JP6563782B2 - Automotive interior parts with amine resistance - Google Patents

Description

  The present invention relates to an automobile interior part formed from a polycarbonate resin capable of suppressing polymer degradation under conditions exposed to a basic environment containing an amine. More specifically, the present invention provides an automobile interior part having excellent scratch resistance, impact resistance, and amine resistance made of a polycarbonate resin having a specific structural unit.

  Polyurethane foam is manufactured using polyol and polyisocyanate as the main raw materials, and is foamed while mixing with foaming agents, foam stabilizers, catalysts, colorants, etc., especially in the automotive field. It is widely used for sound absorbing and damping materials such as door trims, headrests, armrests, handles, floor ceilings, shock absorbers, sun visors, etc. The tertiary amine compound used as a catalyst is an indispensable substance in the reaction of polyurethane foam into resin and foaming / expansion, but the amine catalyst gradually evaporates from the polyurethane foam after production, and discoloration of other interior parts and It is known to cause whitening.

In the automotive field, the use of paintless interior parts is being studied for the purpose of reducing environmental impact and improving production efficiency, and there is a need for paintless materials that do not require a coating process for surface protection. . Therefore, amine resistance is required for such a coating-less material.
Polycarbonate resin is excellent in transparency, impact resistance, heat resistance, and dimensional stability, so as an engineering plastic, it can be used in electrical and electronic equipment casings, automotive interior / exterior parts, building materials, furniture, musical instruments, and miscellaneous goods. It is used in a wide range of fields. Furthermore, since it has a lower specific gravity than inorganic glass, it can be reduced in weight and is excellent in productivity, so it is used for window applications such as automobiles.

Furthermore, the sheet | seat and film using a polycarbonate resin are widely used as various display apparatuses and protection components of a motor vehicle interior by performing additional secondary processes, such as a coating process, a laminated body, and surface modification.
However, a polycarbonate resin that has not been subjected to a coating treatment has a problem that when exposed to a basic environment containing an amine, the polymer is decomposed and the surface of the molded product is whitened to cause poor appearance. Furthermore, the pencil hardness of the polycarbonate resin measured in accordance with JIS K5600-5-4 General test method for paints-Part 5: Mechanical properties of coating film-Section 4: Scratch hardness (pencil method) is 2B The problem is that the surface is easily scratched as a coating-less material.

Therefore, it is known to use a copolymer polycarbonate resin (for example, Patent Document 1) having a high surface hardness. However, the copolymer polycarbonate resin has a high surface hardness and excellent ammonia resistance, but has a problem of poor impact resistance.
Furthermore, a method for preparing a polycarbonate or copolycarbonate having 2,2-bis (4-hydroxy-3-methylphenyl) propane as a structural unit is described. (For example, Patent Documents 2 and 3) Although the surface hardness of the polycarbonate resin is improved, amine resistance is not described.
Accordingly, the present situation is that there are no automobile interior parts formed from a polycarbonate resin having excellent scratch resistance, impact resistance, and amine resistance.

Japanese Patent No. 5173803 JP-A-64-069625 Japanese Patent Laid-Open No. 08-183852

  An object of the present invention is to provide an automobile interior part formed from a polycarbonate resin excellent in scratch resistance, impact resistance, and amine resistance.

  The present inventors have surprisingly found that an automobile interior part that achieves the above object can be obtained by having a specific structural unit even if it is a polycarbonate resin. As a result of further investigation based on this finding, the present invention has been completed.

（式（１）中、Ｒ_１およびＲ_２は、それぞれ独立に、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、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６〜１０のアリール基、炭素原子数７〜２０のアラルキル基、炭素原子数６〜１０のアリールオキシ基または炭素原子数７〜２０のアラルキルオキシ基を示し、Ｒ_３およびＲ_４は、それぞれ独立に、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、炭素原子数６〜２０のシクロアルキル基、炭素数６〜２０のシクロアルコキシ基、炭素数６〜１０のアリール基、炭素数７〜２０のアラルキル基、炭素数６〜１０のアリールオキシ基または炭素数７〜２０のアラルキルオキシ基を示し、Ｘは、単結合、置換もしくは無置換の炭素原子数１〜１０のアルキレン基、置換もしくは無置換の炭素原子数１〜１０のアルキリデン基、炭素原子数６〜１０のアリール基、置換もしくは無置換の炭素原子数３〜８の環状アルキル基、硫黄原子または酸素原子を示す。）
で表される構成単位（Ａ）と、
（Ｂ）下記式（２）

（式（２）中、Ｙは、単結合、無置換の炭素原子数１〜１０のアルキレン基、無置換の炭素原子数１〜１０のアルキリデン基、硫黄原子または酸素原子を示す。）
で表される構成単位（Ｂ）から構成される粘度平均分子量が１５，０００〜４０，０００であるポリカーボネート共重合体１００重量部に対して、主たる構成単位として構成単位（Ｂ）から構成される粘度平均分子量が１８，０００〜２８，０００であるポリカーボネート樹脂１〜２５重量部をブレンドした、 ^１Ｈ−ＮＭＲスペクトルから算出される全構成単位における構成単位（Ａ）の割合が２５〜８５モル％であり、^１３Ｃ−ＮＭＲスペクトルから算出される下記式（Ｉ）で示される結合配列のランダム度（Ｒ）が０．８≦（Ｒ）≦１．２であり、下記式（ＩＩ）で示される構成単位（Ａ）を含む結合配列の割合が全結合配列の４０％以上である、アミン耐性を有するポリカーボネートブレンド物から形成される自動車内装部品。

（結合配列（Ｘ）：構成単位Ａと構成単位Ａからなる結合配列
結合配列（Ｙ）：構成単位Ａと構成単位Ｂからなる結合配列
結合配列（Ｚ）：構成単位Ｂと構成単位Ｂからなる結合配列
Ｐ（Ｘ）：結合配列（Ｘ）に由来する^１３Ｃ−ＮＭＲスペクトルピークの面積比
Ｐ（Ｙ）：結合配列（Ｙ）に由来する^１３Ｃ−ＮＭＲスペクトルピークの面積比
Ｐ（Ｚ）：結合配列（Ｚ）に由来する^１３Ｃ−ＮＭＲスペクトルピークの面積比）

That is, according to the present invention, the following (Configuration 1) to (Configuration 10 ) are provided.
(Configuration 1)
As the main structural unit, (A) the following formula (1)

(In Formula (1), R ₁ and R ₂ are each independently a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl having 6 to 20 carbon atoms. Group, a cycloalkoxy group having 6 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or 7 to 20 carbon atoms. R ₃ and R ₄ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or 6 to 20 carbon atoms. A cycloalkyl group having 6 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or 7 to 7 carbon atoms. 20 represents an aralkyloxy group, and X represents a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted alkylidene group having 1 to 10 carbon atoms, or 6 to 10 carbon atoms. An aryl group, a substituted or unsubstituted cyclic alkyl group having 3 to 8 carbon atoms, a sulfur atom or an oxygen atom.)
A structural unit (A) represented by:
(B) The following formula (2)

(In formula (2), Y represents a single bond , an unsubstituted alkylene group having 1 to 10 carbon atoms , an unsubstituted alkylidene group having 1 to 10 carbon atoms, a sulfur atom, or an oxygen atom.)
The polycarbonate copolymer 100 parts by weight of a viscosity-average molecular weight that consists of in a structural unit represented by (B) is 15,000 to 40,000, and a structural unit (B) as a main structural unit The proportion of the structural unit (A) in the total structural unit calculated from the ¹ H-NMR spectrum obtained by blending 1 to 25 parts by weight of a polycarbonate resin having a viscosity average molecular weight of 18,000 to 28,000 is 25 to 85 mol%. The randomness (R) of the binding sequence represented by the following formula (I) calculated from the ¹³ C-NMR spectrum is 0.8 ≦ (R) ≦ 1.2, and is represented by the following formula (II). allocations of binding sequence, including a unit (a) is not less than 40% of the total binding sequence, automobile interior components formed from Lupolen polycarbonate blends having a amine resistant to.

(Binding array (X): Bonding array consisting of structural unit A and structural unit A Bonding array (Y): Binding array consisting of structural unit A and structural unit B Bonding array (Z): consisting of structural unit B and structural unit B Binding sequence P (X): Area ratio of ¹³ C-NMR spectral peak derived from binding sequence (X) P (Y): Area ratio of ¹³ C-NMR spectral peak derived from binding sequence (Y) P (Z) : Area ratio of ¹³ C-NMR spectrum peak derived from the binding sequence (Z))

(Configuration 2)
R ₁ and R ₂ in Formula (1) each independently represent an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and X represents a single atom. Bond, substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, substituted or unsubstituted alkylidene group having 1 to 10 carbon atoms, aryl group having 6 to 10 carbon atoms, substituted or unsubstituted carbon atoms A cyclic alkyl group having 3 to 8; Y in the formula (2) is a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkylidene group having 1 to 10 carbon atoms; Show The automobile interior part as described in 1 above.
(Configuration 3)
Po polycarbonate blend item 1 or 2 automotive interior part according ratio is 30 to 80 mol% of structural units (A) in the total of all structural units is calculated from ^{1 H-NMR} spectrum of.
(Configuration 4)
Po polycarbonate blend complies with the ISO 75, automotive interior component according to any of the preceding 1-3 deflection temperature under load measured at A method (1.8 MPa) is 110 to 170 ° C..
(Configuration 5)
Po polycarbonate blends, conforming to JIS K7202-2, automotive interior component according to any of the preceding 1-4 Rockwell hardness measured at M scale is 80 to 120.
(Configuration 6)
Automotive interior component according to any of the preceding 1-5 viscosity average molecular weight of Po polycarbonate blend is 15,000 to 40,000.
(Configuration 7)
The structural unit (A) is 2,2-bis (4-hydroxy-3-methylphenyl) propane, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,1-bis (4-hydroxy- 3-methylphenyl) cyclohexane and 1,1-bis (4-hydroxy-3-methylphenyl) -3,3,5-trimethylcyclohexane are structural units derived from at least one selected from the group consisting of 1 to 1 above The automobile interior part according to any one of 6 above.
(Configuration 8)
The structural unit (B) is 2,2-bis (4-hydroxyphenyl) automotive interior component according to any of the preceding 1-7 is a structural unit derived propane or al.
(Configuration 9 )
Automotive interior component according to any one of the above items 1-8 formed by injection molding the port polycarbonate blends.
(Configuration 10 )
Automotive interior component according to any one of the above items 1-8 using sheet or film obtained by extruding the port polycarbonate blends.

  Since the polycarbonate resin used in the present invention is excellent in amine resistance, scratch resistance and impact resistance, it is suitably used for automobile interior parts. Therefore, the industrial effects that it plays are exceptional.

（式（１）中、Ｒ_１およびＲ_２は、それぞれ独立に、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、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６〜１０のアリール基、炭素原子数７〜２０のアラルキル基、炭素原子数６〜１０のアリールオキシ基または炭素原子数７〜２０のアラルキルオキシ基を示し、Ｒ_３およびＲ_４は、それぞれ独立に、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、炭素原子数６〜２０のシクロアルキル基、炭素数６〜２０のシクロアルコキシ基、炭素数６〜１０のアリール基、炭素数７〜２０のアラルキル基、炭素数６〜１０のアリールオキシ基または炭素数７〜２０のアラルキルオキシ基を示し、Ｘは、単結合、置換もしくは無置換の炭素原子数１〜１０のアルキレン基、置換もしくは無置換の炭素原子数１〜１０のアルキリデン基、炭素原子数６〜１０のアリール基、置換もしくは無置換の炭素原子数３〜８の環状アルキル基、硫黄原子または酸素原子を示す。）
で表される構成単位（Ａ）と、
（Ｂ）下記式（２）

（式（２）中、Ｙは、単結合、置換もしくは無置換の炭素原子数１〜１０のアルキレン基、置換もしくは無置換の炭素原子数１〜１０のアルキリデン基、硫黄原子または酸素原子を示す。）
で表される構成単位（Ｂ）から構成される。 Details of the present invention will be described below.
<Polycarbonate resin>
The polycarbonate resin (including polycarbonate copolymer and polycarbonate blend) used in the present invention has the following formula (1) as a main structural unit.

(In Formula (1), R ₁ and R ₂ are each independently a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl having 6 to 20 carbon atoms. Group, a cycloalkoxy group having 6 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or 7 to 20 carbon atoms. R ₃ and R ₄ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or 6 to 20 carbon atoms. A cycloalkyl group having 6 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or 7 to 7 carbon atoms. 20 represents an aralkyloxy group, and X represents a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted alkylidene group having 1 to 10 carbon atoms, or 6 to 10 carbon atoms. An aryl group, a substituted or unsubstituted cyclic alkyl group having 3 to 8 carbon atoms, a sulfur atom or an oxygen atom.)
A structural unit (A) represented by:
(B) The following formula (2)

(In formula (2), Y represents a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted alkylidene group having 1 to 10 carbon atoms, a sulfur atom, or an oxygen atom. .)
It is comprised from the structural unit (B) represented by these.

Here, “main” refers to 70 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more, more preferably 95 mol% or more, among 100 mol% of all carbonate structural units excluding terminals. The ratio is preferably 100 mol%.
Moreover, the ratio of the structural unit (A) in all the structural units is the range of 25-85 mol% in molar ratio, the range of 30-80 mol% is preferable, and the range of 30-75 mol% is more preferable. If the proportion of the structural unit (A) is less than 25 mol%, the amine resistance is insufficient, and if the proportion of the structural unit (A) is more than 85 mol%, the impact resistance is inferior. The proportion of the structural unit (A) may be a polycarbonate copolymer or may be achieved by mixing polycarbonate resins having different composition proportions (polycarbonate blend).

In the case of a polycarbonate blend, the polycarbonate composed of the structural unit (B) as the main structural unit with respect to 100 parts by weight of the polycarbonate copolymer composed of the structural unit (A) and the structural unit (B) as the main structural unit. It is preferably a polycarbonate blend obtained by blending 1 to 25 parts by weight of a resin, and a polycarbonate blend obtained by blending 5 to 20 parts by weight of a polycarbonate resin composed of the structural unit (B) as a main structural unit. More preferred.
Moreover, the viscosity average molecular weight of the polycarbonate copolymer comprised from the said structural unit (A) and a structural unit (B) is 15,000-40,000, and is comprised from a structural unit (B) as a main structural unit. It is preferable that the viscosity average molecular weight of polycarbonate resin is 18,000-28,000.

  The polycarbonate resin used in the present invention is obtained by reacting a dihydric phenol and, if necessary, an aliphatic and / or alicyclic bifunctional alcohol with a carbonate precursor. Examples of the reaction method include an interfacial polycondensation method, a melt transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound. In the case of interfacial polycondensation, a terminal stopper of a monohydric phenol is usually used. Moreover, the branched polycarbonate which polymerized the trifunctional component may be sufficient, and also the copolymer polycarbonate which copolymerized aliphatic dicarboxylic acid, aromatic dicarboxylic acid, and a vinyl-type monomer may be sufficient.

  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.

  For example, a transesterification reaction using a carbonic acid diester as a carbonate precursor is carried out by a method in which an aromatic dihydroxy component in a predetermined ratio is stirred with a carbonic acid diester while heating in an inert gas atmosphere to distill the resulting alcohol or phenol. Is called. 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.

  Monofunctional phenols usually used as a terminal terminator can be used. Particularly in the case of reactions using phosgene as a carbonate precursor, monofunctional phenols are generally used as end-stoppers for molecular weight control, and the resulting polycarbonate resins are based on monofunctional phenols at the ends. Since it is blocked by a group, it is superior in thermal stability as compared to other cases. Specific examples of the monofunctional phenols include, for example, phenol, m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, 1-phenylphenol, 2-phenylphenol, p-tert-butylphenol, p-cumylphenol, isooctylphenol, p-long chain alkylphenol and the like can be mentioned.

In the structural unit (A) represented by the formula (1), R ₁ and R ₂ are each independently an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, or a carbon atom. It is preferable to show an aryl group of several 6 to 10. R ₃ and R ₄ preferably each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, or an aryl group having 6 to 10 carbon atoms. X is a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted alkylidene group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, substituted or unsubstituted It is preferable to show a C3-C8 cyclic alkyl group.

  Examples of the dihydric phenol for deriving the structural unit (A) represented by the formula (1) include 2,2-bis (4-hydroxy-3-methylphenyl) propane (hereinafter referred to as bisphenol C), 2,2 -Bis (4-hydroxy-3-isopropylphenyl) propane, 2,2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-diisopropyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-di-) t-butyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-diphenyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxy-3-methyl) Phenyl) cyclohexane, 1,1-bis (4-hydroxy-3-isopropylphenyl) cyclohexane, 1,1-bis (3-tert-butyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3-phenyl-) 4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5-diisopropyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5-di-t-butyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5-diphenyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy-2,3 , 5,6-tetramethylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-methyl) Nyl) -3,3,5-trimethylcyclohexane, 1,1-bis (4-hydroxy-3-isopropylphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (3-t-butyl-4 -Hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (3-phenyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (3,5-dimethyl) -4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (3,5-diisopropyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (3 , 5-Di-t-butyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (3,5-diphenyl-4- Hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (4-hydroxy-2,3,5,6-tetramethylphenyl) -3,3,5-trimethylcyclohexane, 4,4′- Dihydroxy-3,3′-dimethyl-1,1-biphenyl, 4,4′-dihydroxy-3,3′-dioctyl-1,1-biphenyl, 1,3-bis (2- (4-hydroxy-3- Methylphenyl) -2-propyl) benzene, 1,4-bis (2- (4-hydroxy-3-methylphenyl) -2-propyl) benzene, 9,9-bis (4-hydroxy-3-methylphenyl) Fluorene, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether, 3,3′-dimethyl-4,4′-dihydroxydiphenyl sulfide, bis (4-hydro Cis-2,6-dimethyl-3-methoxyphenyl) methane, 2,2-bis (4-hydroxy-3-ethylphenyl) propane 1,1-bis (3-methyl-4-hydroxyphenyl) decane, 1, 1-bis (2,3-dimethyl-4-hydroxyphenyl) decane is mentioned.

  Among the dihydric phenols, bisphenol C, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 1,1-bis ( 4-Hydroxy-3-methylphenyl) -3,3,5-trimethylcyclohexane is preferred. The most preferred dihydric phenol from which the structural unit (A) is derived is bisphenol C.

  In the structural unit (B) represented by the formula (2), Y represents a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkylidene having 1 to 10 carbon atoms. It is preferable to show a group.

  Examples of the dihydric phenol for deriving the structural unit (B) represented by the formula (2) include 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A), 1,1-bis ( 4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 4,4′- Dihydroxy-1,1-biphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl thioether, 1,3-bis (2- (4-hydroxyphenyl) -2-propyl) benzene, 1,4- Bis (2- (4-hydroxyphenyl) -2-propyl) benzene, α, α'-bis (4-hydroxyphenyl)- o-diisopropylbenzene, α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene, α, α′-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 9,9-bis (4-hydroxy) Phenyl) fluorene, 4,4′-dihydroxydiphenylsulfone, 2,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxydiphenylsulfoxide, 4,4′-dihydroxydiphenylsulfide, 1,1-bis (4-hydroxyphenyl) ) Methane, 2,4′-dihydroxydiphenylmethane, bis (2-hydroxyphenyl) methane, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) cyclohexylmethane, bis (4-hydroxyphenyl) diphenylmethane, 1, 1-bis ( -Hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 4,4-bis (4-hydroxyphenyl) heptane, 2,2-bis (4-hydroxyphenyl) octane and 1,1-bis (4-hydroxyphenyl) decane are exemplified.

  Among the dihydric phenols, bisphenol A, 1,1-bis (4-hydroxyphenyl) cyclohexane, and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane are preferable. The most preferred dihydric phenol from which the structural unit (A) is derived is bisphenol A.

  Furthermore, as the dihydric phenol for deriving the structural unit (C) other than the structural units (A) and (B), 2,6-dihydroxynaphthalene, hydroquinone, resorcinol, or an alkyl group having 1 to 3 carbon atoms is preferable. Resorcinol substituted with 3- (4-hydroxyphenyl) -1,1,3-trimethylindan-5-ol, 1- (4-hydroxyphenyl) -1,3,3-trimethylindan-5-ol, 6,6′-dihydroxy-3,3,3 ′, 3′-tetramethylspiroindane, 1-methyl-1,3-bis (4-hydroxyphenyl) -3-isopropylcyclohexane, 1-methyl-2- ( 4-hydroxyphenyl) -3- [1- (4-hydroxyphenyl) isopropyl] cyclohexane, 1,6-bis (4-hydroxyphenyl) 1,6-hexanedione, and the like. Other details of the polycarbonate are described in, for example, WO03 / 080728 pamphlet, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, and JP-A-2002-117580. Has been.

  The polycarbonate resin used in the present invention can be copolymerized with an aliphatic diol as necessary. For example, isosorbide: 1,4: 3,6-dianhydro-D-sorbitol, tricyclodecane dimethanol (TCDDM), 4,8-bis (hydroxymethyl) tricyclodecane, tetramethylcyclobutanediol (TMCBD), 2, 2,4,4-tetramethylcyclobutane-1,3-diol, mixed isomers, cis / trans-1,4-cyclohexanedimethanol (CHDM), cis / trans-1,4-bis (hydroxymethyl) cyclohexane, Cyclohex-1,4-ylenedimethanol, trans-1,4-cyclohexanedimethanol (tCHDM), trans-1,4-bis (hydroxymethyl) cyclohexane, cis-1,4-cyclohexanedimethanol (cCHDM), cis -1,4-bis (hydroxymethyl Cyclohexane, cis-1,2-cyclohexanedimethanol, 1,1′-bi (cyclohexyl) -4,4′-diol, spiroglycol, dicyclohexyl-4,4′-diol, 4,4′-dihydroxybicyclohexyl, And poly (ethylene glycol).

  The polycarbonate resin used for this invention can copolymerize a fatty acid as needed. For example, 1,10-dodecanedioic acid (DDDA), adipic acid, hexanedioic acid, isophthalic acid, 1,3-benzenedicarboxylic acid, terephthalic acid, 1,4-benzenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, Examples include 3-hydroxybenzoic acid (mHBA) and 4-hydroxybenzoic acid (pHBA).

  The polycarbonate resin used in the present invention contains a polyester carbonate copolymerized with an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid. The aliphatic bifunctional carboxylic acid is preferably α, ω-dicarboxylic acid. Examples of aliphatic difunctional carboxylic acids include sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and linear saturated aliphatic dicarboxylic acids such as icosanedioic acid, and cyclohexanedicarboxylic acid. Preferred are alicyclic dicarboxylic acids such as acids. These carboxylic acids may be copolymerized as long as the purpose is not impaired. The polycarbonate resin used for this invention can also copolymerize the structural unit containing a polyorganosiloxane unit as needed.

  The polycarbonate resin used in the present invention can be made into a branched polycarbonate by copolymerizing a structural unit containing a trifunctional or higher polyfunctional aromatic compound as necessary. Examples of the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate include 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, and 4- {4- [1,1-bis ( A preferred example is trisphenol such as 4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol. Of these, 1,1,1-tris (4-hydroxyphenyl) ethane is preferred. The structural unit derived from such a polyfunctional aromatic compound is preferably 0.03 to 1.5 mol%, more preferably 0.1 to 100 mol% in total with the structural units derived from other divalent components. It is -1.2 mol%, Most preferably, it is 0.2-1.0 mol%.

The branched structural unit is not only derived from a polyfunctional aromatic compound but also derived from a side reaction that occurs during the polymerization reaction by the melt transesterification method without using a polyfunctional aromatic compound. May be. The ratio of such a branched structure can be calculated by ¹ H-NMR measurement.

  The polycarbonate used in the present invention has a viscosity average molecular weight (Mv) of preferably 15,000 to 40,000, more preferably 16,000 to 30,000, still more preferably 17,000 to 28,000. With a polycarbonate resin having a viscosity average molecular weight of less than 15,000, practically sufficient impact resistance may not be obtained. On the other hand, a polycarbonate resin having a viscosity average molecular weight exceeding 40,000 is inferior in versatility because it requires a high molding temperature or requires a special molding method. Furthermore, due to the increase in melt viscosity, the injection speed dependency is also high, and the yield decreases due to poor appearance of the molded product.

The viscosity average molecular weight of the polycarbonate in the present invention is first determined by using an Ostwald viscometer from a solution in which 0.7 g of polycarbonate is dissolved in 100 ml of methylene chloride at 20 ° C., with a specific viscosity (η _SP ) calculated 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]
The viscosity average molecular weight Mv is calculated from the obtained specific viscosity (η _SP ) 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

<Ingredients other than polycarbonate resin>
The polycarbonate resin used in the present invention contains a known functional agent such as a mold release agent, a heat stabilizer, an ultraviolet absorber, a flow modifier, or an antistatic agent within a range not impairing the effects of the present invention. it can.

(I) Release agent The polycarbonate resin used in the present invention may be used in combination with a release agent as long as the effects of the present invention are not impaired. Examples of the release agent include fatty acid esters, polyolefin waxes (polyethylene wax, 1-alkene polymers, etc., which can be modified with a functional group-containing compound such as acid modification), fluorine compounds (polyfluoroalkyl). And fluorine oil represented by ether), paraffin wax, beeswax and the like. Of these, fatty acid esters are preferred from the standpoints of availability, releasability and transparency. The proportion of the release agent to be added is preferably 0.005 to 0.5 parts by weight, more preferably 0.007 to 0.4 parts by weight, and still more preferably 0.01 to 100 parts by weight with respect to 100 parts by weight of the polycarbonate resin. 0.3 parts by weight. When the content is at least the lower limit of the above range, the effect of improving the releasability is clearly exhibited, and when the content is not more than the upper limit, adverse effects such as mold contamination during molding are preferably reduced.

  The fatty acid ester used as a preferable release agent among the above will be described in more detail. Such fatty acid esters are esters of aliphatic alcohols and aliphatic carboxylic acids. Such an aliphatic alcohol may be a monohydric alcohol or a dihydric or higher polyhydric alcohol. Moreover, as carbon number of this alcohol, it is the range of 3-32 suitably, More preferably, it is the range of 5-30. Examples of such monohydric alcohols include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, seryl alcohol, and triacontanol. Examples of such polyhydric alcohols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol. In the fatty acid ester, a polyhydric alcohol is more preferable.

  On the other hand, the aliphatic carboxylic acid preferably has 3 to 32 carbon atoms, and particularly preferably an aliphatic carboxylic acid having 10 to 22 carbon atoms. Examples of the aliphatic carboxylic acid include decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, icosanoic acid, And saturated aliphatic carboxylic acids such as docosanoic acid (behenic acid) and unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and cetreic acid it can. Among the above, aliphatic carboxylic acids having 14 to 20 carbon atoms are preferable. Of these, saturated aliphatic carboxylic acids are preferred. Such aliphatic carboxylic acids are usually produced from natural fats and oils such as animal fats (such as beef tallow and pork fat) and vegetable fats and oils (such as palm oil). Of other carboxylic acid components. Accordingly, in the production of aliphatic carboxylic acid, it is produced from such natural fats and oils and is in the form of a mixture containing other carboxylic acid components. The acid value in the fatty acid ester is preferably 20 or less (can take substantially 0). However, in the case of all esters (full esters), it is preferable to contain at least free fatty acids in order to improve releasability. In this respect, the acid value in the full esters is preferably in the range of 3 to 15. The iodine value of the fatty acid ester is preferably 10 or less (can take substantially 0). These characteristics can be obtained by a method defined in JIS K 0070.

  The above-mentioned fatty acid ester may be either a partial ester or a full ester, but the partial ester is preferable from the viewpoint of better releasability and durability, and glycerol monoester is particularly preferable. Glycerin monoester is mainly composed of monoester of glycerin and fatty acid. Suitable fatty acids include saturated fatty acids such as stearic acid, palmitic acid, behenic acid, arachidic acid, montanic acid, lauric acid, oleic acid, and linoleic acid. And unsaturated fatty acids such as sorbic acid, and those having glycerin monoesters of stearic acid, behenic acid, and palmitic acid as main components are particularly preferred. Such fatty acids are synthesized from natural fatty acids and become a mixture as described above. Even in such a case, the ratio of glycerin monoester in the fatty acid ester is preferably 60% by weight or more.

  In addition, partial esters are often inferior to full esters in terms of thermal stability. In order to improve the thermal stability of such a partial ester, the partial ester preferably has a sodium metal content of less than 20 ppm, more preferably less than 5 ppm, and even more preferably less than 1 ppm. The fatty acid partial ester having a sodium metal content of less than 1 ppm can be produced by producing the fatty acid partial ester by an ordinary method and then purifying it by molecular distillation or the like.

  Specifically, after removing gas components and low-boiling substances with a spray nozzle type degassing apparatus, glycerin is used under the conditions of a distillation temperature of 120 to 150 ° C. and a vacuum degree of 0.01 to 0.03 kPa using a falling film distillation apparatus. For example, a high molecular weight fatty acid ester is distilled off using a centrifugal molecular distillation apparatus at a distillation temperature of 160 to 230 ° C. and a vacuum of 0.01 to 0.2 Torr. The sodium metal can be removed as a distillation residue. By subjecting the resulting distillate to repeated molecular distillation, it is possible to further increase the purity and obtain a fatty acid partial ester having a lower sodium metal content. It is also important to prevent the contamination of the sodium metal component from the external environment by thoroughly washing the inside of the molecular distillation apparatus by an appropriate method in advance and improving airtightness. Such a fatty acid ester is available from a specialist (for example, Riken Vitamin Co., Ltd.).

(Ii) Phosphorus stabilizer It is preferable that the polycarbonate resin used in the present invention is further blended with various phosphorus stabilizers mainly for the purpose of improving the thermal stability during the molding process. Examples of such phosphorus stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. In addition, such phosphorus stabilizers include tertiary phosphines.

  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)- 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.
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, phosphite compounds or phosphonite compounds are preferable. In particular, tris (2,4-di-tert-butylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite and bis (2,4-di-) tert-Butylphenyl) -phenyl-phenylphosphonite is preferred. A combination of these and a phosphate compound is also a preferred embodiment.

(Iii) Hindered phenol stabilizer The polycarbonate resin used in the present invention is blended with a hindered phenol stabilizer mainly for the purpose of improving the heat stability and heat aging resistance during the molding process. be able to. Examples of such hindered phenol stabilizers include α-tocopherol, butylhydroxytoluene, sinapyl 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 ′ -Methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-methylenebis (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-thio Ethylenebis- [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, 1,3,3 5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxyphenyl) Isocyanurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate 1,3,5-tris 2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate and tetrakis [methylene-3- (3 ′, 5′-di- tert-butyl-4-hydroxyphenyl) propionate] methane and the like. All of these are readily available. The said hindered phenolic antioxidant can be used individually or in combination of 2 or more types.

  The amount of the above (ii) phosphorus stabilizer and / or (iii) hindered phenol antioxidant is preferably 0.0001 to 1 part by weight, more preferably 0.001 based on 100 parts by weight of the polycarbonate resin. It is -0.1 weight part, More preferably, it is 0.005-0.1 weight part. It is difficult to obtain a good stabilizing effect when the stabilizer is too small than the above range, and when it is too much beyond the above range, the physical properties of the material may be deteriorated or the mold may be contaminated during molding. There is.

  For the polycarbonate resin used in the present invention, an antioxidant other than the hindered phenol-based antioxidant can be used as appropriate. Examples of such other antioxidants include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-lauryl thiopropionate), and glycerol-3-stearyl thiopropionate. The amount of these other antioxidants used is preferably 0.001 to 0.05 parts by weight with respect to 100 parts by weight of the polycarbonate resin.

(Iv) Ultraviolet absorber The polycarbonate used in the present invention may contain an ultraviolet absorber. 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-benzyloxy. Benzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydride benzophenone, 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-methoxy Phenyl) methane, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone and the like.

  Specific examples of the ultraviolet absorber include benzotriazole-based compounds such as 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2 -(2-hydroxy-3,5-dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2'-methylenebis [ 4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzo Triazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazol 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 2- (2 ′ -Hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole and copolymer with the monomer 2 such as a copolymer with a possible vinyl monomer and a copolymer of 2- (2′-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole with a vinyl monomer copolymerizable with the monomer. Examples include polymers having a -hydroxyphenyl-2H-benzotriazole skeleton.

  Specific examples of the ultraviolet absorber include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol and 2- (4) in hydroxyphenyltriazine series. , 6-Diphenyl-1,3,5-triazin-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-ethyloxy Phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-propyloxyphenol, and 2- (4,6-diphenyl-1,3,5-triazine-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.

As the ultraviolet absorber, specifically, in the cyclic imino ester type, for example, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) ) Bis (3,1-benzoxazin-4-one), 2,2 ′-(2,6-naphthalene) bis (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.

  Further, the ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, whereby the ultraviolet-absorbing monomer and / or the light-stable monomer having a hindered amine structure, and an alkyl (meth) acrylate. A polymer type ultraviolet absorber obtained by copolymerization with a monomer such as may be used. Preferred examples of the UV-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) acrylate. The

Among them, benzotriazole and hydroxyphenyltriazine are preferable from the viewpoint of ultraviolet absorption ability, and cyclic imino ester and cyanoacrylate are preferable from the viewpoint of heat resistance and hue. 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 2 parts by weight, more preferably 0.03 to 2 parts by weight, still more preferably 0.04 to 1 part by weight, particularly preferably 100 parts by weight of the polycarbonate resin. Is 0.05 to 0.5 parts by weight.

(V) Flow modifier The polycarbonate resin used in the present invention can contain a flow modifier as long as the effects of the present invention are not impaired. Such flow modifiers include styrene oligomers, polycarbonate oligomers (including highly branched, hyperbranched and cyclic oligomer types), polyalkylene terephthalate oligomers (including highly branched, hyperbranched and cyclic oligomer types) Preferred examples include branched and hyperbranched aliphatic polyester oligomers, terpene resins, and polycaprolactone. Such a flow modifier is preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight, and still more preferably 2 to 15 parts by weight per 100 parts by weight of the polycarbonate resin. Polycaprolactone is particularly suitable, and the composition ratio is particularly preferably 2 to 7 parts by weight per 100 parts by weight of the polycarbonate resin. The molecular weight of polycaprolactone is 1,000 to 70,000 in terms of number average molecular weight, preferably 1,500 to 40,000, more preferably 2,000 to 30,000, and 2,500 to 15,000. Further preferred.

(Vi) Antistatic Agent The polycarbonate resin used in the present invention can be blended with an antistatic agent for the main purpose of improving antistatic properties. As the antistatic agent, sulfonic acid phosphonium salts, phosphite esters, caprolactone-based polymers, and the like can be used, and sulfonic acid phosphonium salts are preferably used. Specific examples of such phosphonium sulfonate salts include tetrabutylphosphonium dodecylsulfonate, tetrabutylphosphonium dodecylbenzenesulfonate, tributyloctylphosphonium dodecylbenzenesulfonate, tetraoctylphosphonium dodecylbenzenesulfonate, tetraethylphosphonium octadecylbenzenesulfonate, dibutyl Examples thereof include tributylmethylphosphonium benzenesulfonate, triphenylphosphonium dibutylnaphthylsulfonate, and trioctylmethylphosphonium diisopropylnaphthylsulfonate. Of these, tetrabutylphosphonium dodecylbenzenesulfonate is preferred because it is compatible with polycarbonate and easily available. The amount of the antistatic agent is preferably 0.1 to 5.0 parts by weight, more preferably 0.2 to 3.0 parts by weight, still more preferably 0.3 to 2.0 parts by weight based on 100 parts by weight of the polycarbonate resin. Part by weight, particularly preferably 0.5 to 1.8 parts by weight is blended. When the amount is 0.1 parts by weight or more, an antistatic effect is obtained, and when the amount is 5.0 parts by weight or less, the transparency and mechanical strength are excellent, and silver or peeling does not occur on the surface of the molded product, and the appearance is hardly caused.

In addition, the polycarbonate resin used in the present invention may contain various additives such as a bluing agent, a fluorescent dye, a flame retardant, and a dye / pigment. These can be appropriately selected and contained as long as the effects of the present invention are not impaired.
The bluing agent preferably comprises 0.05 to 3.0 ppm (weight ratio) in the polycarbonate resin. Representative examples of the bluing agent include Macrolex Violet B and Macrolex Blue RR manufactured by Bayer, and Polysynthrene Blue RLS manufactured by Clariant.

  Examples of fluorescent dyes (including fluorescent brighteners) include coumarin fluorescent dyes, benzopyran fluorescent dyes, perylene fluorescent dyes, anthraquinone fluorescent dyes, thioindigo fluorescent dyes, xanthene fluorescent dyes, and xanthone fluorescent dyes. And thioxanthene fluorescent dyes, thioxanthone fluorescent dyes, thiazine fluorescent dyes, and diaminostilbene fluorescent dyes. The blending amount of the fluorescent dye (including the fluorescent brightening agent) is preferably 0.0001 to 0.1 parts by weight with respect to 100 parts by weight of the polycarbonate resin.

  Examples of the flame retardant include sulfonic acid metal salt flame retardants, halogen-containing compound flame retardants, phosphorus-containing compound flame retardants, and silicon-containing compound flame retardants. Among these, a sulfonic acid metal salt flame retardant is preferable. The blending amount of the flame retardant is usually preferably 0.01 to 1 part by weight and more preferably 0.05 to 1 part by weight with respect to 100 parts by weight of the polycarbonate.

  The method of adding an additive to the polycarbonate resin used in the present invention is not particularly limited, and a known method can be used. The most widely used method is to premix the polycarbonate resin and additives, then put them into an extruder, melt and knead, cool the extruded threads, and cut them with a pelletizer to produce pellet-shaped molding materials The method of doing is mentioned. In such a production method, it is particularly preferable to use a production method of a molding material for an optical disk made of a polycarbonate resin.

  As the extruder in the above method, any of a single-screw extruder and a twin-screw extruder can be used, but a twin-screw extruder is preferable from the viewpoint of productivity and kneadability. A typical example of such a twin screw extruder is ZSK (trade name, manufactured by Werner & Pfleiderer). Specific examples of similar types include TEX (trade name, manufactured by Nippon Steel Works, Ltd.), TEM (trade name, manufactured by Toshiba Machine Co., Ltd.), KTX (product name, manufactured by Kobe Steel, Ltd.), and the like. Can be mentioned. As the extruder, one having a vent capable of degassing moisture in the raw material and volatile gas generated from the melt-kneaded resin can be preferably used. From the vent, a vacuum pump is preferably installed for efficiently discharging generated moisture and volatile gas to the outside of the extruder. It is also possible to remove a foreign substance from the resin composition by installing a screen for removing foreign substances mixed in the extrusion raw material in the zone in front of the extruder die part. Examples of such a screen include a wire mesh, a screen changer, a sintered metal plate (such as a disk filter), and the like.

  Further, the additive can be independently supplied to the extruder, but it is preferably premixed with the resin raw material as described above. Examples of such premixing means include a Nauter mixer, a V-type blender, a Henschel mixer, a mechanochemical apparatus, and an extrusion mixer. A more preferable method is to prepare a master agent by mixing a part of the raw material resin and an additive with a high-speed stirrer such as a Henschel mixer, and then use the total amount of the resin raw material and the Nauter mixer to leave such a master agent product. It is a method of mixing with a stirrer which is not high speed.

  The resin extruded from the extruder is directly cut into pellets, or after forming strands, the strands are cut with a pelletizer and pelletized. When it is necessary to reduce the influence of external dust or the like, it is preferable to clean the atmosphere around the extruder. Further, in the production of such pellets, various methods already proposed for polycarbonate resin for optical discs are used to narrow the shape distribution of pellets, further reduce miscuts, and generate fine powder during transportation or transportation. It is preferable to further reduce the amount of bubbles and the bubbles (vacuum bubbles) generated in the strands and pellets. To reduce miscuts, measures such as thread temperature control when cutting with a pelletizer, ionic air blowing during cutting, optimization of the rake angle of the pelletizer, and proper formulation of the release agent, as well as cutting For example, a method of filtering a mixture of pellets and water to separate the pellets from water and miscuts may be used. An example of the measuring method is disclosed in, for example, Japanese Patent Application Laid-Open No. 2003-200421. By these prescriptions, it is possible to increase the molding cycle and reduce the occurrence rate of defects such as silver.

  The miscut amount in the molding material (pellet) is preferably 10 ppm or less, more preferably 5 ppm or less. Here, the miscut means a granular material finer than a pellet having a desired size that passes through a JIS standard sieve having an opening of 1.0 mm. The shape of the pellet can take a general shape such as a cylinder, a prism, and a sphere, but is more preferably a cylinder (including an elliptic cylinder), and the diameter of the cylinder is preferably 1.5 to 4 mm, more preferably Is 2 to 3.5 mm. In the elliptic cylinder, the ratio of the minor axis to the major axis is preferably 60% or more, more preferably 65% or more. On the other hand, the length of the cylinder is preferably 2 to 4 mm, more preferably 2.5 to 3.5 mm.

<Characteristics of polycarbonate resin>
The polycarbonate resin used in the present invention can suppress polymer degradation in a basic environment containing an amine. As a result of various studies, it has been found that the depolymerization reaction of the polycarbonate with the amine compound proceeds while the amine compound acts on the carbonate bond of the polycarbonate to produce a carbamate ester oligomer as an intermediate. Then, in order to suppress the reaction to the carbonate bond by an amine compound, the substituent of the aromatic ring with respect to the carbonate bond is constituted by the structural unit (A) represented by the formula (1) as the main structural unit. It was found to play a role of steric hindrance.

The polycarbonate resin used in the present invention is composed of (A) the structural unit (A) represented by the formula (1) and (B) the structural unit (B) represented by the formula (2). As a result, it has been found that heat resistance and impact resistance are improved.
Furthermore, it discovered that the amine tolerance of polycarbonate resin improved by controlling the bond arrangement | sequence in the carbonate coupling | bonding comprised from a structural unit (A) and a structural unit (B).
The binding sequence can be calculated by dissolving 65 mg of polycarbonate resin in 0.5 mL of deuterated chloroform and calculating the area ratio of C═O bonding carbon peak derived from each binding sequence in ¹³ C-NMR spectrum measurement.

  In the case of a polycarbonate composed of the structural unit (A) and the structural unit (B), the bond arrangement is, for example, an example using a derivative composed of bisphenol C as the structural unit (A) and bisphenol A as the structural unit (B). A bond arrangement (X) composed of the structural unit (A) and the structural unit (A) represented by the formula (3), and a bond composed of the structural unit (A) and the structural unit (B) represented by the following formula (4). The array (Y) is composed of a binding array (Z) composed of the structural unit (B) and the structural unit (B) described in the following formula (5).

From the area ratio of ¹³ C-NMR spectrum peaks derived from these binding sequences, the randomness of the binding sequences can be calculated by the following formula (I). It has been found that when the degree of randomness (R) is 0.8 ≦ (R) ≦ 1.2, preferably 0.85 ≦ (R) ≦ 1.1, it has remarkable amine resistance. Furthermore, when the ratio of the binding sequences (X) and (Y) calculated by the following formula (II) to the total binding sequence is 40% or more, preferably 50% or more, it has remarkable amine resistance. I found it.
In addition, about a joint arrangement | sequence, when randomness (R) is 1.0, it is a random body, when randomness is 2.0, it is an alternating body, and when randomness is 0, it becomes a block body.

(Binding sequence (X): binding sequence consisting of structural unit (A) and structural unit (A) Binding sequence (Y): binding sequence consisting of structural unit (A) and structural unit (B) Binding sequence (Z): configuration unit (B) and consisting of structural units (B) binding sequence P (X): the area ratio of the ¹³ C-NMR spectrum peak derived from the binding sequence (X) P (Y): binding sequence (Y) from to ¹³ C-NMR spectral peak area ratio P (Z): ¹³ C-NMR spectral peak area ratio derived from the binding sequence (Z))

  The polycarbonate resin used in the present invention can obtain a desired molded article by a method such as injection molding, injection compression molding, injection blow molding, two-color molding, extrusion molding or blow molding.

  The production method of the polycarbonate resin used in the present invention is not particularly limited. For example, a sheet-like or film-like molded product may be obtained by a method such as a melt extrusion method or a solution casting method (casting method). it can. A specific method of the melt extrusion method is, for example, that a polycarbonate resin is quantitatively supplied to an extruder, heated and melted, and the molten resin is extruded in a sheet form from a tip of a T die onto a mirror surface roll, and a plurality of rolls. A method is used in which it is taken up while being cooled and cut or wound into an appropriate size when solidified. A specific method of the solution casting method is, for example, casting a solution of polycarbonate resin in methylene chloride (concentration 5% to 40%) from a T-die onto a mirror-polished stainless steel plate, and controlling the temperature stepwise. The sheet is peeled off while passing through the oven and the solvent is removed, followed by cooling and winding.

The polycarbonate resin may be a laminate. Any method may be used as a method for producing the laminated body, and it is particularly preferable to carry out by a thermocompression bonding method or a coextrusion method. Any method can be adopted as the thermocompression bonding method. For example, a method in which a polycarbonate resin sheet is subjected to thermocompression bonding with a laminating machine or a press machine, a method in which thermocompression bonding is performed immediately after extrusion is preferable, and it is particularly continuous with a polycarbonate resin sheet immediately after extrusion. The method of thermocompression bonding is industrially advantageous.
The polycarbonate resin used in the present invention preferably has a deflection temperature under load measured according to ISO 75 (Method A) of 110 to 170 ° C, more preferably 110 to 150 ° C, and more preferably 110 to 140 ° C. More preferably, the temperature is C. When the deflection temperature under load is 110 ° C. or higher, the heat resistance is excellent, and when it is 170 ° C. or lower, the molding temperature does not need to be high, and molding becomes easy.

The polycarbonate resin used in the present invention uses a DuPont impact deformation tester, and uses a shooting mold (radius 6.35 mm) and a receiving mold (inner diameter 15.2 mm, outer diameter 25.0 mm). It is preferable that a ductile fracture is formed when a parallel plate having a length and width of 50 mm and a thickness of 2 mm is installed between the shooting molds, and a 2 kg drop weight is dropped from a height of 1 m.
The polycarbonate resin used in the present invention preferably has a Rockwell hardness of 80 or more, more preferably 85 or more, as measured on the M scale in accordance with JIS K7202-2. It is preferable that the Rockwell hardness is 80 or more, since the scratch resistance is excellent.

The polycarbonate resin used in the present invention conforms to JIS K7204 and has a wear wheel with CS-10F, a test load of 4.9 N, and a glossiness (Gs 60 °) retention rate of 50 in a wear region after a test rotation speed of 100 revolutions. % Or more is preferable. Since it is excellent in scratch resistance with it being 50% or more, it is preferable.
The polycarbonate resin used in the present invention is formed by cutting a flexible urethane foam used for seat cushion material into a shape of 50 mm in length and width and 5 mm in thickness, and enclosing it in a glass sealed container, and setting it at 85 ° C. It is preferable that the appearance of the test piece does not change after being left for 1,000 hours in the hot air dryer.

<Amine compound used for forming polyurethane foam>
A polyurethane resin is generally produced by reacting a polyol and a polyisocyanate in the presence of a catalyst and, if necessary, a foaming agent, a surfactant, a flame retardant, a crosslinking agent and the like. It is known that many metal compounds and tertiary amine compounds are used as catalysts for the production of polyurethane resins. These catalysts are often used industrially when used alone or in combination. In the production of polyurethane foam using water, a low-boiling organic compound, or both as a foaming agent, among these catalysts, tertiary amine compounds are widely used because of excellent productivity and moldability. Yes. Examples of such tertiary amine compounds include conventionally known triethylenediamine, N, N, N ′, N′-tetramethylhexanediamine, N, N, N ′, N′-tetramethylpropanediamine, N , N, N ′, N′-tetramethylethylenediamine, bis (2-dimethylaminoethyl) ether, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N, N ′, N′-trimethylamino Examples include ethyl piperazine, N, N-dimethylbenzylamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethylethanolamine and the like.

<Automobile interior parts>
The polycarbonate resin used in the present invention is excellent in scratch resistance, impact resistance, and amine resistance and is therefore used as an automobile interior part. Automotive interior parts include lamp lenses for indoor lighting, meter covers for displays, meter dials, various switch covers, display covers, heat control panels, instrument panels, center clusters, center panels, center consoles, room lamp lenses, heads Various display devices such as an up display, protective components, translucent components, etc. Further, since the automobile interior part of the present invention has the above characteristics, there is an advantage that a polycarbonate resin molded product can be used as it is without requiring a coating treatment.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not limited to these Examples. In the following examples and comparative examples, the measuring method of each characteristic is as follows.

(1) Viscosity average molecular weight The viscosity average molecular weight of the polycarbonate resin composition is measured and calculated by the following method.
First, the polycarbonate resin composition pellets obtained by extrusion were mixed and dissolved with 30 times the weight of methylene chloride, and the soluble component was collected by Celite filtration. Thereafter, the solid obtained after removing the solvent from the obtained solution was sufficiently dried, and the specific viscosity (η _sp ) at 20 ° C. of the solution was obtained from a solution obtained by dissolving 0.7 g of the solid in 100 ml of methylene chloride. It was measured. And Mv computed by the following formula was made into the viscosity average molecular weight.
η _sp /c=[η]+0.45×[η] ² c
[Η] = 1.23 × 10 ⁻⁴ Mv ^0.83
η _sp : specific viscosity η: intrinsic viscosity c: constant (= 0.7)
Mv: viscosity average molecular weight

(2) Composition ratio Polycarbonate resin 40 mg was dissolved in 0.6 ml deuterated chloroform solution, and ¹ H-NMR was measured with a 400 MHz nuclear magnetic resonance apparatus manufactured by JEOL. From the spectral peak area ratio characteristic of each structural unit. The composition ratio of the polycarbonate resin was calculated.

(3) Deflection temperature under load In accordance with ISO 75, measurement was performed by Method A (1.8 MPa).

(4) Weight drop resistance test Using a DuPont impact deformation tester, using a shooting mold (radius 6.35 mm) and a receiving mold (inner diameter 15.2 mm, outer diameter 25.0 mm), receiving mold and shooting mold A parallel flat plate having a length and width of 50 mm and a thickness of 2 mm was installed between the two, and the destruction mode when a 2 kg drop weight was dropped from a height of 1 m was visually observed.

(5) Indentation hardness (Rockwell hardness)
In accordance with JIS K7202-2, the test was conducted on the M scale. The test piece was a flat plate having a length and width of 100 mm and a thickness of 8 mm.

(6) Taber abrasion test In accordance with JIS K7204, CS-10F, a test load of 4.9 N, and a glossiness (Gs 60 °) in a wear region after 100 revolutions of the test were measured. The gloss retention was evaluated based on the gloss before the test. The test piece used a flat plate having a length and width of 100 mm and a thickness of 2 mm, and a matte paint was applied after polishing the back surface to prevent the influence of back surface reflection when measuring the glossiness.

(7) Amine resistance evaluation Using a mold having a cavity surface with an arithmetic average roughness (Ra) of 0.03 μm, using a J-75E3 injection molding machine manufactured by Nippon Steel, a cylinder temperature of 290 ° C. and a mold Under conditions of a temperature of 80 ° C., the width is 50 mm, the length is 90 mm, the thickness is 3 mm (length 20 mm), 2 mm (length 45 mm), 1 mm (length 25 mm) at a holding time of 20 seconds and a cooling time of 20 seconds. ) Was formed. A flexible urethane foam used for automobile seat cushions is cut into a 50mm length and 5mm thickness cutter using a cutter, enclosed in a glass sealed container with a three-stage plate, and set in a hot air dryer set at 85 ° C. The appearance of the test piece after leaving for 1000 hours was visually observed.

(8) Binding sequence of polycarbonate The binding sequence was obtained by dissolving 65 mg of polycarbonate in 0.5 mL of deuterated chloroform, and using a 400 MHz nuclear magnetic resonance apparatus manufactured by JEOL, C═O derived from each binding sequence in ¹³ C-NMR spectrum measurement. Calculation was based on the area ratio of the bound carbon peak. In the case of the polycarbonate composed of the structural unit (A) and the structural unit (B), the bond arrangement is a bond arrangement (X) composed of the structural unit (A) and the structural unit (A), the structural unit (A) and the structural unit (B ) And a binding sequence (Z) consisting of a structural unit (B) and a structural unit (B). From the area ratio derived from these binding sequences, the binding sequence randomness (R) and the binding sequence ratio including the structural unit (A) were calculated by the following formulas (I) and (II), respectively.

結合配列（Ｘ）：構成単位（Ａ）と構成単位（Ａ）からなる結合配列
結合配列（Ｙ）：構成単位（Ａ）と構成単位（Ｂ）からなる結合配列
結合配列（Ｚ）：構成単位（Ｂ）と構成単位（Ｂ）からなる結合配列
Ｐ（Ｘ）：結合配列（Ｘ）に由来する^１３Ｃ−ＮＭＲスペクトルピークの面積比
Ｐ（Ｙ）：結合配列（Ｙ）に由来する^１３Ｃ−ＮＭＲスペクトルピークの面積比

Binding sequence (X): Binding sequence consisting of structural unit (A) and structural unit (A) Binding sequence (Y): binding sequence consisting of structural unit (A) and structural unit (B) Binding sequence (Z): structural unit binding sequence P consisting of (B) and the structural unit (B) (X): the area ratio of the ¹³ C-NMR spectrum peak derived from the binding sequence (X) P (Y): 13 C derived from the binding sequence (Y) -Area ratio of NMR spectrum peak

[ Reference Example 1]
A reactor equipped with a thermometer, a stirrer and a reflux condenser was charged with 4,485 parts of a 48% aqueous sodium hydroxide solution and 22,380 parts of ion-exchanged water, and 1,193 parts of bisphenol C (manufactured by Honshu Chemical). 2,483 parts of bisphenol A (manufactured by Nippon Steel Chemical Co., Ltd.) and 5.12 parts of hydrosulfite (manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved, and 19,813 parts of methylene chloride was added thereto. Then, 2,000 parts of phosgene was blown in over 80 minutes. After completion of the phosgene blowing, 640 parts of a 48% aqueous sodium hydroxide solution and 97.9 parts of p-tert-butylphenol were added, stirring was resumed, 3.94 parts of triethylamine was added after emulsification, and the mixture was further stirred at 28 to 35 ° C. for 1 hour. The reaction was terminated.
After completion of the reaction, the product is diluted with methylene chloride, washed with water, then added with hydrochloric acid, acidified and washed with water, and further washed with water until the conductivity of the aqueous phase becomes substantially the same as that of ion-exchanged water. A methylene solution was obtained. Next, this solution is passed through a filter having an aperture of 0.3 μm, and further dropped into warm water in a kneader with an isolation chamber having a foreign matter outlet at the bearing, and the polycarbonate resin is flaked while distilling off methylene chloride. The liquid-containing flakes were pulverized and dried to obtain a powder.
Then, after adding 0.05 parts by weight of tris (2,4-di-tert-butylphenyl) phosphite and 0.1 parts by weight of stearic acid monoglyceride to 100 parts by weight of the powder and mixing them uniformly The powder was melt-kneaded and extruded while venting with a vented twin-screw extruder [KTX-46, manufactured by Kobe Steel, Ltd.] to obtain polycarbonate resin composition pellets. Various evaluations were performed using the pellets, and the results are shown in Table 1.

[ Reference Example 2]
A polycarbonate resin composition pellet was obtained in the same manner as in Reference Example 1 except that bisphenol C was changed to 1,989 parts, bisphenol A was changed to 1,773 parts, and p-tert-butylphenol was changed to 88.5 parts. The results of evaluation using the pellets are shown in Table 1.

[ Reference Example 3]
A polycarbonate resin composition pellet was obtained in the same manner as in Reference Example 1, except that bisphenol C was changed to 2,784 parts, bisphenol A was changed to 1,064 parts, and p-tert-butylphenol 74.6 parts. The results of evaluation using the pellets are shown in Table 1.

[Example 4]
10 parts by weight of Teijin polycarbonate resin (product name: Panlite (registered trademark) L-1225WX) was added to 100 parts by weight of the powder obtained in Reference Example 2, and tris (2,4-di-tert- (Butylphenyl) phosphite (0.05 parts by weight) and stearic acid monoglyceride (0.1 parts by weight) were added and mixed uniformly, and then the powder was mixed with a vent type twin screw extruder [KTX-46 manufactured by Kobe Steel, Ltd. ] Was melt kneaded and extruded while degassing to obtain polycarbonate resin pellets. Various evaluations were performed using the pellets, and the results are shown in Table 1.

[Example 5]
20 parts by weight of Teijin polycarbonate resin (product: Panlite (registered trademark) L-1225WX) was added to 100 parts by weight of the powder obtained in Reference Example 2, and tris (2,4-di-tert-butyl was added. 0.05 parts by weight of phenyl) phosphite and 0.1 parts by weight of stearic acid monoglyceride were added and mixed uniformly, and then the powder was mixed with a vent type twin screw extruder [KTX-46, manufactured by Kobe Steel, Ltd.] The mixture was melt kneaded and extruded while degassing to obtain polycarbonate resin pellets. Various evaluations were performed using the pellets, and the results are shown in Table 1.

[ Reference Example 6]
A reactor equipped with a thermometer, a stirrer and a reflux condenser was charged with 4,596 parts of a 48% aqueous sodium hydroxide solution and 22,570 parts of ion-exchanged water, and 1,1-bis (4-hydroxy-3) was added thereto. -Methylphenyl) -3,3,5-trimethylcyclohexane (hereinafter abbreviated as C-TMC) 1,412 parts, bisphenol A (manufactured by Nippon Steel Chemical Co., Ltd.) 2,226 parts, and hydrosulfite 7.42 parts After dissolving (manufactured by Wako Pure Chemical Industries, Ltd.), 17,763 parts of methylene chloride was added, and 2,000 parts of phosgene was blown in at about 15-25 ° C. over about 80 minutes with stirring. After completion of the phosgene blowing, 574 parts of a 48% aqueous sodium hydroxide solution and 73.2 parts of p-tert-butylphenol were added, stirring was resumed, and after emulsification, 3.52 parts of triethylamine was added and further stirred at 28 to 35 ° C. for 1 hour. The reaction was terminated.
After completion of the reaction, the product is diluted with methylene chloride, washed with water, then added with hydrochloric acid, acidified and washed with water, and further washed with water until the conductivity of the aqueous phase becomes substantially the same as that of ion-exchanged water. A methylene solution was obtained. Next, this solution is passed through a filter having an aperture of 0.3 μm, and further dropped into warm water in a kneader with an isolation chamber having a foreign matter outlet at the bearing, and the polycarbonate resin is flaked while distilling off methylene chloride. The liquid-containing flakes were pulverized and dried to obtain a powder.
Then, after adding 0.05 parts by weight of tris (2,4-di-tert-butylphenyl) phosphite and 0.1 parts by weight of stearic acid monoglyceride to 100 parts by weight of the powder and mixing them uniformly The powder was melt-kneaded and extruded while venting with a vented twin-screw extruder [KTX-46, manufactured by Kobe Steel, Ltd.] to obtain polycarbonate resin composition pellets. Various evaluations were performed using the pellets, and the results are shown in Table 1.

[Example 7]
20 parts by weight of Teijin polycarbonate resin (product name: Panlite (registered trademark) L-1225WX) was added to 100 parts by weight of the powder obtained in Reference Example 6, and tris (2,4-di-tert-butyl was added. 0.05 parts by weight of phenyl) phosphite and 0.1 parts by weight of stearic acid monoglyceride were added and mixed uniformly, and then the powder was mixed with a vent type twin screw extruder [KTX-46, manufactured by Kobe Steel, Ltd.] The mixture was melt kneaded and extruded while degassing to obtain polycarbonate resin pellets. Various evaluations were performed using the pellets, and the results are shown in Table 1.

[ Reference Example 8]
Without using bisphenol A, 1,392 parts of bisphenol C, 3,131 parts of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (hereinafter abbreviated as bisphenol TMC), p A polycarbonate resin composition pellet was obtained in the same manner as in Reference Example 1, except that the amount was changed to 104.9 parts of -tert-butylphenol. The results of evaluation using the pellets are shown in Table 1.

[ Reference Example 9]
Polycarbonate resin composition in the same manner as in Reference Example 1 except that bisphenol A was not used, bisphenol C was changed to 1,989 parts, bisphenol TMC was changed to 2,408 parts, and p-tert-butylphenol 69.9 parts. Product pellets were obtained. The results of evaluation using the pellets are shown in Table 1.

[Comparative Example 1]
A polycarbonate resin composition pellet was obtained in the same manner as in Reference Example 1 except that Teijin polycarbonate resin (product name: Panlite (registered trademark) L-1225WX) was used as the polycarbonate resin powder. The results of evaluation using the pellets are shown in Table 2.

[Comparative Example 2]
Polycarbonate resin composition pellets were obtained in the same manner as in Reference Example 1, except that bisphenol A was not used and bisphenol C was changed to 3,978 parts and p-tert-butylphenol 74.5 parts. The results of evaluation using the pellets are shown in Table 2.

[Comparative Example 3]
A polycarbonate resin composition pellet was obtained in the same manner as in Reference Example 1, except that 795 parts of bisphenol C, 2,383 parts of bisphenol A, and 116.6 parts of p-tert-butylphenol were used. The results of evaluation using the pellets are shown in Table 2.

[Comparative Example 4]
A polycarbonate resin composition pellet was obtained in the same manner as in Reference Example 1 except that 3580 parts of bisphenol C, 354 parts of bisphenol A, and 65.3 parts of p-tert-butylphenol were changed. The results of evaluation using the pellets are shown in Table 2.

[Comparative Example 5]
2,500 g of the powder obtained in Comparative Example 2 and 2,500 g of Teijin polycarbonate resin (product name: Panlite (registered trademark) L-1225WX) were mixed, and tris (2 , 4-di-tert-butylphenyl) phosphite and 0.1 part by weight of stearic acid monoglyceride were added and mixed uniformly, and then the powder was added to a vent type twin screw extruder [Corporation] It was melt kneaded and extruded while degassing with Kobe Steel KTX-46] to obtain polycarbonate resin pellets. Various evaluations were performed using the pellets, and the results are shown in Table 2.

[Comparative Example 6]
1,500 g of the powder obtained in Comparative Example 2 and 3,500 g of Teijin polycarbonate resin (product name: Panlite (registered trademark) L-1225WX) were mixed, and tris (2) was added to 100 parts by weight of the polymer blend mixture. , 4-di-tert-butylphenyl) phosphite and 0.1 part by weight of stearic acid monoglyceride were added and mixed uniformly, and then the powder was added to a vent type twin screw extruder [Corporation] It was melt kneaded and extruded while degassing with Kobe Steel KTX-46] to obtain polycarbonate resin pellets. Various evaluations were performed using the pellets, and the results are shown in Table 2.

[Comparative Example 7]
3,500 g of the powder obtained in Comparative Example 2 and 1,500 g of Teijin polycarbonate resin (product name: Panlite (registered trademark) L-1225WX) were mixed, and tris (2,2) was added to 100 parts by weight of the polymer mixture. After adding 0.05 parts by weight of 4-di-tert-butylphenyl) phosphite and 0.1 parts by weight of stearic acid monoglyceride and mixing them uniformly, the powder was added to a vent type twin screw extruder [Kobe Corporation It was melt kneaded and extruded while degassing with KTX-46 manufactured by Steel Works to obtain polycarbonate resin pellets. Various evaluations were performed using the pellets, and the results are shown in Table 2.

[Comparative Example 8]
30 parts by weight of Teijin polycarbonate resin (product name: Panlite (registered trademark) L-1225WX) was added to 100 parts by weight of the powder obtained in Reference Example 2, and tris (2,4-di-tert- (Butylphenyl) phosphite (0.05 parts by weight) and stearic acid monoglyceride (0.1 parts by weight) were added and mixed uniformly, and then the powder was mixed with a vent type twin screw extruder [KTX-46 manufactured by Kobe Steel, Ltd. ] Was melt kneaded and extruded while degassing to obtain polycarbonate resin pellets. Various evaluations were performed using the pellets, and the results are shown in Table 2.

[Comparative Example 9]
An aromatic polycarbonate resin composition pellet was obtained in the same manner as in Reference Example 6 except that 471 parts of C-TMC, 2,862 parts of bisphenol A, and 66.8 parts of p-tert-butylphenol were used. The results of evaluation using the pellets are shown in Table 2.

[Comparative Example 10]
Aromatic polycarbonate resin composition in the same manner as in Reference Example 1 except that bisphenol A was not used and bisphenol C was changed to 795 parts, bisphenol TMC was changed to 3,853 parts, and p-tert-butylphenol was 123.2 parts. Product pellets were obtained. The results of evaluation using the pellets are shown in Table 2.

[Comparative Example 11]
In a reactor equipped with a stirrer and a distillation column, 56.3 parts (0.22 mol) of 2,2-bis (4-hydroxy-3-methylphenyl) propane, 49.2 parts (0.23 mol) of diphenyl carbonate As a catalyst, 0.000005 part of sodium hydroxide and 0.0016 part of tetramethylammonium hydroxide were charged, and the atmosphere was replaced with nitrogen. This mixture was dissolved while heating to 180 ° C. Then, the stirrer was rotated and the internal temperature of the reactor was kept at 220 ° C. The pressure in the reactor was reduced from 101.3 kPa to 13.3 kPa over 40 minutes while distilling out the by-produced phenol. Subsequently, a transesterification reaction was performed for 80 minutes while maintaining the pressure in the reactor at 13.3 kPa and further distilling off the phenol.
The internal pressure was reduced from 13.3 kPa to 2 kPa as an absolute pressure, and the temperature was further increased to 260 ° C. to remove the distilled phenol out of the system. Furthermore, the temperature was continuously increased, and after the inside of the reactor reached 0.3 Pa or less, the internal pressure was maintained and a polycondensation reaction was performed. The final internal temperature in the reactor was 295 ° C. The polycondensation reaction was terminated when the agitator of the reactor reached a predetermined stirring power. The polymerization reaction time in the reactor was 120 minutes. Next, in the molten state, 0.0023 part (4 × 10 ⁻⁵ mol / bisphenol 1 mol) of dodecylbenzenesulfonic acid tetrabutylphosphonium salt was added as a catalyst neutralizing agent and reacted at 295 ° C. and 10 Torr or less for 10 minutes. The polymer obtained was sent to a vented twin screw extruder [KTX-46, manufactured by Kobe Steel, Ltd.] with a gear pump. In the middle of the extruder, 0.05 part by weight of tris (2,4-di-tert-butylphenyl) phosphite and 0.03 part by weight of phosphorous acid are added to 100 parts by weight of the polymer, and the barrel at the inlet is added. Temperature 230 ° C, outlet barrel temperature 270 ° C, polycarbonate resin outlet temperature 285 ° C, melt kneading extrusion while degassing, extruding into a strand form from the exit of the twin screw extruder, cooling and solidifying with water, then rotating cutter To obtain polycarbonate resin pellets. The results of evaluation using the pellets are shown in Table 2.

[Comparative Example 12]
2,500 g of pellets obtained in Comparative Example 11 and 2,500 g of Teijin polycarbonate resin (product name: Panlite (registered trademark) AD-5503) were mixed, and tris (2 , 4-di-tert-butylphenyl) phosphite and 0.1 part by weight of stearic acid monoglyceride were added and mixed uniformly, and then the powder was added to a vent type twin screw extruder [Corporation] It was melt kneaded and extruded while degassing with Kobe Steel KTX-46] to obtain polycarbonate resin pellets. Various evaluations were performed using the pellets, and the results are shown in Table 2.

[Comparative Example 13]
2500 g of the pellets obtained in Comparative Example 11 and 2,500 g of Teijin polycarbonate resin (product name: Panlite (registered trademark) L-1250Y) were mixed, and tris (2 , 4-di-tert-butylphenyl) phosphite and 0.1 part by weight of stearic acid monoglyceride were added and mixed uniformly, and then the powder was added to a vent type twin screw extruder [Corporation] It was melt kneaded and extruded while degassing with Kobe Steel KTX-46] to obtain polycarbonate resin pellets. Various evaluations were performed using the pellets, and the results are shown in Table 2.

[Reference Example 10 ]
Various evaluations were performed using PMMA (product name: Acrypet (registered trademark) VH-001) manufactured by Mitsubishi Rayon instead of the polycarbonate resin pellets, and the results are shown in Table 2.

  As is apparent from the results of Tables 1 and 2, the combined arrangement of the structural unit (A) and the structural unit (B) has a randomness in the range of 0.8 ≦ (R) ≦ 1.2, and the structure It can be seen that the amine resistance is excellent when the ratio of the binding sequence including the unit (A) to the total structural units is 40% or more. That is, it can be seen that by using the polycarbonate resin of the present invention, an automotive interior part having excellent amine resistance, scratch resistance, heat resistance, and impact resistance can be obtained.

  Molded articles formed from the polycarbonate resin used in the present invention do not require a coating process, and include a lamp lens for indoor lighting, a meter cover for display, a meter dial, various switch covers, a display cover, a heat control panel, an instrument. This can be used for various display devices such as a maintenance panel, a center cluster, a center panel, a room lamp lens, a head-up display, an automobile interior part such as a protective part and a translucent part.

Claims (10)

As the main structural unit, (A) the following formula (1)

(In Formula (1), R ₁ and R ₂ are each independently a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl having 6 to 20 carbon atoms. Group, a cycloalkoxy group having 6 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or 7 to 20 carbon atoms. R ₃ and R ₄ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or 6 to 20 carbon atoms. A cycloalkyl group having 6 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or 7 to 7 carbon atoms. 20 represents an aralkyloxy group, and X represents a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted alkylidene group having 1 to 10 carbon atoms, or 6 to 10 carbon atoms. An aryl group, a substituted or unsubstituted cyclic alkyl group having 3 to 8 carbon atoms, a sulfur atom or an oxygen atom.)
A structural unit (A) represented by:
(B) The following formula (2)

(In formula (2), Y represents a single bond , an unsubstituted alkylene group having 1 to 10 carbon atoms , an unsubstituted alkylidene group having 1 to 10 carbon atoms, a sulfur atom, or an oxygen atom.)
The polycarbonate copolymer 100 parts by weight of a viscosity-average molecular weight that consists of in a structural unit represented by (B) is 15,000 to 40,000, and a structural unit (B) as a main structural unit The proportion of the structural unit (A) in the total structural unit calculated from the ¹ H-NMR spectrum obtained by blending 1 to 25 parts by weight of a polycarbonate resin having a viscosity average molecular weight of 18,000 to 28,000 is 25 to 85 mol%. The randomness (R) of the binding sequence represented by the following formula (I) calculated from the ¹³ C-NMR spectrum is 0.8 ≦ (R) ≦ 1.2, and is represented by the following formula (II). allocations of binding sequence, including a unit (a) is not less than 40% of the total binding sequence, automobile interior components formed from Lupolen polycarbonate blends having a amine resistant to.

(Binding array (X): Bonding array consisting of structural unit A and structural unit A Bonding array (Y): Bonding array consisting of structural unit A and structural unit B Binding sequence P (X): Area ratio of ¹³ C-NMR spectral peak derived from binding sequence (X) P (Y): Area ratio of ¹³ C-NMR spectral peak derived from binding sequence (Y) P (Z) : Area ratio of ¹³ C-NMR spectrum peak derived from the binding sequence (Z))

R ₁ and R ₂ in Formula (1) each independently represent an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and X represents a single atom. Bond, substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, substituted or unsubstituted alkylidene group having 1 to 10 carbon atoms, aryl group having 6 to 10 carbon atoms, substituted or unsubstituted carbon atoms A cyclic alkyl group having 3 to 8; Y in the formula (2) is a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkylidene group having 1 to 10 carbon atoms; Show The automobile interior part according to claim 1. Po polycarbonate blends automotive interior component according to claim 1 or 2 wherein the ratio is 30 to 80 mol% of structural units (A) in the total of all structural units is calculated from ^{1 H-NMR} spectrum of. Po polycarbonate blends, automotive interior component according to claim 1 conforming to ISO 75, was measured by A method (1.8 MPa) deflection temperature under load is 110 to 170 ° C.. Po polycarbonate blends, conforming to JIS K7202-2, automotive interior component according to any of claims 1 to 4 Rockwell hardness measured at M scale is 80 to 120. Automotive interior component according to any of claims 1 to 5 viscosity average molecular weight of Po polycarbonate blend is 15,000 to 40,000.   The structural unit (A) is 2,2-bis (4-hydroxy-3-methylphenyl) propane, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,1-bis (4-hydroxy- 2. A structural unit derived from at least one selected from the group consisting of 3-methylphenyl) cyclohexane and 1,1-bis (4-hydroxy-3-methylphenyl) -3,3,5-trimethylcyclohexane. The automobile interior part according to any one of? Automotive interior component according to any of claims 1 to 7 structural unit (B) is a structural unit derived 2,2-bis (4-hydroxyphenyl) propane or al. Automotive interior component according to any one of claim 1 to 8, the port polycarbonate blend formed by injection molding. Automotive interior component according to any one of claim 1 to 8 using the sheet or film obtained by extruding the port polycarbonate blends.