JP2009074031A - Automotive component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an automotive component comprising a polycarbonate resin that uses biomass resources excellent in heat resistance, mechanical characteristic and environmental resistance as raw material. <P>SOLUTION: The automotive component is obtained when a polycarbonate resin (component A), composed of carbonate structural units represented by formula (1) and whose melt viscosity as measured with a capillary rheometer at 250°C is in the range of 0.2×10<SP>3</SP>to 4.0×10<SP>3</SP>Pa s under the condition of a shear rate of 600 sec<SP>-1</SP>, is injection molded at cylinder temperatures ranging from 220 to 270°C. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an automobile part made of a specific polycarbonate resin. More specifically, the present invention relates to an automobile part that is obtained by molding a specific polycarbonate resin under specific injection molding conditions and is excellent in heat resistance, mechanical characteristics, and environmental resistance characteristics.

  In recent years, due to concerns about the depletion of petroleum resources and the problem of increased carbon dioxide in the air that causes global warming, biomass resources that do not depend on petroleum as a raw material and that do not increase carbon dioxide even when burned are formed. In the polymer field, biomass plastics produced from biomass resources are actively developed.

  A representative example of biomass plastics is polylactic acid, which has relatively high heat resistance and mechanical properties among biomass plastics, so its application is expanding to tableware, packaging materials, sundries, etc. As a possibility, it has come to be examined.

  However, polylactic acid is insufficient in heat resistance when used as an industrial material, and when a molded product is obtained by injection molding with high productivity, the crystalline polymer has low crystallinity. There is a problem that moldability is inferior.

  As an amorphous polycarbonate resin that uses biomass resources as a raw material and has high heat resistance, a polycarbonate resin using a raw material obtained from an ether diol residue that can be produced from a saccharide has been studied.

に示したエーテルジオールは、たとえば糖類およびでんぷんなどから容易に作られ、３種の立体異性体が知られているが、具体的には下記式（ｂ）

に示す、１，４：３，６ージアンヒドローＤーソルビトール（本明細書では以下「イソソルビド」と呼称する）、下記式（ｃ）

に示す、１，４：３，６ージアンヒドローＤーマンニトール（本明細書では以下「イソマンニド」と呼称する）、下記式（ｄ）

に示す、１，４：３，６ージアンヒドローＬーイジトール（本明細書では以下「イソイディッド」と呼称する）である。 For example, the following formula (a)

The ether diol shown in Fig. 2 is easily made from, for example, sugars and starch, and three stereoisomers are known. Specifically, the following formula (b)

1,4: 3,6-dianhydro-D-sorbitol (hereinafter referred to as “isosorbide”), represented by the following formula (c)

1,4: 3,6-dianhydro-D-mannitol (hereinafter referred to as “isomannide”), represented by the following formula (d):

1,4: 3,6-dianhydro-L-iditol (hereinafter referred to as “isoidid” in the present specification).

  Isosorbide, isomannide, and isoidide are obtained from D-glucose, D-mannose, and L-idose, respectively. For example, isosorbide can be obtained by hydrogenating D-glucose and then dehydrating it using an acid catalyst.

  So far, among the above-mentioned ether diols, in particular, incorporation into polycarbonate using isosorbide as a monomer has been studied. In particular, isosorbide homopolycarbonates are described in Patent Documents 1 and 2 and Non-Patent Documents 1 and 2. Among these, Patent Document 1 reports a homopolycarbonate having a melting point of 203 ° C. using a melt transesterification method. In Non-Patent Document 1, a homopolycarbonate having a glass transition temperature of 166 ° C. is obtained in the melt transesterification method using zinc acetate as a catalyst, but the thermal decomposition temperature (5% weight loss temperature) is 283 ° C. Stability is not enough. In Non-Patent Document 2, homopolycarbonate is obtained by interfacial polymerization using bischloroformate of isosorbide, but the glass transition temperature is 144 ° C. and heat resistance (particularly heat resistance due to moisture absorption) is not sufficient. On the other hand, as an example of high heat resistance, Patent Document 2 reports polycarbonate having a glass transition temperature of 170 ° C. or higher by differential calorimetry at a heating rate of 10 ° C./min. In view of the development of the above, there are problems in obtaining a molded product by injection molding or the like because the glass transition temperature is high, the molding processing temperature is high, and the decomposition of the polymer is promoted. Further, this polycarbonate is produced in the presence of a tin catalyst, has a thermal decomposition temperature (5% weight loss temperature) of around 300 ° C., and there is room for improvement in thermal stability.

  In other words, polycarbonate resin using isosorbide as a monomer that can provide automotive parts that have melt flow characteristics and heat stability suitable for injection molding, and that exhibit excellent heat resistance, mechanical characteristics, and environmental resistance characteristics. It was not yet obtained.

British Patent Application No. 1079686 International Publication No. 2007/013463 Pamphlet “Journal of Applied Polymer Science”, 2002, Vol. 86, p. 872-880 “Macromolecules”, 1996, Vol. 29, p. 8077-8082

  Accordingly, a main object of the present invention is to provide an automobile part made of a polycarbonate resin using as a raw material a biomass resource excellent in heat resistance, mechanical characteristics, and environmental resistance characteristics.

  As a result of diligent research to achieve such an object, the present inventors, as a result of injection molding a polycarbonate resin having a specific structure and melt flow characteristics under specific conditions, an automobile excellent in heat resistance, mechanical characteristics, and environmental resistance characteristics The present invention was completed by finding that parts can be obtained.

２．ポリカーボネート樹脂（Ａ成分）は、ガラス転移温度が１４５〜１６５℃の範囲にある前項１記載の自動車部品、
３．ポリカーボネート樹脂（Ａ成分）は、下記式（ａ）で示されるエーテルジオールと炭酸ジエステルとを、アルカリ金属塩、アルカリ土類金属塩、及び含窒素塩基性化合物からなる群より選ばれた少なくとも一つの化合物を触媒として溶融重縮合された前項１または２記載の自動車部品、

４．弾性重合体（Ｂ成分）を、ポリカーボネート樹脂（Ａ成分）１００重量部あたり、０．２〜５０重量部含んでなる前項１〜３のいずれか１項に記載の自動車部品、
が提供される。 That is, according to the present invention,
1. It consists of a carbonate structural unit represented by the following formula (1), and the melt viscosity measured with a capillary rheometer at 250 ° C. is 0.2 × 10 ^{3 to} 4.0 × 10 ³ Pa under the condition of a shear rate of 600 sec ^-1. -Automobile parts obtained by injection molding polycarbonate resin (component A) in the range of s at a cylinder temperature of 220 to 270 ° C,

2. The polycarbonate resin (component A) has a glass transition temperature in the range of 145 to 165 ° C.
3. The polycarbonate resin (component A) is an ether diol represented by the following formula (a) and a carbonic acid diester, at least one selected from the group consisting of alkali metal salts, alkaline earth metal salts, and nitrogen-containing basic compounds. The automobile part according to the preceding item 1 or 2, which is melt polycondensed using a compound as a catalyst,

4). The automobile part according to any one of the preceding items 1 to 3, comprising 0.2 to 50 parts by weight of the elastic polymer (component B) per 100 parts by weight of the polycarbonate resin (component A),
Is provided.

  Hereinafter, the automobile parts obtained by injection molding of the polycarbonate resin of the present invention will be specifically described sequentially.

<About component A>
The polycarbonate resin (component A) used in the present invention is a polycarbonate resin composed of the carbonate structural unit of the above formula (1), and the biogenic substance content measured according to ASTM D686605 is 83% to 100%. Preferably, 84% to 100% is more preferable. Particularly preferred is a homopolycarbonate resin comprising only the carbonate structural unit of the above formula (1).

The polycarbonate resin (component A) used in the present invention has a melt viscosity measured by a capillary rheometer at 250 ° C. of 0.2 × 10 ^{3 to} 4.0 × 10 ³ Pa · s under the condition of a shear rate of 600 sec ^-1 . It is in the range, more preferably in the range of 0.4 × 10 ^{3 to} 3.0 × 10 ³ Pa · s, and in the range of 0.4 × 10 ^{3 to} 2.0 × 10 ³ Pa · s. More preferably. When the melt viscosity is within this range, injection molding can be performed under favorable conditions in which the decomposition of the polymer is suppressed, and a molded product excellent in various characteristics can be obtained. If the melt viscosity is smaller than the lower limit, the mechanical properties are poor even if injection molding is possible. If the melt viscosity is higher than the upper limit, the melt fluidity is inferior.

  As the polycarbonate resin (component A) used in the present invention, those having a specific viscosity at 20 ° C. of 0.14 to 0.5 of a solution obtained by dissolving 0.7 g of resin in 100 ml of methylene chloride can be preferably used. The lower limit of the specific viscosity is more preferably 0.20 or more, and further preferably 0.22 or more. The upper limit is more preferably 0.45 or less, further preferably 0.37 or less, and particularly preferably 0.34 or less. On the other hand, when the specific viscosity is lower than 0.14, it becomes difficult to give sufficient mechanical strength to the molded product obtained from the polycarbonate resin used in the present invention. On the other hand, if the specific viscosity is higher than 0.5, the melt fluidity becomes too high, and the melting temperature having the fluidity necessary for molding becomes higher than the decomposition temperature.

  The lower limit of the glass transition temperature (Tg) of the polycarbonate resin (component A) used in the present invention is preferably 145 ° C or higher, more preferably 150 ° C or higher, and the upper limit is preferably 165 ° C or lower. When Tg is less than 145 ° C, the heat resistance (particularly heat resistance due to moisture absorption) is poor, and when it exceeds 165 ° C, the melt flowability is poor when molding with the polycarbonate resin used in the present invention, and the temperature at which polymer decomposition is low. It becomes impossible to injection mold in the range. Tg is measured by DSC (model DSC2910) manufactured by TA Instruments.

  The lower limit of the 5% weight loss temperature of the polycarbonate resin (component A) used in the present invention is preferably 330 ° C or higher, more preferably 340 ° C or higher, still more preferably 350 ° C or higher, and the upper limit is It is preferably 400 ° C. or lower, more preferably 390 ° C. or lower, and further preferably 380 ° C. or lower. It is preferable that the 5% weight loss temperature is within the above range since there is almost no decomposition of the resin when molding using the polycarbonate resin used in the present invention. In order to increase the 5% weight loss temperature, it is effective to select a preferable compound as a melt polymerization catalyst as described later. The 5% weight loss temperature is measured by TA Instruments TGA (model TGA2950).

で表されるエーテルジオールおよび炭酸ジエステルとから溶融重合法により製造することができる。エーテルジオールとしては、具体的には下記式（ｂ）、（ｃ）および（ｄ）

で表されるイソソルビド、イソマンニド、イソイディッドなどが挙げられる。 The polycarbonate resin (component A) used in the present invention has the following formula (a):

It can manufacture with the melt polymerization method from the ether diol and carbonic acid diester represented by these. As the ether diol, specifically, the following formulas (b), (c) and (d)

And isosorbide, isomannide, and isoidide represented by the formula:

  These saccharide-derived ether diols are substances obtained from natural biomass and are one of so-called renewable resources. Isosorbide is obtained by hydrogenating D-glucose obtained from starch and then subjecting it to dehydration. Other ether diols can be obtained by the same reaction except for the starting materials.

  In particular, a polycarbonate resin in which the carbonate structural unit includes a carbonate structural unit derived from isosorbide (1,4: 3,6-dianhydro-D-sorbitol) is preferable. Isosorbide is an ether diol that can be easily made from starch, and can be obtained in abundant resources, and is superior in all ease of manufacture, properties, and versatility of use compared to isomannide and isoidide. .

  The reaction temperature is preferably as low as possible in order to suppress decomposition of the ether diol and obtain a highly viscous resin with little coloration, but the polymerization temperature is 180 ° C. to 280 ° C. in order to proceed the polymerization reaction appropriately. It is preferably in the range of ° C, more preferably in the range of 180 ° C to 260 ° C.

Further, the reaction initially with ether diol and a carbonic acid diester by heating under normal pressure, after pre-reacted, the system to 1.3 × 10 ^-3 gradually to the reaction late in the vacuum ~ 1.3, × 10 ^over A method of facilitating the distillation of alcohol or phenol produced by reducing the pressure to about ⁵ MPa is preferred. The reaction time is usually about 0.5 to 4 hours.

  Examples of the carbonic acid diester include esters such as an aryl group or aralkyl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 4 carbon atoms, in which a hydrogen atom may be substituted. Specific examples include diphenyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Diphenyl carbonate is preferred.

  The carbonic acid diester is preferably mixed so as to have a molar ratio of 1.02 to 0.98 with respect to the ether diol, more preferably 1.01 to 0.98, and still more preferably 1.01 to 0.8. 99. If the molar ratio of the carbonic acid diester is more than 1.02, the carbonic acid diester residue acts as a terminal block and a sufficient degree of polymerization cannot be obtained, which is not preferable. Even when the molar ratio of carbonic acid diester is less than 0.98, a sufficient degree of polymerization cannot be obtained, which is not preferable.

  Examples of the polymerization catalyst include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, alkali metal compounds such as sodium salt or potassium salt of dihydric phenol, calcium hydroxide, barium hydroxide, magnesium hydroxide, etc. And alkaline earth metal compounds, nitrogen-containing basic compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylamine, and triethylamine. These may be used alone or in combination of two or more. Among these, it is preferable to use a nitrogen-containing basic compound and an alkali metal compound in combination. Those polymerized using these catalysts are preferred because the 5% weight loss temperature is kept sufficiently high.

The amount of these polymerization catalysts used is preferably in the range of 1 × 10 ⁻⁹ to 1 × 10 ⁻³ equivalent, more preferably 1 × 10 ^{−8 to} 5 × 10 ⁻⁴ equivalent, relative to 1 mol of the carbonic acid diester component. Selected by The reaction system is preferably maintained in an atmosphere of a gas inert to the raw material such as nitrogen, the reaction mixture, and the reaction product. Examples of inert gases other than nitrogen include argon. Furthermore, you may add additives, such as antioxidant, as needed.

  In addition, the polycarbonate resin used in the present invention may be copolymerized with aliphatic diols and / or aromatic bisphenols within a range that does not impair the properties thereof. The proportion of the aliphatic diols and / or aromatic bisphenols in the total diol component is preferably 40 mol% or less, more preferably 30 mol% or less, further preferably 20 mol% or less, and particularly preferably 10 mol% or less. .

（式中、ｍは１〜２０の整数） As the aliphatic diol, an aliphatic diol represented by the following formula (α) is preferably used.

(Where m is an integer from 1 to 20)

  Specifically, linear diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, cyclohexanediol, cyclohexanedimethanol, etc. Among these, 1,3-propanediol, 1,4-butanediol, hexanediol, and cyclohexanedimethanol are preferable.

  Aromatic bisphenols include 2,2-bis (4-hydroxyphenyl) propane (commonly called “bisphenol A”), 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl). -3,3,5-trimethylcyclohexane, 4,4 '-(m-phenylenediisopropylidene) diphenol, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 2,2-bis (4 -Hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) decane, 1,3-bis {2- (4 -Hydroxyphenyl) propyl} benzene and the like.

  In addition to the ether diol represented by the above formula (1), the aliphatic diol represented by the above formula (2) and the aromatic bisphenol, other diol residues can also be contained. Other diols include aromatic diols such as dimethanolbenzene and diethanolbenzene.

  The polycarbonate resin (component A) obtained by carrying out the reaction as described above has a hydroxyl group or a carbonic acid diester residue as the terminal structure, but the polycarbonate resin (component A) used in the present invention loses its properties. You may introduce | transduce a terminal group separately in the range which is not. Such end groups can be introduced by adding a monohydroxy compound during polymerization. As the monohydroxy compound, a hydroxy compound represented by the following formula (2) or (3) is preferably used.

上記式（２），（３）中、Ｒ^１は炭素原子数４〜３０のアルキル基、炭素原子数７〜３０のアラルキル基、炭素原子数４〜３０のパーフルオロアルキル基、または下記式（４）

であり、好ましくは炭素原子数４〜２０のアルキル基、炭素原子数４〜２０のパーフルオロアルキル基、または上記式（４）であり、特に炭素原子数８〜２０のアルキル基、または上記式（４）が好ましい。Ｘは単結合、エーテル結合、チオエーテル結合、エステル結合、アミノ結合およびアミド結合からなる群より選ばれる少なくとも一種の結合が好ましいが、より好ましくは単結合、エーテル結合およびエステル結合からなる群より選ばれる少なくとも一種の結合であり、なかでも単結合、エステル結合が好ましい。ａは１〜５の整数であり、好ましくは１〜３の整数であり、特に１が好ましい。

In the above formulas (2) and (3), R ¹ is an alkyl group having 4 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, a perfluoroalkyl group having 4 to 30 carbon atoms, or the following formula ( 4)

Preferably an alkyl group having 4 to 20 carbon atoms, a perfluoroalkyl group having 4 to 20 carbon atoms, or the above formula (4), particularly an alkyl group having 8 to 20 carbon atoms, or the above formula. (4) is preferred. X is preferably at least one bond selected from the group consisting of a single bond, ether bond, thioether bond, ester bond, amino bond and amide bond, more preferably selected from the group consisting of a single bond, ether bond and ester bond. It is at least one kind of bond, and among them, a single bond and an ester bond are preferable. a is an integer of 1 to 5, preferably an integer of 1 to 3, and 1 is particularly preferable.

In the above formula (4), R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, It is at least one group selected from the group consisting of an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms, preferably each independently a carbon atom. And at least one group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 10 carbon atoms, and particularly at least one group selected from the group consisting of a methyl group and a phenyl group, respectively. Is preferred. b is an integer of 0 to 3, an integer of 1 to 3 is preferable, and an integer of 2 to 3 is particularly preferable. c is an integer of 4 to 100, preferably an integer of 4 to 50, and particularly preferably an integer of 8 to 50. Since the polycarbonate resin (component A) used in the present invention has a carbonate structural unit obtained from the ether diol of the renewable resource represented by the above formula (a) in the main chain structure, these monohydroxy compounds can also be planted. It is preferable that it is a raw material obtained from renewable resources, such as. Examples of monohydroxy compounds obtained from plants include long-chain alkyl alcohols having 14 or more carbon atoms (cetanol, stearyl alcohol, behenyl alcohol) obtained from vegetable oils.

  By introducing these terminal groups, the effect of improving the moisture absorption resistance or surface energy (antifouling property or wear resistance) of the automobile part made of the polycarbonate resin can be obtained. These end groups are preferably contained in an amount of 0.3 to 9.0% by weight, more preferably 0.3 to 7.5% by weight, and particularly preferably 0.3 to 9.0% by weight based on the polymer main chain structure. 5 to 6.0% by weight is contained.

  The automobile part of the present invention may be composed of a resin composition obtained by adding various components to the above-described polycarbonate resin.

<About B component>
In the polycarbonate resin of component A constituting the automobile part of the present invention, when an elastic polymer (component B) is further blended, it is possible to obtain a component that is given impact resistance and has improved safety against collisions. .

  Examples of elastic polymers include natural rubber or a rubber component having a glass transition temperature of 10 ° C. or lower, aromatic vinyl, vinyl cyanide, acrylate ester, methacrylate ester, and vinyl compounds copolymerizable therewith. Mention may be made of graft copolymers in which one or more of the selected monomers are copolymerized. A more preferable elastic polymer is a core-shell type graft copolymer in which one or more shells of the above-mentioned monomer are graft-copolymerized on the core of the rubber component.

  Moreover, the rubber component and the block copolymer of the said monomer are also mentioned. Specific examples of such block copolymers include thermoplastic elastomers such as styrene / ethylenepropylene / styrene elastomers (hydrogenated styrene / isoprene / styrene elastomers) and hydrogenated styrene / butadiene / styrene elastomers. Furthermore, various elastic polymers known as other thermoplastic elastomers such as polyurethane elastomers, polyester elastomers, polyether amide elastomers and the like can also be used.

  A core-shell type graft copolymer is more suitable as an impact modifier. In the core-shell type graft copolymer, the core particle size is preferably 0.05 to 0.8 μm, more preferably 0.1 to 0.6 μm, and more preferably 0.1 to 0.5 μm in weight average particle size. Is more preferable. If it is in the range of 0.05 to 0.8 μm, better impact resistance is achieved. The elastic polymer preferably contains 40% or more of a rubber component, and more preferably contains 60% or more.

  Rubber components include butadiene rubber, butadiene-acrylic composite rubber, acrylic rubber, acrylic-silicone composite rubber, isobutylene-silicone composite rubber, isoprene rubber, styrene-butadiene rubber, chloroprene rubber, ethylene-propylene rubber, nitrile rubber, ethylene- Acrylic rubber, silicone rubber, epichlorohydrin rubber, fluororubber, and those in which hydrogen is added to these unsaturated bonds may include halogen atoms because of concerns about the generation of harmful substances during combustion. No rubber component is preferable in terms of environmental load.

  The glass transition temperature of the rubber component is preferably −10 ° C. or lower, more preferably −30 ° C. or lower. As the rubber component, butadiene rubber, butadiene-acrylic composite rubber, acrylic rubber, and acrylic-silicone composite rubber are particularly preferable. The composite rubber is a rubber obtained by copolymerizing two kinds of rubber components or a rubber polymerized so as to have an IPN structure entangled with each other so as not to be separated.

  Examples of the aromatic vinyl in the vinyl compound copolymerized with the rubber component include styrene, α-methylstyrene, p-methylstyrene, alkoxystyrene, halogenated styrene and the like, and styrene is particularly preferable. Examples of acrylic esters include methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, octyl acrylate, etc., and examples of methacrylic esters include methyl methacrylate, ethyl methacrylate, methacrylic acid. Examples thereof include butyl, cyclohexyl methacrylate, octyl methacrylate and the like, and methyl methacrylate is particularly preferable. Among these, it is particularly preferable to contain a methacrylic acid ester such as methyl methacrylate as an essential component. More specifically, the methacrylic acid ester is contained in 100% by weight of the graft component (in the case of 100% by weight of the shell in the case of the core-shell type polymer), preferably 10% by weight or more, more preferably 15% by weight or more. Is done.

  The elastic polymer containing a rubber component having a glass transition temperature of 10 ° C. or less may be produced by any polymerization method including bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. It can be a single-stage graft or a multi-stage graft. Moreover, the mixture with the copolymer of only the graft component byproduced in the case of manufacture may be sufficient. Furthermore, examples of the polymerization method include a general emulsion polymerization method, a soap-free polymerization method using an initiator such as potassium persulfate, a seed polymerization method, and a two-stage swelling polymerization method. In the suspension polymerization method, the aqueous phase and the monomer phase are individually maintained, both are accurately supplied to the continuous disperser, and the particle diameter is controlled by the rotation speed of the disperser, and the continuous production is performed. In the method, a method may be used in which the monomer phase is supplied by passing it through a fine orifice having a diameter of several to several tens of μm or a porous filter in an aqueous liquid having dispersibility to control the particle size. In the case of a core-shell type graft polymer, the reaction may be one stage or multistage for both the core and the shell.

  Such elastic polymers are commercially available and can be easily obtained. For example, as rubber components mainly composed of butadiene rubber, acrylic rubber or butadiene-acrylic composite rubber, Kane Ace B series (for example, B-56 etc.) of Kanegafuchi Chemical Industry Co., Ltd., Metabrene of Mitsubishi Rayon Co., Ltd. C series (for example, C-223A), W series (for example, W-450A), Paraloid EXL series (for example, EXL-2602) by Kureha Chemical Industry, HIA series (for example, HIA-15), BTA series (E.g., BTA-III), KCA series, Rohm and Haas Paraloid EXL series, KM series (e.g., KM-336P, KM-357P, etc.), and Ube modifier resin series (UMG)・ ABS's MG AXS Resin Series) and the like, and those mainly composed of acrylic-silicone composite rubber as the rubber component are those commercially available from Mitsubishi Rayon Co., Ltd. under the trade name Methbrene S-2001 or SRK-200. It is done.

  The composition ratio of the elastic polymer is preferably 0.2 to 50 parts by weight per 100 parts by weight of the polycarbonate resin (component A), preferably 1 to 30 parts by weight, and more preferably 1.5 to 20 parts by weight. Such a composition range can give good impact resistance to the composition while suppressing a decrease in rigidity.

<About other ingredients>
Various components may be further added to the resin composition constituting the automobile part of the present invention. These usable components are exemplified below.

(I) Filler In the component A polycarbonate resin constituting the automobile part of the present invention, when a filler (component B) is further blended, a part excellent in mechanical characteristics, dimensional characteristics and the like can be obtained. As the filler, inorganic fillers and organic fillers can be used.

  As inorganic fillers, various inorganic fillers generally known such as glass fiber, carbon fiber, glass flake, wollastonite, kaolin clay, mica, talc and various whiskers (potassium titanate whisker, aluminum borate whisker, etc.) Materials can be mentioned. The shape of the inorganic filler can be freely selected from fibrous, flaky, spherical and hollow shapes, and fibrous and flaky materials are suitable for improving the strength and impact resistance of the resin composition.

  Among them, the inorganic filler is preferably an inorganic filler made of a pulverized product of natural mineral, more preferably an inorganic filler made of a pulverized product of a natural mineral of silicate, and from the point of its shape. Are preferably mica, talc, and wollastonite.

  On the other hand, since these inorganic fillers are non-petroleum resource materials compared to petroleum resource materials such as carbon fibers, raw materials with a lower environmental load are used, and as a result, A component with a lower environmental load is used. There is an effect that the significance of use is further enhanced. Furthermore, the above-mentioned more preferable inorganic filler has an advantageous effect that good flame retardancy is exhibited as compared with carbon fiber and the like.

  The mica that can be used in the present invention has an average particle diameter of 10 to 500 μm expressed by a number average particle diameter calculated by a total number of 1000 particles observed by a scanning electron microscope and extracted those having a size of 1 μm or more. More preferably, it is 30-400 micrometers, More preferably, it is 30-200 micrometers, Most preferably, it is 35-80 micrometers. When the number average particle diameter is less than 10 μm, the impact strength may be lowered. On the other hand, if it exceeds 500 μm, the impact strength is improved, but the appearance tends to deteriorate.

  As the thickness of mica, one having a thickness measured by electron microscope observation of 0.01 to 10 μm can be used. Preferably 0.1-5 micrometers thing can be used. An aspect ratio of 5 to 200, preferably 10 to 100 can be used. The mica used is preferably mascobite mica, and its Mohs hardness is about 3. Muscovite mica can achieve higher rigidity and strength than other mica such as phlogopite, and a more suitable injection molded product is provided.

  In addition, as a method for pulverizing mica, a dry pulverization method of pulverizing raw mica ore with a dry pulverizer, and coarsely pulverizing mica rough ore with a dry pulverizer, followed by adding a grinding aid such as water in a slurry state There is a wet pulverization method in which main pulverization is performed by a wet pulverizer, followed by dehydration and drying. The mica of the present invention can be produced by any pulverization method, but the dry pulverization method is generally lower in cost. On the other hand, the wet pulverization method is effective for pulverizing mica more thinly and finely, but is expensive. Mica may be surface-treated with various surface treatment agents such as silane coupling agents, higher fatty acid esters, and waxes, and further granulated with sizing agents such as various resins, higher fatty acid esters, and waxes to form granules. May be.

The talc that can be used in the present invention is a scaly particle having a layered structure, which is a hydrous magnesium silicate in terms of chemical composition, and is generally represented by the chemical formula 4SiO ₂ .3MgO.2H ₂ O. the SiO ₂ 56-65 wt%, the MgO 28 to 35 wt%, and a _{H 2} O about 5 wt%. As other minor components, Fe ₂ O ₃ is 0.03 to 1.2% by weight, Al ₂ O ₃ is 0.05 to 1.5% by weight, CaO is 0.05 to 1.2% by weight, K ₂ O. Is 0.2 wt% or less, Na ₂ O is 0.2 wt% or less, the specific gravity is about 2.7, and the Mohs hardness is 1.

  The average particle diameter of talc that can be used in the present invention is preferably 0.5 to 30 μm. The average particle size is a particle size at a 50% stacking rate obtained from the particle size distribution measured by the Andreazen pipette method measured according to JIS M8016. The particle diameter of talc is more preferably 2 to 30 μm, further preferably 5 to 20 μm, and most preferably 10 to 20 μm. Talc in the range of 0.5 to 30 μm imparts good surface appearance and flame retardancy to the injection molded product in addition to rigidity and low anisotropy.

  In addition, there is no particular restriction on the manufacturing method when talc is crushed from raw stone, and the axial flow mill method, the annular mill method, the roll mill method, the ball mill method, the jet mill method, the container rotary compression shearing mill method, etc. are used. can do. Further, the talc after pulverization is preferably classified by various classifiers and having a uniform particle size distribution. There are no particular restrictions on the classifier, impactor type inertial force classifier (variable impactor, etc.), Coanda effect type inertial force classifier (elbow jet, etc.), centrifugal field classifier (multistage cyclone, microplex, dispersion separator) , Accucut, Turbo Classifier, Turboplex, Micron Separator, and Super Separator).

  Further, talc is preferably in an agglomerated state in view of its handleability and the like, and as such a production method, there are a method by deaeration compression, a method of compression using a sizing agent, and the like. In particular, the method by deaeration and compression is preferable because it is simple and does not include unnecessary sizing agent resin components in the molded article of the present invention.

The wollastonite that can be used in the present invention is substantially represented by the chemical formula CaSiO ₃ , and usually SiO ₂ is about 50 wt% or more, CaO is about 47 wt% or more, and other Fe ₂ O ₃ , Al ₂ O _3. Etc. Wollastonite is a white acicular powder obtained by crushing and classifying raw wollastonite, and has a Mohs hardness of about 4.5. The average fiber diameter of wollastonite used is preferably 0.5 to 20 μm, more preferably 0.5 to 10 μm, and most preferably 1 to 5 μm. The average fiber diameter is observed by a scanning electron microscope, and is calculated by a number average of a total of 1000 samples having a diameter of 0.1 μm or more extracted.

  The blending amount of these inorganic fillers is preferably 0.3 to 200 parts by weight, more preferably 1.0 to 100 parts by weight, and most preferably 3 to 50 parts by weight per 100 parts by weight of the polycarbonate resin (component A). When the blending amount is less than 0.3 parts by weight, the reinforcing effect on the mechanical properties of the molded product of the present invention is not sufficient, and when it exceeds 200 parts by weight, the molding processability and hue deteriorate, which is not preferable. .

  In addition, in the resin composition which comprises the electric / electronic component of this invention, when using a fibrous inorganic filler and a flaky inorganic filler, the folding inhibitor for suppressing those folding can be included. The folding inhibitor inhibits adhesion between the matrix resin and the inorganic filler, reduces stress acting on the inorganic filler during melt kneading, and suppresses the folding of the inorganic filler. Examples of the effect of the folding inhibitor include (1) improvement of rigidity (increase in aspect ratio of inorganic filler), (2) improvement of toughness, and (3) improvement of conductivity (in the case of conductive inorganic filler). Can do. Specifically, the crease suppressor has (i) a compound having a low affinity with the resin, and (ii) a structure having a low affinity with the resin when the surface of the inorganic filler is directly coated with the compound. It is a compound having a functional group capable of reacting with the surface of the inorganic filler.

  Representative examples of the compound having a low affinity for the resin include various lubricants. Examples of the lubricant include mineral oil, synthetic oil, higher fatty acid ester, higher fatty acid amide, polyorganosiloxane (silicone oil, silicone rubber, etc.), olefinic wax (paraffin wax, polyolefin wax, etc.), polyalkylene glycol, fluorinated fatty acid. Fluorine oils such as esters, trifluorochloroethylene, and polyhexafluoropropylene glycol are listed.

  As a method of directly coating the surface of the inorganic filler with a compound having a low affinity for the resin, (1) a method of directly immersing the compound or a solution or emulsion of the compound in the inorganic filler; A method of passing an inorganic filler in the vapor or powder of a compound, (3) a method of irradiating the inorganic filler with the powder of the compound at high speed, and (4) a mechanochemical that rubs the inorganic filler and the compound. And the like.

  Examples of the compound having a structure having a low affinity with the resin and having a functional group capable of reacting with the surface of the inorganic filler include the above-described lubricants modified with various functional groups. Examples of such functional groups include a carboxyl group, a carboxylic acid anhydride group, an epoxy group, an oxazoline group, an isocyanate group, an ester group, an amino group, and an alkoxysilyl group.

  One suitable folding inhibitor is an alkoxysilane compound in which an alkyl group having 5 or more carbon atoms is bonded to a silicon atom. The number of carbon atoms of the alkyl group bonded to the silicon atom is preferably 5 to 60, more preferably 5 to 20, still more preferably 6 to 18, and particularly preferably 8 to 16. The alkyl group is preferably 1 or 2, and particularly preferably 1. Further, preferred examples of the alkoxy group include a methoxy group and an ethoxy group. Such alkoxysilane compounds are preferred in that they have high reactivity with the inorganic filler surface and excellent coating efficiency. Therefore, it is suitable for a finer inorganic filler.

  One suitable folding inhibitor is a polyolefin wax having at least one functional group selected from a carboxyl group and a carboxylic anhydride group. The molecular weight is preferably 500 to 20,000, more preferably 1,000 to 15,000 in terms of weight average molecular weight. In such a polyolefin wax, the amount of carboxyl group and carboxylic anhydride group is in the range of 0.05 to 10 meq / g per gram of lubricant having at least one functional group selected from carboxyl group and carboxylic anhydride group. Is preferable, more preferably 0.1 to 6 meq / g, and still more preferably 0.5 to 4 meq / g. It is preferable that the ratio of the functional group in the folding inhibitor is the same as the ratio of the carboxyl group and the carboxylic anhydride group in the functional group other than the carboxyl group.

  A particularly preferred example of the folding inhibitor is a copolymer of an α-olefin and maleic anhydride. Such a copolymer can be produced by melt polymerization or bulk polymerization in the presence of a radical catalyst according to a conventional method. Here, as the α-olefin, those having 10 to 60 carbon atoms as an average value can be preferably exemplified. More preferable examples of the α-olefin include those having an average carbon number of 16 to 60, and more preferably 25 to 55.

  The folding inhibitor is preferably 0.01 to 2 parts by weight, more preferably 0.05 to 1.5 parts by weight, and still more preferably 0.1 to 0.8 parts by weight per 100 parts by weight of the polycarbonate resin (component A). .

  Examples of the organic filler include synthetic fibers such as aramid fiber, polyester fiber, and nylon fiber, and natural fibers such as kenaf, hemp, and bamboo. As for the organic filler, it is preferable to use natural fibers from the viewpoint of environmental load. A preferable blending amount of the organic filler is the same as that of the inorganic filler.

(Ii) Flame retardant A flame retardant can also be mix | blended with the resin composition which comprises the motor vehicle part of this invention. Flame retardants include brominated epoxy resins, brominated polystyrenes, brominated polycarbonates, brominated polyacrylates, halogenated flame retardants such as chlorinated polyethylene, phosphate ester flame retardants such as monophosphate compounds and phosphate oligomer compounds, Organic phosphorus flame retardants other than phosphate ester flame retardants such as phosphinate compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, phosphonic acid amide compounds, organic sulfonate alkali (earth) metal salts, borate metal salt flame retardants And organic metal salt flame retardants such as metal stannate flame retardants, silicone flame retardants, ammonium polyphosphate flame retardants, and triazine flame retardants. Separately, a flame retardant aid (for example, sodium antimonate, antimony trioxide, etc.), an anti-drip agent (polytetrafluoroethylene having fibril-forming ability, etc.), etc. may be blended and used together with the flame retardant.

  Among the above-mentioned flame retardants, compounds that do not contain chlorine and bromine atoms have reduced features that are undesirable when performing incineration and thermal recycling. It is more suitable as a flame retardant in the molded article of the present invention.

  In the polycarbonate resin composition constituting the automobile part of the present invention, when these flame retardants are blended, the range of 0.05 to 50 parts by weight per 100 parts by weight of the polycarbonate resin (component A) is preferable. If it is less than 0.05 part by weight, sufficient flame retardancy will not be exhibited, and if it exceeds 50 parts by weight, the strength and heat resistance of the molded product will be impaired.

(Iii) Thermal stabilizer The resin composition constituting the automobile part of the present invention preferably contains a phosphorus-based stabilizer in order to obtain a better hue and stable fluidity. In particular, a pentaerythritol-type phosphite compound represented by the following general formula (5) is preferably blended as a phosphorus stabilizer.

［式中Ｒ^２１、Ｒ^２２はそれぞれ水素原子、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基ないしアルキルアリール基、炭素数７〜３０のアラルキル基、炭素数４〜２０のシクロアルキル基、または炭素数１５〜２５の２−（４−オキシフェニル）プロピル置換アリール基を示す。なお、シクロアルキル基およびアリール基は、アルキル基で置換されていてもよい。］

[Wherein R ²¹ and R ²² are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an alkylaryl group, an aralkyl group having 7 to 30 carbon atoms, and an alkyl group having 4 to 20 carbon atoms. A cycloalkyl group or a 2- (4-oxyphenyl) propyl-substituted aryl group having 15 to 25 carbon atoms is shown. In addition, the cycloalkyl group and the aryl group may be substituted with an alkyl group. ]

  More specifically, examples of the pentaerythritol type phosphite compound include distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, and bis (2,6 -Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, Examples thereof include bis (nonylphenyl) pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite, etc. Among them, distearyl pentaerythritol diphosphite, bis (2,4-di-tert- Butylphenyl) pentaerythritol diphosphite and bis (2,6-di -tert- butyl-4-methylphenyl) pentaerythritol diphosphite.

  Examples of other phosphorus stabilizers include various other phosphite compounds, phosphonite compounds, and phosphate compounds.

  Examples of the phosphite compound include 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) phos Phyto, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite Ito, and tris (2,6-di -tert- butylphenyl) phosphite and the like.

  Still other phosphite compounds that 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)- 4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, and the like, 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.

  Said phosphorus stabilizer can be used individually or in combination of 2 or more types, It is preferable to mix | blend an effective amount of a pentaerythritol type | mold phosphite compound at least. The phosphorus stabilizer is preferably 0.001 to 1 part by weight, more preferably 0.01 to 0.5 part by weight, still more preferably 0.01 to 0.3 part by weight per 100 parts by weight of the polycarbonate resin (component A). Partly formulated.

(Iv) Other additives The resin composition constituting the automobile part of the present invention includes other thermoplastic resins (for example, other polycarbonate resins, aromatic polyester resins, fats, and the like within the range where the effects of the present invention are exhibited). Group polyester resin, polyarylate resin, liquid crystalline polyester resin, polyamide resin, polyimide resin, polyetherimide resin, polyurethane resin, silicone resin, polyphenylene ether resin, polyphenylene sulfide resin, polysulfone resin, polyolefin resin such as polyethylene and polypropylene, polystyrene Resin, acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), polystyrene resin, high impact polystyrene resin, syndiotactic polystyrene tree Fats, polymethacrylate resins, phenoxy or epoxy resins, etc.), antioxidants (eg, hindered phenol compounds, sulfur antioxidants, etc.), UV absorbers (benzotriazoles, triazines, benzophenones, etc.) ), Light stabilizers (HALS, etc.), mold release agents (saturated fatty acid esters, unsaturated fatty acid esters, polyolefin waxes, fluorine compounds, paraffin wax, beeswax, etc.), flow modifiers (polycaprolactone, etc.), colorants ( Carbon black, titanium dioxide, various organic dyes, metallic pigments, etc.), light diffusing agents (acrylic crosslinked particles, silicone crosslinked particles, etc.), fluorescent brighteners, phosphorescent pigments, fluorescent dyes, antistatic agents, inorganic and organic Antibacterial agent, photocatalytic antifouling agent (fine particle titanium oxide, fine particle zinc oxide, etc.), infrared absorption Agents, and the like photochromic agent ultraviolet absorber may be blended. These various additives can be used in known blending amounts when blended with a thermoplastic resin such as bisphenol A polycarbonate.

<About the manufacturing method of a resin composition>
Arbitrary methods are employ | adopted in order to manufacture the resin composition which comprises the motor vehicle part of this invention. For example, each component and optionally other components can be premixed and then melt-kneaded and pelletized. Examples of the premixing means include a Nauter mixer, a V-type blender, a Henschel mixer, a mechanochemical apparatus, and an extrusion mixer. In the preliminary mixing, granulation can be performed by an extrusion granulator or a briquetting machine depending on the case. After the preliminary mixing, the mixture is melt-kneaded by a melt-kneader represented by a vent type twin-screw extruder and pelletized by a device such as a pelletizer. Other examples of the melt kneader include a Banbury mixer, a kneading roll, and a constant temperature stirring vessel, but a vent type twin screw extruder is preferred. In addition, each component and optionally other components can be independently supplied to a melt-kneader represented by a twin-screw extruder without being premixed. The cylinder temperature at the time of melt kneading is preferably in the range of 220 to 270 ° C, more preferably in the range of 230 to 260 ° C, and still more preferably in the range of 230 to 250 ° C. When the cylinder temperature exceeds 270 ° C., the progress of thermal decomposition of the polycarbonate of the present invention becomes large.

<Manufacture of automotive parts>
The automobile part of the present invention is obtained by injection molding at a cylinder temperature of 220 to 270 ° C. In order to suppress coloration and molecular weight reduction due to polymer decomposition, the temperature range is more preferably 230 to 260 ° C, and further preferably 230 to 250 ° C. When the cylinder temperature exceeds 270 ° C., the decomposition of the polymer is greatly accelerated. The mold temperature can be preferably in the range of 40 to 140 ° C., but in order to shorten the molding cycle and shorten the melt residence time of the resin, 40 to 120 ° C. is more preferable, and more preferably 40 to 100 ° C. It is a range.

  Regarding the injection molding for obtaining the automobile part of the present invention, not only a normal cold runner molding method but also a hot runner molding method is possible. 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.

  The automobile parts of the present invention include vehicle exterior parts, vehicle interior parts, drive system mechanism parts, electronic control system electronic / electric parts, electronic control system mechanism parts, internal combustion engine related parts, exhaust system related parts, various display device parts, Various lighting device parts, etc. are mentioned. Specifically, back panel, fender, bumper, facer, door panel, side garnish, pillar, radiator grill, side protector, side molding, rear protector, rear molding, various spoilers, bonnet, roof panel, trunk lid, detachable top, wind Reflector, headlamp lens, mirror housing, outer door handle, wiper part, window washer nozzle, auto antenna part, trim, lamp socket, lamp reflector, lamp housing, instrument panel, center console panel, deflector part, meter part, air Flow meter, actuator, ignition coil, distributor parts, gas cap, fuse Sensor housing, harness connector, various switches, various relays, fuel piping parts, engine rocker cover, engine ornament cover, timing belt cover, belt tensioner pulley, chain guide, cam sprocket, generator bobbin, air cleaner case, air intake Ducts, surge tanks, fuel tanks, intake manifolds, fuel injection parts, car navigation parts, car audio visual parts, auto mobile computer parts, and the like can be suitably exemplified.

  Furthermore, the automobile part of the present invention can be further provided with other functions by surface modification. Surface modification here means a new layer on the surface of resin molded products such as vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot dipping, etc.), painting, coating, printing, etc. The method used for normal resin molded products can be applied.

  The present invention is an automotive part obtained from a polycarbonate resin made from biomass resources, which has good heat resistance, mechanical properties, and environmental resistance properties, and in addition, has a reduced environmental impact. For this reason, it is useful for various automotive parts applications, and its industrial effect is exceptional.

Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to these.
A polycarbonate resin was produced by the method shown in the following production example. Moreover, each value in an Example was calculated | required with the following method.

(1) Melt viscosity Obtained as a result of measurement using a capillary rheometer (Capillograph Model 1D) manufactured by Toyo Seiki Co., Ltd. with a capillary length of 10.0 mm, a capillary diameter of 1.0 mm, and a measurement temperature of 250 ° C. The melt viscosity at 600 sec ⁻¹ was read from the obtained Shear Rate / Viscosity curve.
(2) Glass transition temperature The glass transition temperature was measured by DSC (model DSC2910) manufactured by TA Instruments.
(3) 5% weight loss temperature Measured with TGA (model TGA2950) manufactured by TA Instruments.

<Production Example 1: Production of Polycarbonate A-1 Component>
1608 parts by weight (11 moles) of isosorbide and 2356 parts by weight (11 moles) of diphenyl carbonate were placed in a reactor, and 1.0 part by weight of tetramethylammonium hydroxide was used as a polymerization catalyst (1 × with respect to 1 mole of diphenyl carbonate component). ^10-4 mol) and 1.1 × 10 ⁻³ parts by weight of sodium hydroxide (0.25 × 10 ⁻⁶ mol with respect to 1 mol of diphenyl carbonate component), and heated to 180 ° C. under a nitrogen atmosphere at normal pressure And melted.

Under stirring, the pressure in the reaction vessel was gradually reduced over 30 minutes, and the pressure was reduced to 13.3 × 10 ⁻³ MPa while the produced phenol was distilled off. After reacting in this state for 20 minutes, the temperature was raised to 200 ° C., then the pressure was gradually reduced over 20 minutes, and the reaction was carried out at 4.00 × 10 ⁻³ MPa for 20 minutes while distilling off the phenol. The mixture was heated to 250 ° C. for 30 minutes and reacted for 30 minutes.

Next, the pressure was gradually reduced, and the reaction was continued at 2.67 × 10 ⁻³ MPa for 10 minutes and 1.33 × 10 ⁻³ MPa for 10 minutes, and further reduced in pressure to reach 4.00 × 10 ⁻⁵ MPa. The temperature was gradually raised, and the reaction was finally carried out at 250 ° C. and 6.66 × 10 ⁻⁵ MPa for 40 minutes. As a result, a polymer having a glass transition temperature of 156 ° C., a melt viscosity at a shear rate of 600 sec ⁻¹ of 0.53 × 10 ³ Pa · s, and a 5% weight reduction temperature of 360 ° C. was obtained.

<Production Example 2: Production of Polycarbonate A-2 Component>
A polymer was obtained in the same manner as in Production Example 1 except that the reaction was finally carried out at 260 ° C. and 6.66 × 10 ⁻⁵ MPa for 60 minutes. The polymer had a glass transition temperature of 164 ° C. and a shear rate of 600 sec ⁻¹ . The melt viscosity was 1.7 × 10 ³ Pa · s, and the 5% weight loss temperature was 362 ° C.

<Production Example 3: Production of Polycarbonate A-3 Component>
1590 parts by weight (10.88 moles) of isosorbide and 36 parts by weight (0.24 moles) of p-tert-butylphenol were placed in a thermometer and a reactor equipped with a stirrer, purged with nitrogen, and 5500 parts by weight of pyridine well dried beforehand. Then, 32400 parts by weight of methylene chloride was added and dissolved. Under stirring, 1400 parts by weight (14.14 mol) of phosgene was blown in for 100 minutes at 25 ° C. After the completion of phosgene blowing, the reaction was terminated by stirring for about 20 minutes. After completion of the reaction, the product was diluted with methylene chloride, pyridine was neutralized and removed with hydrochloric acid, washed repeatedly with water until the conductivity was almost the same as that of ion-exchanged water, and then methylene chloride was evaporated. As a result, a polymer having a glass transition point of 172 ° C. and a melt viscosity of 5.1 × 10 ³ Pa · s at a shear rate of 600 sec ⁻¹ and a 5% weight reduction temperature of 362 ° C. was obtained.

<Production Example 4: Production of Polycarbonate A-4 Component>
A polymer was obtained in the same manner as in Production Example 1, except that 1608 parts by weight (11 moles) of isosorbide and 2427 parts by weight (11.33 moles) of diphenyl carbonate were used. This polymer had a glass transition temperature of 138 ° C., a melt viscosity at a shear rate of 600 sec ⁻¹ of 0.13 × 10 ³ Pa · s, and a 5% weight loss temperature of 355 ° C.

Molded articles were produced by the methods shown in the following examples and comparative examples. Moreover, each value in an Example was calculated | required with the following method.
(1) Heat resistance: In accordance with ISO75-1 and 2, the deflection temperature under load was measured under the condition of load: 1.80 MPa.
(2) Bending strength and flexural modulus: Bending characteristics were measured according to ISO178 (test piece shape: length 80 mm × width 10 mm × thickness 4 mm).
(3) Impact resistance: Notched Charpy impact strength was measured in accordance with ISO179.
(4) Chemical resistance: A 3.2 mm-thick test piece prepared according to ISO 527-1 and 2 was immersed in essoregular gasoline for 12 hours at room temperature with a 0.5% bending strain. The appearance of the molded product was visually observed and judged by the presence or absence of cracks. An outline of the test piece attachment is shown in FIG.
○: No crack occurred ×: Crack occurred Note that the bending strain (ε = 0.005) is L (100 mm) for the span at two ends of the three points, and h (3.2 mm) for the thickness of the test piece. ), and when the height lifting the specimen from the horizontal state to the y (mm), a ε = (6hy) / value calculated from the equation of L ^2.
(5) Hydrolysis resistance: The molecular weight after treating a molded article (the test piece prepared in (4) above) in a constant temperature and humidity chamber at 80 ° C. × 90% relative humidity for 10 days is treated. Evaluation was based on the retention rate relative to the previous value.

The following were used as raw materials.
(B-1) Acrylic elastic polymer (EXL-2602 manufactured by Kureha Chemical Industry Co., Ltd.)
(Appendix-1) Antioxidant: Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (Adeka ADEKA STAB PEP-36)
(Appendix-2) Mold release agent: stearic acid monoglyceride (Rikenmar S-100A manufactured by Riken Vitamin Co., Ltd.)
Further, the following resins were used as comparative resins.
(Ratio-1) Bisphenol A-polycarbonate resin: L-1250 (manufactured by Teijin Chemicals Ltd.)
(Ratio-2) Poly-L-lactic acid resin: LACEA H-100J (manufactured by Mitsui Chemicals, Inc.)

<Examples 1-3, Comparative Examples 1-5>
Polycarbonate resin and other components having the composition shown in Table 1 are supplied to a vent type twin screw extruder [TEX30XSST manufactured by Nippon Steel Works, Ltd.] having a diameter of 30 mmφ, cylinder temperature 250 ° C., screw rotation speed 150 rpm, discharge amount 20 kg. / H, and melt-extruded at a reduced pressure of 3 kPa for pelletization.

  The screw configuration is the first kneading zone (consisting of feed kneading disk x 2, feed rotor x 1, return rotor x 1 and return kneading disk x 1) before the side feeder position. A second-stage kneading zone (consisting of a feed rotor × 1 and a return rotor × 1) was provided after the feeder position.

  The obtained pellets were dried with a hot air circulation dryer at 100 ° C. for 12 hours. After drying, test pieces for various characteristic evaluations were molded by an injection molding machine (JSWJ-75EIII, manufactured by Nippon Steel Works) at a cylinder temperature, a mold temperature of 90 ° C., and a molding cycle of 180 seconds. . Bisphenol A-polycarbonate resin has a cylinder temperature of 300 ° C., a mold temperature of 90 ° C., and a molding cycle of 180 seconds. Poly-L-lactic acid has a cylinder temperature of 200 ° C., a mold temperature of 25 ° C., and a molding cycle of 300 seconds. Was molded. Each characteristic was measured using these molded articles. Their injection moldability and measurement results are shown in Tables 1-3.

  As is clear from the results of Tables 1 to 3, the polycarbonate resin used in the present invention having a specific melt viscosity and glass transition temperature can obtain a favorable automobile part when injection molded in a specific temperature range, It can be seen that it has excellent heat resistance and mechanical properties. Furthermore, it has better chemical resistance than bisphenol A-polycarbonate resin, which is the most representative engineering plastic, and has hydrolysis resistance comparable to that, and it is a plastic made from the most representative biomass resource. It has also been found that it has better chemical resistance and hydrolysis resistance than -L-lactic acid, and its environmental resistance is also at a very high level.

It is the perspective view which showed the outline | summary of the jig which performs 3 point | piece bending in evaluation of chemical resistance which is one of the evaluation items of the said Example.

Explanation of symbols

1. First fixing rod (made of stainless steel with a diameter of 3.9 mmφ)
2. Center part of the test piece (installed to be located at the top of the arc drawn by the test piece)
3. Moving rod for strain loading (made of stainless steel with a diameter of 3.9 mmφ)
4). Screw screw for strain loading (penetrated through the back surface of the pedestal 57. The screw screw is turned from the position in contact with the unloaded test piece, and a predetermined amount of strain is loaded on the test piece based on the screw pitch)
5). Test piece 6. Second fixing rod (made of stainless steel with a diameter of 3.9 mmφ)
7). Pedestal 8. Horizontal distance between the second fixed rod and the moving rod for strain load (50.0mm)
9. Horizontal distance from the first fixed rod to the moving rod for strain load (50.0mm)

Claims (4)

It consists of a carbonate structural unit represented by the following formula (1), and the melt viscosity measured by a capillary rheometer at 250 ° C. is 0.2 × 10 ^{3 to} 4.0 × 10 ³ Pa under the condition of a shear rate of 600 sec ^-1. Automobile parts obtained by injection molding a polycarbonate resin (component A) in the range of s at a cylinder temperature of 220 to 270 ° C.

  The automobile part according to claim 1, wherein the polycarbonate resin (component A) has a glass transition temperature in the range of 145 to 165 ° C. The polycarbonate resin (component A) is an ether diol represented by the following formula (a) and a carbonic acid diester, at least one selected from the group consisting of alkali metal salts, alkaline earth metal salts, and nitrogen-containing basic compounds. The automobile part according to claim 1 or 2, which has been melt polycondensed using a compound as a catalyst.

  The automobile part according to any one of claims 1 to 3, comprising 0.2 to 50 parts by weight of an elastic polymer (component B) per 100 parts by weight of the polycarbonate resin (component A).

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