joining with the same material or different materials by heat caulking is separately performed after injection molding (Patent Document 1). With the recent expansion of resinization, there is an increasing demand for a heat-caulking bonded body with less rattling under various environments. With conventional glass-reinforced polycarbonate resin compositions, sufficient heat is required particularly from the viewpoint of durability. A caulking conjugate cannot be obtained.

  A resin composition using a thermoplastic resin and glass flakes having an average thickness of 0.5 to 7.0 μm is known (Patent Documents 2 and 3). In this patent document, there is a description of the strength of the glass-reinforced resin composition and the thermal stability at the time of extrusion or molding, but there is no description about the heat-caulking bonded body. As a method for improving the durability of the glass-reinforced polycarbonate resin composition, methods using a polycarbonate-polydiorganosiloxane copolymer resin are known (Patent Documents 4 to 6). In these documents, it is stated that the impact resistance of the glass reinforced resin composition is improved by using a polycarbonate-polydiorganosiloxane copolymer resin as the polycarbonate resin, but there is no example using glass flakes, and There is no description regarding the heat caulking conjugate.

WO2008 / 139620 Japanese Examined Patent Publication No. 6-74333 Japanese Patent No. 5562220 Japanese Patent Laid-Open No. 55-160052 JP-A-7-26149 WO2012 / 26236

  It is an object of the present invention to provide a heat caulking assembly with less parts rattling after heat caulking.

  As a result of intensive research aimed at achieving the above object, the present inventors use a glass-reinforced polycarbonate resin composition containing a polycarbonate resin, a polycarbonate-polydiorganosiloxane copolymer resin, and glass flakes having a specific thickness. As a result, the inventors have found that a heat caulking combined body having excellent heat caulking characteristics, in particular, having less shakiness of parts even under various environments can be obtained, and the present invention has been achieved.

That is, according to the present invention, (1) a heat caulking assembly in which a plastic part and another part are fixed by heat caulking, the plastic part is (A) polycarbonate resin (component A) 0 to 90% by weight and ( B) Glass flake (C component) having an average thickness of 0.2 to 0.7 μm with respect to 100 parts by weight of the resin component comprising 10 to 100% by weight of polycarbonate-polydiorganosiloxane copolymer resin (B component) ) A heat caulking combined body characterized in that it is a molded body made of a glass-reinforced polycarbonate resin composition containing 10 to 100 parts by weight.
One of the more preferable embodiments of the present invention is (2) the heat-caulking assembly according to the configuration (1), wherein the plastic part is a cylindrical molded body.
One of the more preferred embodiments of the present invention is (3) a glass-reinforced polycarbonate resin composition constituting the plastic part according to the above-mentioned constitution (1) or (2).

Hereinafter, the present invention will be specifically described.
(A component: polycarbonate resin)
The polycarbonate resin used as the component A of the present invention is usually obtained by reacting a dihydroxy compound and a carbonate precursor by an interfacial polycondensation method or a melt transesterification method, or a carbonate prepolymer by a solid phase transesterification method. Or obtained by polymerizing by a ring-opening polymerization method of a cyclic carbonate compound. The dihydroxy component used here may be any one that is usually used as a dihydroxy component of an aromatic polycarbonate, and may be a bisphenol or an aliphatic diol. Examples of bisphenols include 4,4′-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 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, 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-hydroxypheny) ) 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′-sulfoni Diphenol, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-dimethyl Diphenyl 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, 1,4-bis {2- (4-hydroxyphenyl) propyl } Benzene, 1,4-bis (4-hydroxyphenyl) cyclohexane, 1,3-bis (4-hydro Cyphenyl) cyclohexane, 4,8-bis (4-hydroxyphenyl) tricyclo [5.2.1.02,6] decane, 4,4 ′-(1,3-adamantanediyl) diphenol, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane and the like.

  Examples of the aliphatic diols include 2,2-bis- (4-hydroxycyclohexyl) -propane, 1,14-tetradecanediol, octaethylene glycol, 1,16-hexadecanediol, 4,4′-bis (2- Hydroxyethoxy) biphenyl, bis {(2-hydroxyethoxy) phenyl} methane, 1,1-bis {(2-hydroxyethoxy) phenyl} ethane, 1,1-bis {(2-hydroxyethoxy) phenyl} -1- Phenylethane, 2,2-bis {(2-hydroxyethoxy) phenyl} propane, 2,2-bis {(2-hydroxyethoxy) -3-methylphenyl} propane, 1,1-bis {(2-hydroxyethoxy) ) Phenyl} -3,3,5-trimethylcyclohexane, 2,2-bis {4- (2-hydroxy) Ethoxy) -3,3′-biphenyl} propane, 2,2-bis {(2-hydroxyethoxy) -3-isopropylphenyl} propane, 2,2-bis {3-tert-butyl-4- (2-hydroxy) Ethoxy) phenyl} propane, 2,2-bis {(2-hydroxyethoxy) phenyl} butane, 2,2-bis {(2-hydroxyethoxy) phenyl} -4-methylpentane, 2,2-bis {(2 -Hydroxyethoxy) phenyl} octane, 1,1-bis {(2-hydroxyethoxy) phenyl} decane, 2,2-bis {3-bromo-4- (2-hydroxyethoxy) phenyl} propane, 2,2- Bis {3,5-dimethyl-4- (2-hydroxyethoxy) phenyl} propane, 2,2-bis {3-cyclohexyl-4- (2-hydroxyethyl) Xyl) phenyl} propane, 1,1-bis {3-cyclohexyl-4- (2-hydroxyethoxy) phenyl} cyclohexane, bis {(2-hydroxyethoxy) phenyl} diphenylmethane, 9,9-bis {(2-hydroxy) Ethoxy) phenyl} fluorene, 9,9-bis {4- (2-hydroxyethoxy) -3-methylphenyl} fluorene, 1,1-bis {(2-hydroxyethoxy) phenyl} cyclohexane, 1,1-bis { (2-hydroxyethoxy) phenyl} cyclopentane, 4,4′-bis (2-hydroxyethoxy) diphenyl ether, 4,4′-bis (2-hydroxyethoxy) -3,3′-dimethyldiphenyl ether Ter, 1,3-bis [2-{(2-hydroxyethoxy) phenyl} propyl] benzene, 1 , 4-bis [2-{(2-hydroxyethoxy) phenyl} propyl] benzene, 1,4-bis {(2-hydroxyethoxy) phenyl} cyclohexane, 1,3-bis {(2-hydroxyethoxy) phenyl} Cyclohexane, 4,8-bis {(2-hydroxyethoxy) phenyl} tricyclo [5.2.1.02,6] decane, 1,3-bis {(2-hydroxyethoxy) phenyl} -5,7-dimethyl Adamantane, 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro (5,5) undecane, 1,4: 3,6-dianhydro-D-sorbitol (Isosorbide), 1,4: 3,6-dianhydro-D-mannitol (isomannide), 1,4: 3,6-dianhydro-L-iditol Isoidide), and the like.

  Among these, aromatic bisphenols are preferable, and among them, 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'-sulfonyl Diphenol, 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, particularly 2,2-bis 4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-sulfonyl diphenol, and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene is preferred. Among them, 2,2-bis (4-hydroxyphenyl) propane having excellent strength and good durability is most preferable. Moreover, you may use these individually or in combination of 2 or more types.

  The polycarbonate resin used as the component A of the present invention may be a branched polycarbonate resin by using a branching agent in combination with the dihydroxy compound. Examples of the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate resin include phloroglucin, phloroglucid, or 4,6-dimethyl-2,4,6-tris (4-hydroxydiphenyl) 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- [ Trisphenol such as 1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol, tetra (4-hydride) Loxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acids Among them, 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable. 1-Tris (4-hydroxyphenyl) ethane is preferred.

  These polycarbonate resins are produced by a reaction means known per se for producing ordinary aromatic polycarbonate resins, for example, a method of reacting an aromatic dihydroxy component with a carbonate precursor such as phosgene or carbonic acid diester. The basic means of the manufacturing method will be briefly described.

  In a reaction using, for example, phosgene as a carbonate precursor, the reaction is usually performed in the presence of an acid binder and a solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. In order to accelerate the reaction, a catalyst such as a tertiary amine or a quaternary ammonium salt can also be used. In that case, reaction temperature is 0-40 degreeC normally, and reaction time is several minutes-5 hours. The transesterification reaction using a carbonic acid diester as a carbonate precursor is performed by a method in which an aromatic dihydroxy component in a predetermined ratio is stirred with a carbonic acid diester while heating with an inert gas atmosphere to distill the generated alcohol or phenols. . The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 300 ° C. The reaction is completed while distilling off the alcohol or phenol produced under reduced pressure from the beginning. Moreover, in order to accelerate | stimulate reaction, the catalyst normally used for transesterification can also be used. Examples of the carbonic acid diester used in the transesterification include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Of these, diphenyl carbonate is particularly preferred.

  In the present invention, a terminal terminator is used in the polymerization reaction. The end terminator is used for molecular weight control, and the obtained polycarbonate resin is excellent in thermal stability as compared with the other one because the end is blocked. Examples of the terminal terminator include monofunctional phenols represented by the following general formulas [1] to [3].

［式中、Ａは水素原子、炭素数１〜９のアルキル基、アルキルフェニル基（アルキル部分の炭素数は１〜９）、フェニル基、またはフェニルアルキル基（アルキル部分の炭素数１〜９）であり、ｒは１〜５、好ましくは１〜３の整数である。］

[In the formula, A is a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, an alkylphenyl group (the alkyl portion has 1 to 9 carbon atoms), a phenyl group, or a phenylalkyl group (the alkyl portion having 1 to 9 carbon atoms). And r is an integer of 1 to 5, preferably 1 to 3. ]

［式中、Ｙは−Ｒ−Ｏ−、−Ｒ−ＣＯ−Ｏ−または−Ｒ−Ｏ−ＣＯ−である、ここでＲは単結合または炭素数１〜１０、好ましくは１〜５の二価の脂肪族炭化水素基を示し、ｎは１０〜５０の整数を示す。］

[Wherein Y is —R—O—, —R—CO—O— or —R—O—CO—, wherein R is a single bond or a carbon number of 1 to 10, preferably 1 to 5; A valent aliphatic hydrocarbon group, and n represents an integer of 10 to 50. ]

  Specific examples of the monofunctional phenols represented by the general formula [1] include, for example, phenol, isopropylphenol, p-tert-butylphenol, p-cresol, p-cumylphenol, 2-phenylphenol, 4-phenyl. Phenol, isooctylphenol, etc. are mentioned. The monofunctional phenols represented by the general formulas [2] to [3] are phenols having a long-chain alkyl group or an aliphatic ester group as a substituent, and using these, the terminal of the polycarbonate resin is used. These not only function as a terminal terminator or molecular weight regulator, but also improve the melt fluidity of the resin and facilitate molding, as well as reducing the water absorption rate of the resin. used. The substituted phenols represented by the general formula [2] preferably have n of 10 to 30, particularly 10 to 26, and specific examples thereof include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, Examples include eicosylphenol, docosylphenol, and triacontylphenol. In addition, as the substituted phenols of the above general formula [3], compounds in which Y is —R—CO—O— and R is a single bond are suitable, and n is 10 to 30, particularly 10 to 26. Specific examples thereof include decyl hydroxybenzoate, dodecyl hydroxybenzoate, tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate and triacontyl hydroxybenzoate. Among these monofunctional phenols, monofunctional phenols represented by the above general formula [1] are preferable, more preferably alkyl-substituted or phenylalkyl-substituted phenols, particularly preferably p-tert-butylphenol, p -Cumylphenol or 2-phenylphenol. It is desirable that these monofunctional phenolic terminal terminators be introduced at least 5 mol%, preferably at least 10 mol%, based on the total terminals of the obtained polycarbonate resin. Or a mixture of two or more thereof.

  The polycarbonate resin used as the component A of the present invention may be a polyester carbonate copolymerized with an aromatic dicarboxylic acid, for example, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid or a derivative thereof, as long as the gist of the present invention is not impaired. Good.

  The viscosity average molecular weight of the polycarbonate resin used as the component A of the present invention is preferably in the range of 13,000 to 25,000, more preferably 13,000 to 21,000, and in the range of 16,000 to 21,000. Even more preferred is the range of 16,000 to 20,000, most preferred. If the molecular weight exceeds 25,000, the melt viscosity becomes too high and the moldability may be inferior, and if the molecular weight is less than 13,000, there may be a problem in mechanical strength. In addition, the viscosity average molecular weight as used in the field of this invention was calculated | required and calculated | required first using the Ostwald viscometer from the solution which melt | dissolved the polycarbonate resin 0.7g in 20 ml of methylene chloride in the specific viscosity computed by following Formula. The viscosity average molecular weight M is determined by inserting the specific viscosity by the following formula.

Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

  The polycarbonate resin used as the component A of the present invention has a total Cl (chlorine) amount in the resin of preferably 0 to 200 ppm, more preferably 0 to 150 ppm. If the total Cl content in the polycarbonate resin exceeds 200 ppm, the hue and thermal stability deteriorate, which is not preferable.

<Component B: Polycarbonate-polydiorganosiloxane copolymer resin>
The polycarbonate-polydiorganosiloxane copolymer resin used as the component B of the present invention is a polycarbonate comprising a polycarbonate block represented by the following general formula [4] and a polydiorganosiloxane block represented by the following general formula [6] A polydiorganosiloxane copolymer resin is preferred.

［上記一般式〔４〕において、Ｒ^１及びＲ^２は夫々独立して水素原子、ハロゲン原子、炭素原子数１〜１８のアルキル基、炭素原子数１〜１８のアルコキシ基、炭素原子数６〜２０のシクロアルキル基、炭素原子数６〜２０のシクロアルコキシ基、炭素原子数２〜１０のアルケニル基、炭素原子数６〜１４のアリール基、炭素原子数６〜１４のアリールオキシ基、炭素原子数７〜２０のアラルキル基、炭素原子数７〜２０のアラルキルオキシ基、ニトロ基、アルデヒド基、シアノ基及びカルボキシル基からなる群から選ばれる基を表し、それぞれ複数ある場合はそれらは同一でも異なっていても良く、ａ及びｂは夫々１〜４の整数であり、Ｗは単結合もしくは下記一般式〔５〕で表される基からなる群より選ばれる少なくとも一つの基である。

[In General Formula [4], R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or 6 to 6 carbon atoms. 20 cycloalkyl groups, C6-C20 cycloalkoxy groups, C2-C10 alkenyl groups, C6-C14 aryl groups, C6-C14 aryloxy groups, carbon atoms Represents a group selected from the group consisting of 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. A and b are each an integer of 1 to 4, and W is a single bond or at least one group selected from the group consisting of groups represented by the following general formula [5]. .

（上記一般式〔５〕においてＲ^１１，Ｒ^１２，Ｒ^１３，Ｒ^１４，Ｒ^１５，Ｒ^１６，Ｒ^１７及びＲ^１８は夫々独立して水素原子、炭素原子数１〜１８のアルキル基、炭素原子数６〜１４のアリール基及び炭素原子数７〜２０のアラルキル基からなる群から選ばれる基を表し、Ｒ^１９及びＲ^２０は夫々独立して水素原子、ハロゲン原子、炭素原子数１〜１８のアルキル基、炭素原子数１〜１０のアルコキシ基、炭素原子数６〜２０のシクロアルキル基、炭素原子数６〜２０のシクロアルコキシ基、炭素原子数２〜１０のアルケニル基、炭素原子数６〜１４のアリール基、炭素原子数６〜１０のアリールオキシ基、炭素原子数７〜２０のアラルキル基、炭素原子数７〜２０のアラルキルオキシ基、ニトロ基、アルデヒド基、シアノ基及びカルボキシル基からなる群から選ばれる基を表し、複数ある場合はそれらは同一でも異なっていても良く、ｃは１〜１０の整数、ｄは４〜７の整数である。）］

(In the above general formula [5], R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, carbon Represents a group selected from the group consisting of an aryl group having 6 to 14 atoms and an aralkyl group having 7 to 20 carbon atoms, and R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a halogen atom, or a carbon atom having 1 to 18 carbon atoms. An alkyl group having 1 to 10 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, and 6 carbon atoms. -14 aryl group, aryloxy group having 6 to 10 carbon atoms, aralkyl group having 7 to 20 carbon atoms, aralkyloxy group having 7 to 20 carbon atoms, nitro group, aldehyde group, cyano group and Represents a group selected from the group consisting of carboxyl groups, and when there are a plurality of them, they may be the same or different, c is an integer of 1 to 10, and d is an integer of 4 to 7).

（上記一般式〔６〕において、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は、各々独立に水素原子、炭素数１〜１２のアルキル基又は炭素数６〜１２の置換若しくは無置換のアリール基であり、Ｒ^９及びＲ^１０は夫々独立して水素原子、ハロゲン原子、炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基であり、ｅ及びｆは夫々１〜４の整数であり、ｐは自然数であり、ｑは０又は自然数であり、ｐ＋ｑは４以上１５０以下の自然数である。Ｘは炭素数２〜８の二価脂肪族基である。）

(In the above general formula ^{(6), R 3, R 4, R} 5, R 6, R 7 and ^{R 8} are each independently a hydrogen atom, substituted 6-12 alkyl group carbon atoms or from 1 to 12 carbon atoms Or an unsubstituted aryl group, and R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and e and f Is an integer of 1 to 4, p is a natural number, q is 0 or a natural number, p + q is a natural number of 4 to 150. X is a divalent aliphatic group having 2 to 8 carbon atoms. .)

  Examples of the dihydric phenol (I) for deriving the carbonate structural unit represented by the general formula [4] 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-methyl) Phenyl) propane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxy-3,3′-biphenyl) propane, 2,2-bis ( 4-hydroxy-3-isopropylphenyl) propane, 2,2-bis (3-tert-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-hydroxy) Phenyl) 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'- Hydroxy-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, 1,4-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, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, and the like.

  Among them, 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 is preferred, especially 2,2-bis (4-hydroxyphenyl) propane, 1,1-biphenyl. (4-hydroxyphenyl) cyclohexane, 4,4'-sulfonyl diphenol, and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene is preferred. Among them, 2,2-bis (4-hydroxyphenyl) propane having excellent strength and good durability is most preferable. Moreover, you may use these individually or in combination of 2 or more types.

In the carbonate structural unit represented by the general formula [5], 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 carbon. A substituted or unsubstituted aryl group having 6 to 12 carbon atoms, preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a hydrogen atom, carbon An alkyl group of 1 to 6 or a phenyl group is particularly preferable. R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, preferably a hydrogen atom or 1 to 10 carbon atoms. An alkyl group, particularly preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. As the dihydroxyaryl-terminated polydiorganosiloxane (II) for deriving the carbonate structural unit represented by the above formula [6], for example, a compound represented by the following general formula (I) is preferably used.

  P representing the degree of diorganosiloxane polymerization is a natural number, q is 0 or a natural number, p + q is a natural number of 4 to 150, preferably a natural number of 4 to 120, more preferably a natural number of 4 to 60. A natural number of 4 to 40 is more preferable, and a natural number of 20 to 40 is most preferable. When p + q is less than 4, the releasability during heat caulking is insufficient, and when it exceeds 150, gas generation increases.

The polydiorganosiloxane component content in the total weight of the polycarbonate-polydiorganosiloxane copolymer resin used as the component B of the present invention is preferably 1.0 to 20.0% by weight, more preferably 2.0 to 20.0. % By weight, more preferably 2.0 to 12.0% by weight, even more preferably 3.0 to 12.0% by weight, most preferably 3.0 to 10.0% by weight. is there. If the polydiorganosiloxane component content is less than 1.0% by weight, the releasability during heat caulking is not sufficient, and if it exceeds 20.0% by weight, synthesis may not be possible. In addition, this diorganosiloxane polymerization degree and polydiorganosiloxane component content can be calculated by ¹ H-NMR measurement.

  Next, the manufacturing method of said preferable polycarbonate polydiorganosiloxane copolymer resin is demonstrated below. By reaction of dihydric phenol (I) with a chloroformate-forming compound such as chloroformate of phosgene or dihydric phenol (I) in a mixture of an organic solvent insoluble in water and an aqueous alkali solution in advance. A mixed solution of a chloroformate compound of divalent phenol (I) and / or a carbonate oligomer of dihydric phenol (I) having a terminal chloroformate group is prepared. As the chloroformate-forming compound, phosgene is preferred.

  In producing the chloroformate compound from the dihydric phenol (I), all the dihydric phenol (I) derived from the carbonate structural unit represented by the general formula [1] can be converted to the chloroformate compound at once. Alternatively, a part thereof may be added as a reaction raw material to a subsequent interfacial polycondensation reaction as a post-added monomer. The post-added monomer is added to allow the subsequent polycondensation reaction to proceed rapidly, and it is not necessary to add it when it is not necessary.

  The method for this chloroformate compound formation reaction is not particularly limited, but usually a method of carrying out in a solvent in the presence of an acid binder is preferred. Furthermore, if desired, a small amount of an antioxidant such as sodium sulfite and hydrosulfide may be added, and it is preferable to add them.

  The use ratio of the chloroformate-forming compound may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction. Moreover, when using the phosgene which is a suitable chloroformate formation compound, the method of blowing gasified phosgene into a reaction system can be employ | adopted suitably.

  Examples of the acid binder 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, and mixtures thereof. Is used.

  The use ratio of the acid binder may be appropriately determined in consideration of the stoichiometric ratio (equivalent) of the reaction as described above. Specifically, 2 equivalents or slightly more than 2 equivalents per mole of dihydric phenol (I) used for forming the chloroformate compound of dihydric phenol (I) (usually 1 mole corresponds to 2 equivalents). It is preferable to use an acid binder.

  As said solvent, what is necessary is just to use a solvent inert to various reaction, such as what is used for manufacture of a well-known polycarbonate, individually or as a mixed solvent. Representative examples include hydrocarbon solvents such as xylene, and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. In particular, a halogenated hydrocarbon solvent such as methylene chloride is preferably used.

  The pressure in the formation reaction of the chloroformate compound is not particularly limited and may be any of normal pressure, pressurization, or reduced pressure, but it is usually advantageous to carry out the reaction under normal pressure. The reaction temperature is selected from the range of -20 to 50 ° C, and in many cases, heat is generated with the reaction, so it is desirable to cool with water or ice. Although the reaction time depends on other conditions and cannot be defined unconditionally, it is usually carried out in 0.2 to 10 hours.

  As the pH range in the formation reaction of the chloroformate compound, known interfacial reaction conditions can be used, and the pH is usually adjusted to 10 or more.

  In the production of the polycarbonate-polydiorganosiloxane copolymer resin used as the component B of the present invention, the dihydric phenol (I) having the chloroformate and terminal chloroformate groups of the dihydric phenol (I) is thus obtained. The dihydroxyaryl-terminated polydiorganosiloxane (II) for deriving the carbonate constituent unit represented by the general formula [6] while preparing the mixed solution of the chloroformate compound containing the carbonate oligomer of The dihydroxyaryl-terminated polydiorganosiloxane (II) and the chloroformate compound are added at a rate of 0.01 mol / min or less per 1 mol of the dihydric phenol (I) charged in preparing the mixed solution. Polycarbonate by interfacial polycondensation Obtaining a lysine organosiloxane copolymer resin.

  The polycarbonate-polydiorganosiloxane copolymer resin used as the component B of the present invention can be made into a branched polycarbonate-polydiorganosiloxane copolymer resin by using a branching agent in combination with a dihydric phenol compound. Examples of the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate resin include phloroglucin, phloroglucid, or 4,6-dimethyl-2,4,6-tris (4-hydroxydiphenyl) 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- [ Trisphenol such as 1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol, tetra (4-hydride) Loxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acids Among them, 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable. 1-Tris (4-hydroxyphenyl) ethane is preferred.

Even when the branched polycarbonate-polydiorganosiloxane copolymer resin is produced by a method in which the branching agent is contained in the mixed solution during the production reaction of the chloroformate compound, the interfacial polycondensation after the completion of the production reaction is performed. It may be a method in which a branching agent is added during the reaction. The proportion of the carbonate constituent unit derived from the branching agent is preferably 0.005 to 1.5 mol%, more preferably 0.01 to 1.2 mol%, in the total amount of carbonate constituent units constituting the copolymer resin. Especially preferably, it is 0.05-1.0 mol%. Such a branched structure amount can be calculated by ¹ H-NMR measurement.

The pressure in the system in the polycondensation reaction can be any of reduced pressure, normal pressure, or increased pressure, but can usually be suitably performed at normal pressure or about the pressure of the reaction system. The reaction temperature is selected from the range of −20 to 50 ° C., and in many cases, heat is generated with the polymerization, so it is desirable to cool with water or ice. Since the reaction time varies depending on other conditions such as the reaction temperature, it cannot be generally specified, but it is usually performed in 0.5 to 10 hours. In some cases, the obtained polycarbonate-polydiorganosiloxane copolymer resin is appropriately subjected to physical treatment (mixing, fractionation, etc.) and / or chemical treatment (polymer reaction, crosslinking treatment, partial decomposition treatment, etc.) to obtain a desired reduction. It can also be obtained as a polycarbonate-polydiorganosiloxane copolymer resin having a viscosity [η _SP / c]. The obtained reaction product (crude product) can be recovered as a polycarbonate-polydiorganosiloxane copolymer resin having a desired purity (purity) after various post-treatments such as a known separation and purification method.

  The viscosity-average molecular weight of the polycarbonate-polydiorganosiloxane copolymer resin used as the component B of the present invention is preferably in the range of 13,000 to 25,000, more preferably 13,000 to 21,000, and 16,000 to A range of 21,000 is even more preferred, with a range of 16,000-20,000 being most preferred. If the molecular weight exceeds 25,000, the melt viscosity becomes too high and the moldability may be inferior, and if the molecular weight is less than 13,000, there may be a problem in mechanical strength.

The viscosity average molecular weight of the polycarbonate-polydiorganosiloxane copolymer resin used as the component B of the present invention is calculated as follows. First, the specific viscosity (η _SP ) calculated by the following formula is obtained from an solution obtained by dissolving 0.7 g of a polycarbonate-polydiorganosiloxane copolymer resin in 100 ml of methylene chloride at 20 ° C. using an Ostwald viscometer,
Specific viscosity (η _SP ) = (t−t ⁰ ) / t ⁰
[T ⁰ is methylene chloride falling seconds, t is sample solution falling seconds]
From the obtained specific viscosity (η _SP ), the viscosity average molecular weight Mv is calculated by the following formula.
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ Mv ^0.83
c = 0.7

  The content of the polydiorganosiloxane block represented by the following general formula [7] contained in the above general formula [6] contained in the component B is 1.0 to 12 based on the total weight of the polycarbonate resin composition. It is preferably 0% by weight, more preferably 2.0 to 10.0% by weight, even more preferably 2.0 to 8.0% by weight, still more preferably 3.0 to 8.0% by weight. 0.0 to 8.0% by weight is most preferred. If this ratio is less than 1.0% by weight, the releasability at the time of heat caulking is insufficient, and if it exceeds 12.0% by weight, gas generation may increase, which is not preferable.

（上記一般式〔７〕において、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は、各々独立に水素原子、炭素数１〜１２のアルキル基又は炭素数６〜１２の置換若しくは無置換のアリール基であり、ｐは自然数であり、ｑは０又は自然数であり、ｐ＋ｑは４以上１５０以下の自然数である。）

(In the above general formula ^{(7), R 3, R 4, R} 5, R 6, R 7 and ^{R 8} are each independently a hydrogen atom, substituted 6-12 alkyl group carbon atoms or from 1 to 12 carbon atoms Or an unsubstituted aryl group, 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.)

  The average size of the polydiorganosiloxane domain contained in the polycarbonate-polydiorganosiloxane copolymer resin used as component B of the present invention is suitably in the range of 5 to 100 nm. The lower limit of the average size is preferably 6 nm, and the upper limit of the average size is preferably 90 nm, more preferably 80 nm, and particularly preferably 70 nm. If the amount is less than the lower limit of the preferable range, the releasability during heat caulking is insufficient, and if the upper limit of the preferable range is exceeded, the appearance of the molded product and the paintability may be deteriorated.

  In addition, the average domain size of this polydiorganosiloxane domain is evaluated by the small angle X-ray scattering method (Small Angle X-ray Scattering: SAXS). The small-angle X-ray scattering method is a method for measuring diffuse scattering / diffraction generated in a small-angle region where the scattering angle (2θ) is less than 10 °. In this small-angle X-ray scattering method, if there is a region of about 1 to 100 nm in which the electron density is different in a substance, the X-ray diffuse scattering is measured by the difference in the electron density. The particle diameter of the measurement object is obtained based on the scattering angle and the scattering intensity. When the polydiorganosiloxane domain is dispersed in the matrix of the polycarbonate-polydiorganosiloxane copolymer resin used as the component B of the present invention, the diffuse scattering of X-rays is caused by the difference in electron density between the polycarbonate matrix and the polydiorganosiloxane domain. Occurs. The scattering intensity I at each scattering angle (2θ) in the range where the scattering angle (2θ) is less than 10 ° is measured, the small-angle X-ray scattering profile is measured, the polydiorganosiloxane domain is a spherical domain, and the particle size distribution varies. Assuming the presence of, the simulation is performed using a commercially available analysis software from the temporary particle size and the temporary particle size distribution model to obtain the average size of the polydiorganosiloxane domain. According to the small-angle X-ray scattering method, the average size of polydiorganosiloxane domains dispersed in a polycarbonate polymer matrix, which cannot be accurately measured by transmission electron microscopy, can be measured accurately, simply, and with good reproducibility. Can do. The average domain size means the number average of individual domain sizes.

  The term “average domain size” used in connection with the present invention is a three-stage plate made by injection molding (width 50 mm, length 90 mm, thickness 3.0 mm (length 20 mm), 2.0 mm from the gate side) The measurement value obtained by measuring the thickness 1.0mm part of length 45mm) and 1.0mm (length 25mm) by a small angle X ray scattering method is shown.

  Content of B component is 10-100 weight% in 100 weight% of resin components, 20-99 weight% is preferable, 20-95 weight% is more preferable, 40-95 weight% is further more preferable, 50- 95% by weight is most preferred. When the content of the component B is less than 10% by weight, not only the releasability at the time of thermal caulking becomes insufficient, but also the impact resistance decreases.

(C component: glass flakes)
The glass flakes used as the component C of the present invention are glass flakes having an average thickness of 0.2 to 0.7 μm, preferably 0.3 to 0.7 μm, more preferably 0.4 to 0.7 μm. When glass flakes with an average thickness in the above range are used, the thermal caulking bonding stability and mechanical properties are greatly improved as compared with the case where glass flakes with an average thickness of greater than 0.7 μm are used. Appears the same characteristics. On the other hand, when the average thickness is less than 0.2 μm, the glass flakes are not cracked sufficiently when the resin is kneaded, and a sufficient reinforcing effect is not exhibited. Here, the average thickness is measured by the following method. That is, using a scanning electron microscope (SEM), each thickness is measured for 100 or more glass flakes, and the measured values are averaged. In this case, the glass flake alone may be measured by observing with a scanning electron microscope, or the glass flake may be filled with a resin and molded, and the glass flake may be broken and observed by observing the fracture surface. In any measurement method, it is necessary to adjust the sample stage of the scanning electron microscope with the sample stage fine movement device so that the glass flake cross section (thickness surface) is perpendicular to the irradiation electron beam axis of the scanning electron microscope.

  Such glass flakes are preferably glass flakes surface-treated with a surface treatment agent. The amount of the surface treatment agent is preferably 1.5 to 5 parts by weight, more preferably 1.7 to 5 parts by weight, still more preferably 2 to 5 parts by weight, particularly 2.5 to 4 parts per 100 parts by weight of the glass flakes. .5 parts by weight. When glass flakes having a surface treatment agent amount of less than 1.5 parts by weight are used, the mechanical strength may not be improved. On the other hand, when glass flakes having a surface treatment agent amount of more than 5 parts by weight are used, the thermal stability during molding may be deteriorated during extrusion, and the resin is colored and the appearance of the molded product is impaired. There is a case. Such a surface treatment agent includes at least one resin selected from the group consisting of polyvinyl acetate resins, polyacrylate resins, polyurethane resins, epoxy resins, copolymers thereof, and modified products thereof, and these A coupling agent such as a silane coupling agent, a titanium coupling agent, an aluminate coupling agent, and a zirconia coupling agent as a coupling agent is preferable from the viewpoint of improving mechanical strength, and more A combination of an epoxy resin and a silane coupling agent is preferred. The surface treatment is one or more resins selected from the group consisting of polyvinyl acetate resins, polyacrylate resins, polyurethane resins, epoxy resins, copolymers thereof, and modified products thereof, and couplings thereof. A coupling agent such as a silane coupling agent, titanium coupling agent, aluminate coupling agent, zirconia coupling agent, etc. as an agent is mixed at a predetermined ratio, and further about 2 to 100 times with water or an organic solvent. This is carried out by preparing a diluted processing solution, spraying the processing solution on glass flakes, and then drying. Further, glass flakes that are granulated or converged with a binder such as an acrylic resin, urethane resin, epoxy resin, or unsaturated polyester resin are preferred in terms of handling. However, the glass flake average particle diameter range and the thickness range described above are not applied to the granular material or the converging material obtained by the granulation or converging. Various glass compositions represented by A glass, C glass, E glass, etc. are applied and the glass composition of said glass flakes is not specifically limited. Moreover, 10-300 micrometers is preferable, as for the average particle diameter of this glass flakes, More preferably, it is 15-250 micrometers, More preferably, it is 20-200 micrometers. Here, the average particle diameter is calculated as the median diameter of the weight distribution of the particle diameter obtained by the standard sieving method.

  Content of C component is 10-100 weight part with respect to 100 weight part of resin components, 10-80 weight part is preferable, 10-60 weight part is more preferable, 20-60 weight part is further more preferable. If the content of component C is less than 10 parts by weight, the strength is insufficient, and if it exceeds 100 parts by weight, the thermal caulking binding property and the thermal caulking binding stability are lowered.

(Other additives)
In order to improve the thermal stability and design of the glass-reinforced polycarbonate resin composition constituting the heat-caulking bonded body of the present invention, additives used for these improvements are advantageously used. Hereinafter, these additives will be specifically described.

(I) Thermal Stabilizer The glass-reinforced polycarbonate resin composition constituting the heat-caulking bonded body of the present invention can be blended with various known stabilizers. Examples of the stabilizer include phosphorus stabilizers and hindered phenol antioxidants.

(I) Phosphorus stabilizer It is preferable that the glass-reinforced polycarbonate resin composition constituting the heat-caulking conjugate of the present invention is blended with a phosphorus stabilizer to the extent that it does not promote hydrolyzability. Such phosphorus stabilizers improve thermal stability during production or molding, and improve mechanical properties, hue, and molding stability. Examples of phosphorus stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and tertiary phosphine. Specifically, as the phosphite compound, for example, triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl Phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, tris ( Diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylpheny) ) Phosphite, tris (2,6-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2 , 6-Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite Phyto, bis (nonylphenyl) pentaerythritol diphosphite, dicyclohexyl pentaerythritol diphosphite, and the like. Further, as other phosphite compounds, those which react with dihydric phenols and have a cyclic structure can be used. For example, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert- Butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-methylenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite 2,2′-ethylidenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite. Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, Examples thereof include diisopropyl phosphate, and triphenyl phosphate and trimethyl phosphate are preferable.

  Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenedi. Phosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite Tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylene diphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl)- Examples include 4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, and tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite, bis. (Di-tert-butylphenyl) -phenyl-phenylphosphonite is preferred, tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl)- More preferred is phenyl-phenylphosphonite. Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted. Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate. Tertiary phosphine includes triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, tri-p-tolyl. Examples include phosphine, trinaphthylphosphine, and diphenylbenzylphosphine. A particularly preferred tertiary phosphine is triphenylphosphine. The phosphorus stabilizers can be used alone or in combination of two or more. Among the phosphorus stabilizers, an alkyl phosphate compound typified by trimethyl phosphate is preferably blended. A combination of such an alkyl phosphate compound and a phosphite compound and / or phosphonite compound is also a preferred embodiment.

(Ii) Hindered phenol-based stabilizer A hindered phenol-based stabilizer can be further added to the glass-reinforced polycarbonate resin composition constituting the heat-caulked conjugate of the present invention. Such blending exhibits an effect of suppressing, for example, hue deterioration during molding and hue deterioration during long-term use. Examples of the hindered phenol-based stabilizer include α-tocopherol, butylhydroxytoluene, sinapir alcohol, vitamin E, n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-tert-butylfel). 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, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′- Methylene bis (4-ethyl-6-tert-butylphenol), 4,4′-methylene bis (2,6- Di-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-dimethylene-bis (6-α-methyl-benzyl-p-cresol) 2,2′- Ethylidene-bis (4,6-di-tert-butylphenol), 2,2'-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-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-methyl 6- (3-tert-butyl) -5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -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), 2,2-thiodiethyl Nbis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 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, tris (3,5-di-tert-butyl-4-hydroxyphenyl) iso Anurate, 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 and the like. All of these are readily available. The said hindered phenol type stabilizer can be used individually or in combination of 2 or more types. The blending amount of the phosphorus stabilizer and the hindered phenol stabilizer is preferably 0.0001 to 1 part by weight, more preferably 0.001 to 0.5 part by weight, and further preferably 100 parts by weight of the resin component. Is 0.005 to 0.3 parts by weight.

(Iii) Heat stabilizer other than the above The glass-reinforced polycarbonate resin composition constituting the heat-caulking conjugate of the present invention is blended with a heat stabilizer other than the phosphorus stabilizer and the hindered phenol stabilizer. You can also. Preferable examples of such other heat stabilizers include lactone stabilizers represented by a reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene. Is done. Details of such a stabilizer are described in JP-A-7-233160. Such a compound is commercially available as Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS) and can be used. Furthermore, a stabilizer obtained by mixing the compound with various phosphite compounds and hindered phenol compounds is commercially available. For example, Irganox HP-2921 manufactured by the above company is preferably exemplified. The blending amount of the lactone stabilizer is preferably 0.0005 to 0.05 parts by weight, more preferably 0.001 to 0.03 parts by weight with respect to 100 parts by weight of the resin component. Other stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. Illustrated. The amount of the sulfur-containing stabilizer is preferably 0.001 to 0.1 parts by weight, more preferably 0.01 to 0.08 parts by weight with respect to 100 parts by weight of the resin component. An epoxy compound can be mix | blended with the resin composition of this invention as needed. Such an epoxy compound is blended for the purpose of suppressing mold corrosion, and basically any compound having an epoxy functional group can be applied. Specific examples of preferable epoxy compounds include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate, 1,2-epoxy-4-butane of 2,2-bis (hydroxymethyl) -1-butanol. Examples include (2-oxiranyl) cyclosexane adduct, a copolymer of methyl methacrylate and glycidyl methacrylate, and a copolymer of styrene and glycidyl methacrylate. The amount of the epoxy compound added is preferably 0.003 to 0.2 parts by weight, more preferably 0.004 to 0.15 parts by weight, and still more preferably 0.005 to 100 parts by weight of the resin component. -0.1 parts by weight.

(II) Flame retardant A flame retardant can be mix | blended with the glass reinforced polycarbonate resin composition which comprises the heat crimping | bonding body of this invention. The compounding of such a compound brings about an improvement in flame retardancy, but besides that, based on the properties of each compound, for example, an improvement in antistatic property, fluidity, rigidity and thermal stability is brought about. Examples of such flame retardants include (i) organic metal salt flame retardants (for example, organic sulfonate alkali (earth) metal salts, organic borate metal salt flame retardants, organic stannate metal salt flame retardants, etc.), ii) organophosphorous flame retardants (for example, organic group-containing monophosphate compounds, phosphate oligomer compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, phosphonic acid amide compounds, etc.), (iii) silicone flame retardants comprising silicone compounds (Iv) fibrillated PTFE, among which organometallic salt flame retardants and organic phosphorus flame retardants are preferred. These may be used alone or in combination.

(I) Organometallic salt flame retardant The organometallic salt compound is an alkali (earth) metal salt of an organic acid having 1 to 50 carbon atoms, preferably 1 to 40, preferably an alkali (earth) metal salt of an organic sulfonate. It is preferable that The alkali (earth) metal salt of the organic sulfonate includes a fluorine-substituted alkyl sulfone such as a metal salt of a perfluoroalkyl sulfonic acid having 1 to 10, preferably 2 to 8 carbon atoms and an alkali metal or an alkaline earth metal. Metal salts of acids and metal salts of aromatic sulfonic acids having 7 to 50 carbon atoms, preferably 7 to 40 carbon atoms, and alkali metals or alkaline earth metals are included. Examples of the alkali metal constituting the metal salt include lithium, sodium, potassium, rubidium and cesium, and examples of the alkaline earth metal include beryllium, magnesium, calcium, strontium and barium. More preferred is an alkali metal. Among such alkali metals, rubidium and cesium having larger ionic radii are suitable when the requirement for transparency is higher, but these are not general-purpose and difficult to purify, resulting in cost. It may be disadvantageous. On the other hand, metals with smaller ionic radii such as lithium and sodium may be disadvantageous in terms of flame retardancy. Considering these, the alkali metal in the sulfonic acid alkali metal salt can be properly used. In any respect, the sulfonic acid potassium salt having an excellent balance of properties is most preferable. Such potassium salts and sulfonic acid alkali metal salts comprising other alkali metals can be used in combination.

  Specific examples of alkali metal perfluoroalkyl sulfonates include potassium trifluoromethane sulfonate, potassium perfluorobutane sulfonate, potassium perfluorohexane sulfonate, potassium perfluorooctane sulfonate, sodium pentafluoroethane sulfonate, perfluoro Sodium butanesulfonate, sodium perfluorooctanesulfonate, lithium trifluoromethanesulfonate, lithium perfluorobutanesulfonate, lithium perfluoroheptanesulfonate, cesium trifluoromethanesulfonate, cesium perfluorobutanesulfonate, perfluorooctanesulfonate Cesium, cesium perfluorohexane sulfonate, rubidium perfluorobutane sulfonate, and perf Oro hexane sulfonate rubidium, and these may be used in combination of at least one or two. Here, the carbon number of the perfluoroalkyl group is preferably in the range of 1-18, more preferably in the range of 1-10, and still more preferably in the range of 1-8.

  Of these, potassium perfluorobutanesulfonate is particularly preferred. In the alkali (earth) metal salt of perfluoroalkylsulfonic acid composed of an alkali metal, usually not a few fluoride ions (F-) are mixed. The presence of such fluoride ions can be a factor that lowers the flame retardancy, so it is preferably reduced as much as possible. The ratio of such fluoride ions can be measured by ion chromatography. The content of fluoride ions is preferably 100 ppm or less, more preferably 40 ppm or less, and particularly preferably 10 ppm or less. Moreover, it is suitable that it is 0.2 ppm or more in terms of production efficiency. Such alkali (earth) metal salt of perfluoroalkylsulfonic acid having a reduced amount of fluoride ion is contained in a raw material when producing a fluorine-containing organometallic salt using a known production method. A method for reducing the amount of fluoride ions, a method for removing hydrogen fluoride and the like obtained by the reaction by a gas generated during the reaction or heating, and a purification method such as recrystallization and reprecipitation for producing a fluorine-containing organometallic salt Can be produced by a method of reducing the amount of fluoride ions using, for example. In particular, organic metal salt flame retardants are relatively soluble in water, and therefore ion-exchanged water, especially water that has an electric resistance of 18 MΩ · cm or more, that is, an electric conductivity of about 0.55 μS / cm or less is used. In addition, it is preferable to produce by a process of dissolving at a temperature higher than room temperature and washing, then cooling and recrystallization.

  Specific examples of the aromatic (earth) metal salt of an aromatic sulfonate include, for example, disodium diphenyl sulfide-4,4′-disulfonate, dipotassium diphenyl sulfide-4,4′-disulfonate, potassium 5-sulfoisophthalate, Sodium 5-sulfoisophthalate, polysodium polyethylene terephthalate polysulfonate, calcium 1-methoxynaphthalene-4-sulfonate, disodium 4-dodecylphenyl ether disulfonate, polysodium poly (2,6-dimethylphenylene oxide) polysulfonate Poly (1,3-phenylene oxide) polysulfonic acid polysodium, poly (1,4-phenylene oxide) polysulfonic acid polysodium, poly (2,6-diphenylphenylene oxide) polysulfonic acid poly Lithium, poly (2-fluoro-6-butylphenylene oxide) polysulfonate, potassium sulfonate of benzenesulfonate, sodium benzenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, dipotassium p-benzenedisulfonate, naphthalene-2 , 6-disulfonic acid dipotassium, biphenyl-3,3'-disulfonic acid calcium, diphenylsulfone-3-sulfonic acid sodium, diphenylsulfone-3-sulfonic acid potassium, diphenylsulfone-3,3'-disulfonic acid dipotassium, diphenylsulfone -3,4'-dipotassium disulfonate, α, α, α-trifluoroacetophenone-4-sodium sulfonate, dipotassium benzophenone-3,3'-disulfonate, thiof 2,5-disulfonic acid disodium, thiophene-2,5-disulfonic acid dipotassium, thiophene-2,5-disulfonic acid calcium, benzothiophene sodium sulfonate, diphenyl sulfoxide-4- potassium sulfonate, naphthalene sulfone Examples thereof include a formalin condensate of sodium acid and a formalin condensate of sodium anthracene sulfonate. Among these aromatic sulfonate alkali (earth) metal salts, potassium salts are particularly preferable. Among these aromatic sulfonate alkali (earth) metal salts, potassium diphenylsulfone-3-sulfonate and dipotassium diphenylsulfone-3,3′-disulfonate are preferable, and particularly a mixture thereof (the former and the latter). Is preferably 15/85 to 30/70).

  Preferable examples of the organic metal salt other than the alkali (earth) metal sulfonate include an alkali (earth) metal salt of a sulfate ester and an alkali (earth) metal salt of an aromatic sulfonamide. Examples of alkali (earth) metal salts of sulfates include alkali (earth) metal salts of sulfates of monovalent and / or polyhydric alcohols, and such monovalent and / or polyhydric alcohols. Examples of sulfuric acid esters include methyl sulfate, ethyl sulfate, lauryl sulfate, hexadecyl sulfate, polyoxyethylene alkylphenyl ether sulfate, pentaerythritol mono-, di-, tri-, tetra-sulfate, and lauric acid monoglyceride sulfate. Examples include esters, sulfates of palmitic acid monoglyceride, and sulfates of stearic acid monoglyceride. The alkali (earth) metal salts of these sulfates are preferably alkali (earth) metal salts of lauryl sulfate. Alkali (earth) metal salts of aromatic sulfonamides include, for example, saccharin, N- (p-tolylsulfonyl) -p-toluenesulfonimide, N- (N′-benzylaminocarbonyl) sulfanilimide, and N- ( And an alkali (earth) metal salt of phenylcarboxyl) sulfanilimide. The content of the organometallic salt flame retardant is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.5 part by weight, and still more preferably 0.01 to 0 part per 100 parts by weight of the resin component. .3 parts by weight, particularly preferably 0.03 to 0.15 parts by weight.

(Ii) Organophosphorus Flame Retardant As the organophosphorus flame retardant, an aryl phosphate compound or a phosphazene compound is preferably used. Since these organophosphorous flame retardants have a plasticizing effect, they are advantageous in that molding processability can be improved. Various known phosphate compounds as conventional flame retardants can be used as the aryl phosphate compound, and more preferably, one or more phosphate compounds represented by the following general formula [8] can be mentioned.

（但し上記式中のＸは、二価フェノールから誘導される二価の有機基を表し、Ｒ^１、Ｒ^２、Ｒ^３、およびＲ^４はそれぞれ一価フェノールから誘導される一価の有機基を表す。ｊ、ｋ、ｌ及びｍはそれぞれ独立して０または１であり、ｎは０〜５の整数であり、重合度ｎの異なるリン酸エステルの混合物の場合はｎはその平均値を表し、０〜５の値である。）

(However, X in the above formula represents a divalent organic group derived from a dihydric phenol, and R ¹ , R ² , R ³ and R ⁴ are each a monovalent organic group derived from a monohydric phenol. J, k, l and m are each independently 0 or 1, n is an integer of 0 to 5, and in the case of a mixture of phosphate esters having different degrees of polymerization, n is an average value thereof. Represents a value between 0 and 5.)

  The phosphate compound of the above formula may be a mixture of compounds having different n numbers, in which case the average n number is preferably 0.5 to 1.5, more preferably 0.8 to 1. 2, More preferably, it is 0.95-1.15, Most preferably, it is the range of 1-1.14.

  Preferable specific examples of the dihydric phenol for deriving X include hydroquinone, resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4 -Hydroxyphenyl) ketone and bis (4-hydroxyphenyl) sulfide are exemplified, among which resorcinol, bisphenol A, and dihydroxydiphenyl are preferable.

Preferable specific examples of the monohydric phenol for deriving R ¹ , R ² , R ³ , and R ⁴ include phenol, cresol, xylenol, isopropylphenol, butylphenol, and p-cumylphenol. Are phenol and 2,6-dimethylphenol.

  The monohydric phenol may be substituted with a halogen atom. Specific examples of the phosphate compound having a group derived from the monohydric phenol include tris (2,4,6-tribromophenyl) phosphate and tris. Examples include (2,4-dibromophenyl) phosphate, tris (4-bromophenyl) phosphate, and the like.

  On the other hand, specific examples of the phosphate compound not substituted with a halogen atom include monophosphate compounds such as triphenyl phosphate and tri (2,6-xylyl) phosphate, and resorcinol bisdi (2,6-xylyl) phosphate). Preferred are phosphate oligomers mainly composed of phosphate oligomers, phosphate oligomers mainly composed of 4,4-dihydroxydiphenyl bis (diphenyl phosphate), and phosphate oligomers mainly composed of bisphenol A bis (diphenyl phosphate). Indicates that it may contain a small amount of other components having different degrees of polymerization, more preferably the component of n = 1 in the formula [8] is 80% by weight or more, more preferably 85% by weight or more, and still more preferably Contains over 90% by weight Are shown.).

  As the phosphazene compound, various known phosphazene compounds can be used as conventional flame retardants, and phosphazene compounds represented by the following general formulas [9] and [10] are preferable.

（式中、Ｘ^１、Ｘ^２、Ｘ^３、Ｘ^４は、水素、水酸基、アミノ基、またはハロゲン原子を含まない有機基を表す。また、ｒは３〜１０の整数を表す）。上記式〔９〕、〔１０〕中、Ｘ^１、Ｘ^２、Ｘ^３、Ｘ^４で表されるハロゲン原子を含まない有機基としては、例えば、アルコキシ基、フェニル基、アミノ基、アリル基などが挙げられる。中でも上記式〔９〕で表される環状ホスファゼン化合物が好ましく、更に、上記式〔９〕中のＸ^１、Ｘ^２がフェノキシ基である環状フェノキシホスファゼンが特に好ましい。

(Wherein, X ¹ , X ² , X ³ and X ⁴ represent hydrogen, a hydroxyl group, an amino group, or an organic group containing no halogen atom. R represents an integer of 3 to 10). In the above formulas [9] and [10], examples of the organic group not containing a halogen atom represented by X ¹ , X ² , X ³ , X ⁴ include an alkoxy group, a phenyl group, an amino group, and an allyl group. Is mentioned. Among them, a cyclic phosphazene compound represented by the above formula [9] is preferable, and a cyclic phenoxyphosphazene in which X ¹ and X ² in the above formula [9] are phenoxy groups is particularly preferable.

  The content of the organophosphorus flame retardant is preferably 1 to 50 parts by weight, more preferably 2 to 30 parts by weight, and still more preferably 5 to 20 parts by weight with respect to 100 parts by weight of the resin component. If the blending amount of the organic phosphorus flame retardant is less than 1 part by weight, it is difficult to obtain a flame retardant effect, and if it exceeds 50 parts by weight, strand breakage or surging occurs during kneading extrusion, resulting in reduced productivity. May occur.

(Iii) Silicone Flame Retardant A silicone compound used as a silicone flame retardant improves flame retardancy by a chemical reaction during combustion. As the compound, various compounds conventionally proposed as a flame retardant for aromatic polycarbonate resin can be used. Silicone compounds are highly flame retardant, especially when polycarbonate resins are used, either by themselves when bonded or by bonding with components derived from the resin to form a structure, or by a reduction reaction during the formation of the structure. It is thought to provide an effect.

  Therefore, it is preferable that a group having high activity in such a reaction is contained, and more specifically, a predetermined amount of at least one group selected from an alkoxy group and a hydrogen (ie, Si—H group) is contained. preferable. As a content rate of this group (alkoxy group, Si-H group), the range of 0.1-1.2 mol / 100g is preferable, the range of 0.12-1 mol / 100g is more preferable, 0.15-0. The range of 6 mol / 100 g is more preferable. Such a ratio can be determined by measuring the amount of hydrogen or alcohol generated per unit weight of the silicone compound by the alkali decomposition method. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and particularly preferably a methoxy group.

Generally, the structure of a silicone compound is constituted by arbitrarily combining the following four types of siloxane units. That is, M units: (CH ₃ ) ₃ SiO _1/2 , H (CH ₃ ) ₂ SiO _1/2 , H ₂ (CH ₃ ) SiO _1/2 , (CH ₃ ) ₂ (CH ₂ = CH) SiO _{1 / 2} , monofunctional siloxane units such as (CH ₃ ) ₂ (C ₆ H ₅ ) SiO _1/2 , (CH ₃ ) (C ₆ H ₅ ) (CH ₂ ═CH) SiO _1/2 , D unit: _{2 such as} (CH ₃ ) ₂ SiO, H (CH ₃ ) SiO, H ₂ SiO, H (C ₆ H ₅ ) SiO, (CH ₃ ) (CH ₂ ═CH) SiO, (C ₆ H ₅ ) ₂ SiO Functional siloxane unit, T unit: (CH ₃ ) SiO _3/2 , (C ₃ H ₇ ) SiO _3/2 , HSiO _3/2 , (CH ₂ ═CH) SiO _3/2 , (C ₆ H ₅ ) trifunctional siloxane units SiO _3/2, etc., Q unit: 4 represented by SiO ₂ It is a functional siloxane units.

  Specific examples of the structure of the silicone compound used in the silicone-based flame retardant include Dn, Tp, MmDn, MmTp, MmQq, MmDnTp, MmDnQq, MmTpQq, MmDnTpQq, DnTp, DnQq, and DnTpQq. Among these, preferred structures of the silicone compound are MmDn, MmTp, MmDnTp, and MmDnQq, and a more preferred structure is MmDn or MmDnTp.

  Here, the coefficients m, n, p, and q in the above formula are integers of 1 or more that indicate the degree of polymerization of each siloxane unit, and the sum of the coefficients in each formula is the average degree of polymerization of the silicone compound. . This average degree of polymerization is preferably in the range of 3 to 150, more preferably in the range of 3 to 80, still more preferably in the range of 3 to 60, and particularly preferably in the range of 4 to 40. The better the range, the better the flame retardancy. Further, as described later, a silicone compound containing a predetermined amount of an aromatic group is excellent in transparency and hue. As a result, good reflected light can be obtained. When any of m, n, p, and q is a numerical value of 2 or more, the siloxane unit with the coefficient can be two or more types of siloxane units having different hydrogen atoms or organic residues to be bonded. .

  The silicone compound may be linear or have a branched structure. The organic residue bonded to the silicon atom is preferably an organic residue having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms. Specific examples of such an organic residue include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a decyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, And aralkyl groups such as tolyl groups. More preferably, they are a C1-C8 alkyl group, an alkenyl group, or an aryl group. As the alkyl group, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, and a propyl group is particularly preferable. Further, the silicone compound used as the silicone flame retardant preferably contains an aryl group. On the other hand, silane compounds and siloxane compounds as organic surface treatment agents for titanium dioxide pigments are clearly distinguished from silicone-based flame retardants in their preferred embodiments in that it is preferable to contain no aryl group. . The silicone compound used as the silicone-based flame retardant may contain a reactive group in addition to the Si-H group and the alkoxy group. Examples of the reactive group include an amino group, a carboxyl group, an epoxy group, and a vinyl group. Examples thereof include a group, a mercapto group, and a methacryloxy group.

  The content of the silicone flame retardant is preferably 0.01 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, and still more preferably 1 to 5 parts by weight with respect to 100 parts by weight of the resin component.

(Iv) Polytetrafluoroethylene (fibrillated PTFE) having fibril-forming ability
The fibrillated PTFE may be fibrillated PTFE alone or a mixed form of fibrillated PTFE, that is, a polytetrafluoroethylene-based mixture composed of fibrillated PTFE particles and an organic polymer. Fibrilized PTFE has an extremely high molecular weight and tends to be bonded to each other by an external action such as shearing force to form a fiber. Its number average molecular weight ranges from 1.5 million to tens of millions. The lower limit is more preferably 3 million. The number average molecular weight is calculated based on the melt viscosity of polytetrafluoroethylene at 380 ° C. as disclosed in, for example, JP-A-6-145520. That is, the fibrillated PTFE has a melt viscosity at 380 ° C. measured by the method described in this publication in the range of 10 ⁷ to 10 ¹³ poise, preferably in the range of 10 ⁸ to 10 ¹² poise. Such PTFE can be used in solid form or in the form of an aqueous dispersion. Such fibrillated PTFE can also be used in a mixed form with other resins in order to improve dispersibility in the resin and to obtain better flame retardancy and mechanical properties.

  Further, as disclosed in JP-A-6-145520, those having a structure having such a fibrillated PTFE as a core and a low molecular weight polytetrafluoroethylene as a shell are also preferably used.

  Examples of such commercially available fibrillated PTFE include Teflon (registered trademark) 6J from Mitsui DuPont Fluorochemical Co., Ltd., Polyflon MPA FA500, F-201L from Daikin Chemical Industries, Ltd., and the like.

  As a mixed form of fibrillated PTFE, (1) a method in which an aqueous dispersion of fibrillated PTFE and an aqueous dispersion or solution of an organic polymer are mixed and co-precipitated to obtain a co-agglomerated mixture (JP-A-60-258263). (2) A method of mixing an aqueous dispersion of fibrillated PTFE and dried organic polymer particles (Japanese Patent Laid-Open No. 4-272957). Described method), (3) A method in which an aqueous dispersion of fibrillated PTFE and an organic polymer particle solution are uniformly mixed, and the respective media are simultaneously removed from the mixture (Japanese Patent Laid-Open Nos. 06-220210, (Method described in Japanese Patent Application Laid-Open No. 08-188653), (4) A method of polymerizing monomers forming an organic polymer in an aqueous dispersion of fibrillated PTFE (Method described in JP-A-9-95583), and (5) an aqueous dispersion of PTFE and an organic polymer dispersion are uniformly mixed, and then a vinyl monomer is further polymerized in the mixed dispersion. Thereafter, those obtained by a method for obtaining a mixture (a method described in JP-A-11-29679, etc.) can be used.

  Commercial products of these mixed forms of fibrillated PTFE include methabrene represented by Mitsubishi Rayon Co., Ltd.'s "methabrene A3000" (trade name), "methabrene A3700" (trade name), and "methabrene A3800" (trade name). Examples include A series, SN3300B7 (trade name) manufactured by Shine Polymer, and “BLENDEX B449” (trade name) manufactured by GE Specialty Chemicals.

  The proportion of fibrillated PTFE in the mixed form is preferably 1% by weight to 95% by weight, more preferably 10% by weight to 90% by weight, and more preferably 20% by weight in 100% by weight of the mixture. Most preferred is from 80% to 80% by weight.

  When the ratio of fibrillated PTFE in the mixed form is within such a range, good dispersibility of the fibrillated PTFE can be achieved. The content of fibrillated PTFE is preferably 0.001 to 0.5 parts by weight, more preferably 0.01 to 0.5 parts by weight, with respect to 100 parts by weight of the resin component. 5 parts by weight is more preferable.

(III) Dye / pigment The glass-reinforced polycarbonate resin composition constituting the heat-caulking-bonded body of the present invention can further contain various dyes / pigments and can provide a molded product exhibiting various design properties. Examples of dyes used in the present invention include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as bitumen, perinone dyes, quinoline dyes, quinacridone dyes, Examples thereof include dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Furthermore, the polycarbonate resin composition of the present invention can be blended with a metallic pigment to obtain a better metallic color. As the metallic pigment, aluminum powder is suitable. In addition, by blending a fluorescent brightening agent or other fluorescent dyes that emit light, a better design effect utilizing the luminescent color can be imparted.

(IV) Fluorescent whitening agent In the glass-reinforced polycarbonate resin composition constituting the heat-caulking conjugate of the present invention, the fluorescent whitening agent can be used as long as it is used to improve the color tone of the resin to white or bluish white. There is no restriction | limiting in particular, For example, a stilbene type | system | group, a benzimidazole type | system | group, a benzoxazole type | system | group, a naphthalimide type | system | group, a rhodamine type | system | group, a coumarin type | system | group, an oxazine type compound etc. are mentioned. Specifically, for example, CI Fluorescent Brightener 219: 1, Eastman Chemical OB-1 manufactured by Eastman Chemical Co., Ltd., “Hackol PSR” manufactured by Showa Chemical Co., Ltd., and the like can be mentioned. Here, the fluorescent whitening agent has an action of absorbing energy in the ultraviolet part of the light and radiating this energy to the visible part. The content of the fluorescent brightening agent is preferably 0.001 to 0.1 parts by weight, more preferably 0.001 to 0.05 parts by weight with respect to 100 parts by weight of the resin component. Even if it exceeds 0.1 parts by weight, the effect of improving the color tone of the composition is small.

(V) Compound having heat ray absorbing ability The glass-reinforced polycarbonate resin composition constituting the heat caulking-bonded body of the present invention may contain a compound having heat ray absorbing ability. Such compounds include phthalocyanine-based near infrared absorbers, metal oxide-based near infrared absorbers such as ATO, ITO, iridium oxide and ruthenium oxide, imonium oxide, and titanium oxide, lanthanum boride, cerium boride, and tungsten boride. Preferable examples include various metal compounds having excellent near-infrared absorptivity such as metal borides and tungsten oxide-based near-infrared absorbers, and carbon fillers. As such a phthalocyanine-based near infrared absorber, for example, MIR-362 manufactured by Mitsui Chemicals, Inc. is commercially available and easily available. Examples of the carbon filler include carbon black, graphite (including both natural and artificial) and fullerene, and carbon black and graphite are preferable. These can be used alone or in combination of two or more. The content of the phthalocyanine-based near infrared absorber is preferably 0.0005 to 0.2 parts by weight, more preferably 0.0008 to 0.1 parts by weight, based on 100 parts by weight of the resin component, and 0.001 to 0.00. More preferred is 07 parts by weight. The content of the metal oxide near-infrared absorber, the metal boride-based near infrared absorber and the carbon filler is preferably in the range of 0.1 to 200 ppm (weight ratio) in the polycarbonate resin composition of the present invention. A range of 5 to 100 ppm is more preferable.

(VI) Light Diffusing Agent The glass reinforced polycarbonate resin composition constituting the heat caulking combined body of the present invention can be blended with a light diffusing agent to give a light diffusing effect. Examples of such light diffusing agents include polymer fine particles, inorganic fine particles having a low refractive index such as calcium carbonate, and composites thereof. Such polymer fine particles are fine particles that are already known as light diffusing agents for polycarbonate resins. More preferably, acrylic crosslinked particles having a particle size of several μm, silicone crosslinked particles represented by polyorganosilsesquioxane, and the like are exemplified. Examples of the shape of the light diffusing agent include a spherical shape, a disk shape, a column shape, and an indefinite shape. Such spheres need not be perfect spheres, but include deformed ones, and such columnar shapes include cubes. A preferred light diffusing agent is spherical, and the more uniform the particle size is. The content of the light diffusing agent is preferably 0.005 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, still more preferably 0.01 to 3 parts by weight, based on 100 parts by weight of the resin component. Two or more light diffusing agents can be used in combination.

(VII) White pigment for high light reflection The glass reinforced polycarbonate resin composition constituting the heat caulking combined body of the present invention can be provided with a light reflection effect by blending a white pigment for high light reflection. As such a white pigment, a titanium dioxide (particularly titanium dioxide treated with an organic surface treating agent such as silicone) pigment is particularly preferred. The content of the white pigment for high light reflection is preferably 3 to 30 parts by weight, more preferably 8 to 25 parts by weight based on 100 parts by weight of the resin component. Two or more kinds of white pigments for high light reflection can be used in combination.

(VIII) Ultraviolet Absorber The glass reinforced polycarbonate resin composition constituting the heat-caulking bonded body of the present invention can be blended with an ultraviolet absorber to impart weather resistance. Specific examples of the ultraviolet absorber include benzophenone-based compounds such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 2-hydroxy-4-benzi. Loxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy- 4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2-hydroxy -4-n-dodecyloxybenzophenone, and And 2-hydroxy-4-methoxy-2′-carboxybenzophenone. Specific examples of the ultraviolet absorber include, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazole and 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole in the benzotriazole series. 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-benzotriazol-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) ) Benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -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, and Copolymerizable with 2- (2′-hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole and the monomer 2-hydroxy such as copolymers with vinyl monomers and copolymers of 2- (2′-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole and vinyl monomers copolymerizable with the monomers Examples thereof include a polymer having a phenyl-2H-benzotriazole skeleton. Specifically, the ultraviolet absorber is, for example, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol, 2- (4, 4-hydroxyphenyltriazine). 6-diphenyl-1,3,5-triazin-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-ethyloxyphenol 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-propyloxyphenol, and 2- (4,6-diphenyl-1,3,5-triazin-2-yl) ) -5-butyloxyphenol and the like. Furthermore, the phenyl group of the above exemplary compounds such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol is 2,4-dimethyl. Examples of the compound are phenyl groups. Specifically, in the case of the cyclic imino ester, the ultraviolet absorber is, for example, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2′-m-phenylenebis (3,1). -Benzoxazin-4-one), 2,2'-p, p'-diphenylenebis (3,1-benzoxazin-4-one) and the like. Further, as the ultraviolet absorber, specifically, for cyanoacrylate, for example, 1,3-bis-[(2′-cyano-3 ′, 3′-diphenylacryloyl) oxy] -2,2-bis [(2- Examples include cyano-3,3-diphenylacryloyl) oxy] methyl) propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene. Furthermore, the ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, so that the ultraviolet absorbent monomer and / or the light stable monomer and a single amount of alkyl (meth) acrylate or the like can be obtained. It may be a polymer type ultraviolet absorber copolymerized with a body. Preferred examples of the ultraviolet absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in the ester substituent of (meth) acrylic acid ester. The Among them, benzotriazole and hydroxyphenyltriazine are preferable in terms of ultraviolet absorption ability, and cyclic imino ester and cyanoacrylate are preferable in terms of heat resistance and hue. Specifically, for example, Chemipro Kasei Co., Ltd. “Chemisorb 79”, BASF Japan Co., Ltd. “Tinubin 234” and the like can be mentioned. You may use the said ultraviolet absorber individually or in mixture of 2 or more types.

  The content of the ultraviolet absorber is preferably 0.01 to 3 parts by weight, more preferably 0.01 to 1 part by weight, still more preferably 0.05 to 1 part by weight, particularly 100 parts by weight of the resin component. Preferably it is 0.05-0.5 weight part.

(IX) Antistatic Agent The glass-reinforced polycarbonate resin composition constituting the heat-caulking bonded body of the present invention may require antistatic performance, and in such a case, it is preferable to include an antistatic agent. Examples of the antistatic agent include (1) aryl sulfonic acid phosphonium salts represented by dodecylbenzenesulfonic acid phosphonium salts, organic sulfonic acid phosphonium salts such as alkyl sulfonic acid phosphonium salts, and tetrafluoroboric acid phosphonium salts. Examples thereof include phosphonium borate salts. The content of the phosphonium salt is suitably 5 parts by weight or less with respect to 100 parts by weight of the resin component, preferably 0.05 to 5 parts by weight, more preferably 1 to 3.5 parts by weight, and still more preferably 1 part. The range is from 5 to 3 parts by weight. Examples of the antistatic agent include: (2) lithium organic sulfonate, organic sodium sulfonate, organic potassium sulfonate, cesium organic sulfonate, rubidium organic sulfonate, calcium organic sulfonate, magnesium organic sulfonate, and barium organic sulfonate. And organic sulfonate alkali (earth) metal salts. Such metal salts are also used as flame retardants as described above. More specific examples of such metal salts include metal salts of dodecylbenzene sulfonic acid and metal salts of perfluoroalkane sulfonic acid. The content of the organic sulfonate alkali (earth) metal salt is suitably 0.5 parts by weight or less, preferably 0.001 to 0.3 parts by weight, more preferably 0, based on 100 parts by weight of the resin component. 0.005 to 0.2 parts by weight. In particular, alkali metal salts such as potassium, cesium, and rubidium are preferable.

  Examples of the antistatic agent include (3) organic sulfonic acid ammonium salts such as alkyl sulfonic acid ammonium salt and aryl sulfonic acid ammonium salt. The ammonium salt is suitably 0.05 parts by weight or less based on 100 parts by weight of the resin component. Examples of the antistatic agent include (4) a polymer containing a poly (oxyalkylene) glycol component such as polyether ester amide as a constituent component. The polymer is suitably 5 parts by weight or less based on 100 parts by weight of the resin component.

(X) Filler Various known fillers other than glass flakes can be blended in the glass-reinforced polycarbonate resin composition constituting the heat-caulking bonded body of the present invention. As such a filler, various fibrous fillers, plate-like fillers, and granular fillers can be used. Here, the fibrous filler has a fibrous shape (including a rod shape, a needle shape, or a shape whose axis extends in a plurality of directions), and the plate-like filler has a plate shape (surface) (Including those having irregularities and those having a curved plate). The granular filler is a filler having a shape other than these including an indefinite shape. The fiber-like and plate-like shapes are often clear from the observation of the shape of the filler. For example, a difference from a so-called indeterminate shape can be said to be a fiber-like or plate-like one having an aspect ratio of 3 or more.

  Examples of the plate-like filler include talc, mica, kaolin, metal flake, carbon flake, and graphite, and a plate-like filler in which a different material such as metal or metal oxide is surface-coated with respect to these fillers. Preferably exemplified. The particle size is preferably in the range of 0.1 to 300 μm. The particle size is about 10 μm in terms of the median diameter (D50) of the particle size distribution measured by the X-ray transmission method, which is one of the liquid phase precipitation methods. In the region of 10-50 μm, laser diffraction is performed. -The value by the median diameter (D50) of the particle size distribution measured by the scattering method is referred to, and in the region of 50 to 300 μm, the value is by the vibration sieving method. Such a particle size is a particle size in the resin composition. The plate-like filler may be surface-treated with various coupling agents such as silane, titanate, aluminate, and zirconate, and olefin resin, styrene resin, acrylic resin, polyester resin. It may be a granulated product that has been subjected to a bundling treatment or compression treatment with various resins such as epoxy resins and urethane resins, higher fatty acid esters, and the like.

  The fiber diameter of the fibrous filler is preferably in the range of 0.1 to 20 μm. The upper limit of the fiber diameter is more preferably 18 μm and even more preferably 15 μm. On the other hand, the lower limit of the fiber diameter is preferably 1 μm, and more preferably 6 μm. The fiber diameter here refers to the number average fiber diameter. The number average fiber diameter is obtained by scanning the residue collected after dissolving the molded product in a solvent, or decomposing the resin with a basic compound, and the ash residue collected after ashing with a crucible. It is a value calculated from an image observed with an electron microscope. Examples of the fibrous filler include glass fiber, carbon fiber, carbon milled fiber, metal fiber, asbestos, rock wool, ceramic fiber, slag fiber, potassium titanate whisker, boron whisker, aluminum borate whisker, and calcium carbonate whisker. , Titanium Oxide Whisker, Wollastonite, Zonolite, Palygorskite (Attapulgite), Sepiolite and other fibrous inorganic fillers, Fibrous heat-resistant organic fillings typified by heat-resistant organic fibers such as aramid fibers, polyimide fibers and polybenzthiazole fibers Examples of the material and the fibrous filler in which a different material such as a metal or a metal oxide is surface-coated with respect to these fillers. Examples of the filler whose surface is coated with a different material include metal-coated glass fiber and metal-coated carbon fiber. The surface coating method of different materials is not particularly limited. For example, various known plating methods (for example, electrolytic plating, electroless plating, hot-dip plating, etc.), vacuum deposition methods, ion plating methods, CVD methods ( For example, thermal CVD, MOCVD, plasma CVD, etc.), PVD method, sputtering method, etc. can be mentioned. Here, the fibrous filler means a fibrous filler having an aspect ratio of 3 or more, preferably 5 or more, more preferably 10 or more. The upper limit of the aspect ratio is about 10,000, preferably 200. The aspect ratio of such a filler is a value in the resin composition. The fibrous filler may be surface-treated with various coupling agents in the same manner as the plate-like filler, may be converged with various resins, and may be granulated by compression. The content of the filler is preferably 200 parts by weight or less based on 100 parts by weight of the resin component, more preferably 100 parts by weight or less, still more preferably 50 parts by weight or less, and particularly preferably 30 parts by weight or less.

(XI) Other resins and elastomers In the glass-reinforced polycarbonate resin composition constituting the heat-caulking bonded body of the present invention, a range in which other resins and elastomers exhibit the effects of the present invention instead of a part of the resin component Can be used in small proportions. The blending amount of other resins and elastomers is preferably 20% by weight or less, more preferably 10% by weight or less, still more preferably 5% by weight or less, in a total of 100% by weight of component A and component B. Examples of such other resins include 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, and polymethacrylate resins. And resins such as phenol resins and epoxy resins. As the elastomer, for example, isobutylene / isoprene rubber, styrene / butadiene rubber, ethylene / propylene rubber, acrylic elastomer, polyester elastomer, polyamide elastomer, MBS (methyl methacrylate / sterene / butadiene) which is a core-shell type elastomer. Examples thereof include rubber, MB (methyl methacrylate / butadiene) rubber, MAS (methyl methacrylate / acrylonitrile / styrene) rubber, and the like.

(XII) Other Additives The glass-reinforced polycarbonate resin composition constituting the heat-caulking conjugate of the present invention includes other flow modifiers, antibacterial agents, dispersants such as liquid paraffin, photocatalytic antifouling agents, and photochromic. An agent or the like can be blended.

<About production of resin composition>
The glass-reinforced polycarbonate resin composition constituting the heat-caulking bonded body of the present invention can be pelletized by melt-kneading using an extruder such as a single screw extruder or a twin screw extruder. In producing such pellets, the above-mentioned various reinforcing fillers and additives can be blended. The resin composition of the present invention can be usually produced by injection-molding pellets produced as described above to produce various products. Furthermore, the resin melt-kneaded by an extruder can be directly made into a sheet, a film, a profile extrusion molded product, a direct blow molded product, and an injection molded product without going through pellets. In such injection molding, not only a normal molding method but also an injection compression molding, an injection press molding, a gas assist injection molding, a foam molding (including those by injection of a supercritical fluid), an insert molding, depending on the purpose as appropriate. A molded product can be obtained using an injection molding method such as in-mold coating molding, heat insulating mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, and ultrahigh-speed injection molding. The advantages of these various molding methods are already widely known. In addition, either a cold runner method or a hot runner method can be selected for molding. Moreover, the resin composition of this invention can also be utilized in the form of various profile extrusion-molded articles, a sheet | seat, a film, etc. by extrusion molding. For forming sheets and films, an inflation method, a calendar method, a casting method, or the like can also be used. It is also possible to form a heat-shrinkable tube by applying a specific stretching operation. The resin composition of the present invention can be formed into a molded product by rotational molding, blow molding or the like.

<Manufacture of molded products>
The resin molding which comprises the heat crimping | bonding body of this invention can usually obtain such a molded article by injection molding such a pellet. In such injection molding, not only a normal cold runner type molding method but also a hot runner that enables runnerlessness can be used. Also in injection molding, not only ordinary molding methods, but also gas-assisted injection molding, injection compression molding, ultra-high speed injection molding, injection press molding, two-color molding, sandwich molding, in-mold coating molding, insert molding, foam molding (ultra-molding) Including those using critical fluids), rapid heating / cooling mold forming, heat insulating mold forming and in-mold remelt molding, and combinations of these, etc. can be used. As the heat caulking method for forming the heat caulking assembly of the present invention, a known method can be used.

  The heat caulking assembly of the present invention is useful in various applications such as various electronic / electrical equipment parts, camera parts, OA equipment parts, precision machine parts, machine parts, vehicle parts, other agricultural materials, transport containers, playground equipment, and miscellaneous goods. And the industrial effects that it plays are exceptional.

It is a figure which shows the heat crimping method.

  The form of the present invention considered to be the best by the present inventor is a collection of the preferable ranges of the above requirements. For example, typical examples are described in the following examples. Of course, the present invention is not limited to these forms.

(1) Evaluation of Glass Reinforced Polycarbonate Resin Composition (1) -1 Flexural Strength After pellets obtained from each composition of the examples were dried at 120 ° C. for 5 hours, an injection molding machine (Sumitomo Heavy Industries, Ltd. ) SG-150U), a test piece (dimensions: length 80 mm × width 10 mm × thickness 4 mm) was molded at a cylinder temperature of 300 ° C. and a mold temperature of 80 ° C. The bending strength was measured according to ISO 178 (measurement condition 23 ° C.). The larger this value, the better the strength of the resin portion of the heat caulking conjugate.

(1) -2 Charpy impact strength A test piece (dimensions: length 80 mm × width 10 mm × thickness 4 mm) molded under the same conditions as in (1) -1 above was measured for notched Charpy impact strength by a method in accordance with ISO179. did. The larger this value, the better the impact resistance of the resin part of the heat caulking bonded body.

(1) -3 Gas generation amount 10 mg of the pellets obtained from each composition of the Examples were weighed, placed in a heating furnace (Pyrolyzer PY-2020iD manufactured by Frontier Laboratories), held at 150 ° C. for 30 minutes, and the generated gas was GC / MS analysis was performed using a cryotrap GC-MS. The measurement conditions are as follows.
GC / MS: GC6890 + MSD5973 (Agilent)
Column: SPB-1 Sulfur (30 m × 0.32 mm ID film thickness 4.0 μm)
-Oven temperature: 40 ° C to 300 ° C (10 ° C / min)
Scan range: m / z 29-600
Next, a calibration curve was prepared using hexadecane as a standard substance and quantified. Judgment is as follows.
○: Gas generation amount ≦ 1 μg / g
×: Gas generation amount> 1 μg / g

(2) Evaluation of Thermal Caulking Conjugate FIG. 1 is a diagram for explaining a thermal caulking method. In the figure, a component 1 is made of the glass-reinforced resin composition of the present invention and has columnar convex portions. The component 2 is fastened to the component 1 and has a hole for fitting the convex portion of the component 1. 3 is a crimping chip | tip, and the pressurization surface is dented in circular arc shape. The crimping chip 3 is provided with a heater (not shown), and the crimping chip 3 can be raised to a desired temperature. As shown in FIG. 1A, first, the component 1 and the component 2 are overlapped, the convex portion of the component 1 is passed through the hole of the component 2, and the crimping chip 3 heated to 220 ° C. is lowered. As shown in FIG. 1 (b), the lowered crimping chip 3 comes into contact with the convex part of the component 1, melts it momentarily, and presses it with a low pressure load, thereby pressing the convex part of the component 1 into the crimping chip 3. It deforms in accordance with the shape of the pressure surface, and a crimped part is formed. After the molding is completed, as shown in FIG. 1C, the crimping chip 3 is detached from the component 1 to complete the thermal crimping.

(2) -1. Thermal caulking releasability After the pellets obtained from each composition of the examples were dried at 120 ° C. for 5 hours, the cylinder temperature was 300 ° C. and gold was used with an injection molding machine (SG-150U manufactured by Sumitomo Heavy Industries, Ltd.). A part 1 (dimensions: bottom diameter 50 mm, height 60 mm, convex diameter 20 mm) shown in FIG. 1 was molded at a mold temperature of 80 ° C. Next, a part 2 having a hole with a diameter of 21 mm was formed in the center of a steel plate (material: SS400, size 100 mm × 100 mm × 10 mm). Using the part 1 and the part 2, a heat caulking joined body was prepared by the above method. In the preparation process, as shown in FIG. 1C, the releasability of the heat caulking component when the caulking chip 3 was detached from the component 1 was evaluated according to the following criteria.
◯: No resin fusion is seen on the crimping chip 3, and no deformation is seen on the thermal crimping part.
(Triangle | delta): Although the melt | fusion of resin is not looked at by the crimping | crimping chip | tip 3, a deformation | transformation is seen by a heat caulking part.
X: Resin fusion is observed on the crimping chip 3.

(2) -2. Thermal caulking binding property The thermal caulking binding property of the thermal caulking conjugate produced in “(2) -1” was evaluated according to the following criteria.
○: No rattling is observed in the caulking portion of the heat caulking conjugate.
X: Shaking is observed in the caulking portion of the heat caulking conjugate.

(2) -3. Thermal caulking bond stability The heat caulking bonded body prepared in “(2) -1” was subjected to wet heat treatment under the following conditions.
(Wet heat treatment conditions)
Equipment used: PR-3KP (Espec Corp.)
Temperature: 75 ° C
Humidity: 85% RH
Test time: The thermal caulking binding property of the thermal caulking conjugate after 1,000 hours of treatment was evaluated according to the following criteria.
○: No rattling is observed in the caulking portion of the heat caulking conjugate.
X: Shaking is observed in the caulking portion of the heat caulking conjugate.

[Examples 1 to 11 and Comparative Examples 1 to 5]
The components A to C and various additives were mixed in the blending amounts shown in Table 1 with a blender, and then melt-kneaded using a vent type twin screw extruder to obtain pellets. Various additives to be used were prepared in advance by premixing with a polycarbonate resin with a concentration of 10 to 100 times the blending amount as a guide, and then the whole was mixed by a blender. The vent type twin screw extruder used was TEX30α (completely meshing, rotating in the same direction, two-thread screw) manufactured by Nippon Steel Works. The extrusion conditions are a discharge rate of 20 kg / h, a screw rotation speed of 150 rpm, a vent vacuum of 3 kPa, and an extrusion temperature of 270 ° C. from the first supply port to the second supply port and 280 ° C. from the second supply port to the die part. did. Table 1 shows the evaluation results of the obtained pellets.

In addition, the detail of each used component is as follows.
(A component)
A-1: Polycarbonate resin powder having a viscosity average molecular weight of 22,400 obtained by the following production method [Production method]
A reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 2340 parts of ion-exchanged water, 947 parts of a 25% aqueous sodium hydroxide solution and 0.7 parts of hydrosulfite, and 2,2-bis (4-hydroxyphenyl) under stirring. ) After dissolving 710 parts of propane (hereinafter sometimes referred to as “bisphenol A”) (bisphenol A solution), 2299 parts of methylene chloride and 112 parts of 48.5% aqueous sodium hydroxide solution were added, and the temperature was 15-25 ° C. The phosgenation reaction was performed by blowing 354 parts of phosgene over about 90 minutes. After completion of the phosgenation, 125 parts of 11% strength p-tert-butylphenol in methylene chloride and 88 parts of 48.5% aqueous sodium hydroxide solution were added to stop stirring. After 5 minutes of emulsification, the mixture was processed with a homomixer (Special Machine Industries Co., Ltd.) at a rotational speed of 1200 rpm and a pass count of 35 times to obtain a highly emulsified dope. The highly emulsified dope was reacted in a polymerization tank (with a stirrer) at a temperature of 35 ° C. for 3 hours under non-stirring conditions to complete the polymerization. After completion of the reaction, the organic phase is separated, diluted with methylene chloride, washed with water, acidified with hydrochloric acid, washed with water, and poured into a kneader filled with warm water when the conductivity of the aqueous phase is almost the same as that of ion-exchanged water. Then, methylene chloride was evaporated with stirring to obtain polycarbonate powder. After dehydration, it was dried at 120 ° C. for 12 hours with a hot air circulation dryer to obtain a polycarbonate resin powder.

A-2: Polycarbonate resin powder having a viscosity average molecular weight of 19,800 obtained by the following production method [Production method]
A polycarbonate resin powder was obtained in the same manner as in the production method of A-1, except that the methylene chloride solution of 11% concentration of p-tert-butylphenol was changed to 128 parts.

(B component)
B-1: Polycarbonate-polydiorganosiloxane copolymer resin powder having a viscosity average molecular weight of 19,400 obtained by the following production method [Production method]
Into a reactor equipped with a thermometer, a stirrer, and a reflux condenser, 21591 parts of ion-exchanged water and 3673 parts of 48.5% aqueous sodium hydroxide solution were placed, and 3880 parts of 2,2-bis (4-hydroxyphenyl) propane (bisphenol A). , And 7.6 parts of hydrosulfite were dissolved, 14565 parts of methylene chloride (14 moles relative to 1 mole of dihydroxy compound (I)) was added, and 1900 parts of phosgene was required for 60 minutes at 22-30 ° C. with stirring. Blew in. Next, a solution obtained by dissolving 1131 parts of 48.5% aqueous sodium hydroxide solution and 105 parts of p-tert-butylphenol in 800 parts of methylene chloride was added, and the polydiorganosiloxane compound represented by the following formula [11] ( The average number of repetitions in the formula p = about 37) A solution of 430 parts in 1600 parts of methylene chloride was added to 0.0008 mole / dihydroxyaryl-terminated polydiorganosiloxane (II) per mole of dihydric phenol (I). The mixture was added at a speed of min to obtain an emulsified state, and then vigorously stirred again. Under such stirring, 4.3 parts of triethylamine was added while the reaction solution was at 26 ° C., and stirring was continued for 45 minutes at a temperature of 26 to 31 ° C. to complete the reaction. After completion of the reaction, the organic phase is separated, diluted with methylene chloride, washed with water, acidified with hydrochloric acid, washed with water, and poured into a kneader filled with warm water when the conductivity of the aqueous phase is almost the same as that of ion-exchanged water. Then, methylene chloride was evaporated while stirring to obtain a polycarbonate-polydiorganosiloxane copolymer resin powder. After dehydration, it was dried at 120 ° C. for 12 hours with a hot air circulation dryer to obtain a polycarbonate-polydiorganosiloxane copolymer resin powder. (Polydiorganosiloxane component content 8.2%, viscosity average molecular weight 19,400)

B-2: Polycarbonate-polydiorganosiloxane copolymer resin powder having a viscosity average molecular weight of 22,400 obtained by the following production method [Production method]
Except having changed p-tert- butylphenol into 85 parts, it carried out similarly to the manufacturing method of B-1, and obtained polycarbonate resin powder. (Polydiorganosiloxane component content 8.2%, viscosity average molecular weight 22,400)

(C component)
C-1: Thin glass flakes (average thickness 0.7 μm, average particle diameter 160 μm, surface treatment agent amount 3% by weight, surface treatment agent: silane coupling agent and epoxy resin)
C-2: Thin glass flakes (average thickness 0.4 μm, average particle size 160 μm, surface treatment agent amount 5% by weight, surface treatment agent: silane coupling agent and urethane resin)
C-3: Thin glass flakes (average thickness 0.1 μm, average particle size 160 μm, surface treatment agent amount 5% by weight, surface treatment agent: silane coupling agent and epoxy resin)
C-4: Glass flake (average thickness 5.0 μm, average particle size 160 μm, surface treatment agent amount 5% by weight, surface treatment agent: silane coupling agent and epoxy resin)

(Other ingredients)
PBT: Polybutylene terephthalate (manufactured by Polyplastics Co., Ltd .: DURANEX 500FP EF202X (trade name), IV value: 0.85, terminal carboxyl group: 55 eq / ton)
AS: Acrylonitrile-styrene copolymer resin (AS resin) (manufactured by Japan A & L Co., Ltd .: Litec BS-218 (trade name))
RW: Mold release agent (Mitsui Chemicals, Inc .: High Wax 405MP (trade name))
TMP: Phosphate stabilizer (manufactured by Daihachi Chemical Industry Co., Ltd .: TMP (trade name))
F114: perfluorobutanesulfonic acid potassium salt (Megafac F-114P (trade name) manufactured by Dainippon Ink, Inc.)
CB: Carbon black (RB-961S manufactured by Koshigaya Chemical Co., Ltd.)

1. 1. Parts having convex portions 2. Parts with holes Caulking chips

Claims (3)

  A heat caulking assembly in which a plastic part and another part are fixed by heat caulking, wherein the plastic part is (A) polycarbonate resin (component A) 0 to 90% by weight and (B) polycarbonate-polydiorganosiloxane copolymer It contains 10 to 100 parts by weight of glass flake (C component) having an average thickness of 0.2 to 0.7 μm with respect to 100 parts by weight of resin component consisting of 10 to 100% by weight of resin (B component). A heat caulking bonded body, which is a molded body made of a glass-reinforced polycarbonate resin composition.   The heat caulking assembly according to claim 1, wherein the plastic part is a cylindrical molded body.   A glass-reinforced polycarbonate resin composition constituting the plastic part according to claim 1.

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