JP2009102537A - Resin molding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a large-sized resin molding consisting of polycarbonate resin whose material is taken from a bio-mass resource excellent in the heat resistance, thermal stability, and the mechanical characteristics. <P>SOLUTION: The resin molding having a maximum projection area of 500-50,000 cm<SP>2</SP>is produced by injection molding a polycarbonate resin composition containing 0.001-1 pts.wt. oxidation preventive agent (B-component) with respect to 100 pts.wt. polycarbonate resin (A-component) containing carbonate structural units given by formula (1). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a resin molded article comprising a specific polycarbonate resin composition. More specifically, the present invention relates to a large-sized resin molded product excellent in heat resistance, thermal stability, and mechanical properties obtained by molding a specific polycarbonate resin composition.

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

  A representative example of biomass plastic is polylactic acid, which has relatively high heat resistance and mechanical properties among biomass plastics, so its application is expanding to tableware, packaging materials, sundries, etc. In order to improve the possibility, the possibility as a large-sized molded article use including the exterior parts of a car is also examined (patent document 1). However, it is difficult to obtain a large-sized molded product with high accuracy with a crystalline resin, and there are still many problems in molding processability and the like.

  For large-sized resin molded products centering on automobile parts, it is a representative of amorphous resin, and the application of aromatic polycarbonate resin with excellent transparency, heat resistance and impact resistance is being actively studied. In addition, by substituting metal and glass, it contributes not only to freedom of design but also to weight reduction of the car body. Much attention has been paid to material design. Therefore, if a biomass plastic with characteristics and molding processability comparable to an aromatic polycarbonate resin is developed, not only the use of petroleum resources from the raw material side will be suppressed, but also the fuel consumption during transportation by reducing the weight of the product, When applied to vehicles such as automobile parts, fuel consumption is suppressed by improving its own fuel efficiency, which can greatly contribute to environmental conservation.

  As a polycarbonate resin using biomass resources as a raw material, a polycarbonate resin using a raw material obtained from an ether diol residue that can be produced from a saccharide is being studied.

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

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

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

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

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

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

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

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

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

  So far, among the above-mentioned ether diols, in particular, incorporation into polycarbonate using isosorbide as a monomer has been studied. In particular, isosorbide homopolycarbonates are described in Patent Documents 2 and 3 and Non-Patent Documents 1 and 2. Among these, Patent Document 2 reports a homopolycarbonate having a melting point of 203 ° C. using a melt transesterification method. In Non-Patent Document 1, a homopolycarbonate having a glass transition temperature of 166 ° C. is obtained in the melt transesterification method using zinc acetate as a catalyst, but the thermal decomposition temperature (5% weight loss temperature) is 283 ° C. Stability is not enough. In Non-Patent Document 2, homopolycarbonate is obtained by interfacial polymerization using bischloroformate of isosorbide, but the glass transition temperature is 144 ° C. and heat resistance (particularly heat resistance due to moisture absorption) is not sufficient. On the other hand, as an example of high heat resistance, Patent Document 3 reports a polycarbonate having a glass transition temperature of 170 ° C. or higher by differential calorimetry at a heating rate of 10 ° C./min. In this case, in order to obtain a molded product by injection molding or the like, there is a problem that since the glass transition temperature is high, the molding processing temperature becomes high and the decomposition of the polymer is promoted.

  That is, a polycarbonate resin-based material using a biomass raw material that has a heat-resistant stability suitable for injection molding of a large resin molded product and can provide a large resin molded product that exhibits excellent characteristics has not yet been obtained. There wasn't.

JP 2003-128900 A British Patent Application No. 1079686 International Publication No. 2007/013463 Pamphlet “Journal of Applied Polymer Science”, 2002, 86, p. 872-880. “Macromolecules”, 1996, Vol. 29, p. 8077-8082

  Accordingly, a main object of the present invention is to provide a large-sized resin molded article made of a polycarbonate resin using a biomass resource having excellent heat resistance, thermal stability and mechanical properties as a raw material.

  As a result of diligent research to achieve such an object, the present inventors made a biomass resource as a raw material by heat-molding a resin composition in which a specific antioxidant is blended with a polycarbonate resin having a specific structure. The inventors have found that a large-sized resin molded product excellent in thermal stability and mechanical properties can be obtained, and completed the present invention.

２．前記樹脂成形品は、樹脂組成物を射出プレス成形することにより得られたものである前項１記載の樹脂成形品、
３．前記樹脂成形品は、シート形状でありその少なくとも１つの表面にハードコート処理がなされたものである前項１または２記載の樹脂成形品、および
４．ポリカーボネート樹脂（Ａ成分）は、含窒素塩基性化合物、アルカリ金属化合物およびアルカリ土類金属化合物からなる群より選ばれた少なくとも一つの化合物を重合触媒として使用し、下記式（ａ）で示されるエーテルジオールと炭酸ジエステルとを、常圧で加熱反応させ、次いで減圧下、１８０℃〜２８０℃の温度で加熱しながら溶融重縮合させて得られたものである前項１〜３のいずれか１項に記載の樹脂成形品、

が提供される。 That is, according to the present invention,
1. A polycarbonate resin composition comprising 0.001 to 1 part by weight of an antioxidant (component B) with respect to 100 parts by weight of a polycarbonate resin (component A) containing a carbonate constituent unit represented by the following formula (1) A resin molded product having a maximum projected area of 500 to 50,000 cm ² obtained by injection molding an object,

2. The resin molded product according to item 1, wherein the resin molded product is obtained by injection press molding a resin composition;
3. 3. The resin molded product according to 1 or 2 above, wherein the resin molded product has a sheet shape and a hard coat treatment is applied to at least one surface thereof; The polycarbonate resin (component A) uses at least one compound selected from the group consisting of a nitrogen-containing basic compound, an alkali metal compound and an alkaline earth metal compound as a polymerization catalyst, and an ether represented by the following formula (a) In any one of the preceding items 1 to 3, which is obtained by heat-reacting a diol and a carbonic acid diester at normal pressure and then melt polycondensation while heating at a temperature of 180 ° C. to 280 ° C. under reduced pressure. The resin molded product as described,

Is provided.

  Hereinafter, the resin molded products obtained by injection molding of the resin composition of the present invention will be specifically described sequentially.

<About component A>
The polycarbonate resin (component A) used in the present invention is a polycarbonate resin containing a carbonate constituent unit represented by the formula (1), and among all the carbonate constituent units, the constituent unit represented by the formula (1) is 60. It is preferably at least mol%, more preferably at least 70 mol%, further preferably at least 80 mol%, particularly preferably at least 90 mol%. Most preferably, it is a homopolycarbonate resin consisting only of the carbonate structural unit of the formula (1).

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

であり、好ましくは炭素原子数４〜２０のアルキル基、炭素原子数４〜２０のパーフルオロアルキル基、または上記式（４）であり、特に炭素原子数８〜２０のアルキル基、または上記式（４）が好ましい。Ｘは単結合、エーテル結合、チオエーテル結合、エステル結合、アミノ結合およびアミド結合からなる群より選ばれる少なくとも一種の結合が好ましいが、より好ましくは単結合、エーテル結合およびエステル結合からなる群より選ばれる少なくとも一種の結合であり、なかでも単結合、エステル結合が好ましい。ａは１〜５の整数であり、好ましくは１〜３の整数であり、特に１が好ましい。 In the above formulas (2) and (3), R ¹ is an alkyl group having 4 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, a perfluoroalkyl group having 4 to 30 carbon atoms, or the following formula ( 4)

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

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

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

<About B component>
The resin composition constituting the resin molded article of the present invention contains an antioxidant in order to obtain a better hue and stable fluidity. In particular, it is preferable to use a phosphorus-based antioxidant and / or a hindered phenol-based antioxidant as the antioxidant.
Examples of the phosphorus antioxidant include various phosphite compounds, phosphate compounds, phosphonite compounds, and phosphonate compounds.

  Examples of the phosphite compound include triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl Monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, tris (diethylphenyl) phos Phyto, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite Ito, and tris (2,6-di -tert- butylphenyl) phosphite and the like. In particular, as the phosphite compound, it is preferable to blend a pentaerythritol type phosphite compound represented by the following general formula (5).

［式中Ｒ^１１、Ｒ^１２はそれぞれ水素原子、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基ないしアルキルアリール基、炭素数７〜３０のアラルキル基、炭素数４〜２０のシクロアルキル基、炭素数１５〜２５の２−（４−オキシフェニル）プロピル置換アリール基を示す。なお、シクロアルキル基およびアリール基は、アルキル基で置換されていてもよい。］

[Wherein R ¹¹ and R ¹² are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an alkylaryl group, an aralkyl group having 7 to 30 carbon atoms, and an alkyl group having 4 to 20 carbon atoms. A cycloalkyl group, a 2- (4-oxyphenyl) propyl-substituted aryl group having 15 to 25 carbon atoms is shown. In addition, the cycloalkyl group and the aryl group may be substituted with an alkyl group. ]

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

  Still other phosphite compounds that react with dihydric phenols and have a cyclic structure can be used. For example, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert- Butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-methylenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite 2,2′-ethylidenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite.

  Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, Examples thereof include diisopropyl phosphate, and triphenyl phosphate and trimethyl phosphate are preferable.

  Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenedi. Phosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite Tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylene diphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl)- 4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, and the like, and tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite, bis (Di-tert-butylphenyl) -phenyl-phenylphosphonite is preferred, tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl)- More preferred is phenyl-phenylphosphonite. Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted.

Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.
Said phosphorus antioxidant can be used individually or in combination of 2 or more types.

Moreover, as a hindered phenolic antioxidant, the hindered phenolic antioxidant containing the structure represented by following formula (6) is preferable.

In the above formula (6), R ²¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, particularly a methyl group, an ethyl group, or an isopropyl group. , An isobutyl group and a tertbutyl group are preferable.
R ²² is an alkyl group having 4 to 10 carbon atoms, preferably an alkyl group having 4 to 6 carbon atoms, and particularly preferably an isobutyl group, a tertbutyl group, or a cyclohexyl group.

R ²³ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, or a carbon atom. From an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aralkyloxy group having 7 to 20 carbon atoms At least one group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and the number of carbon atoms At least one group selected from the group consisting of 6 to 10 aryl groups and aralkyl groups having 7 to 20 carbon atoms is preferred, particularly hydrogen atoms or alkyl groups having 1 to 10 carbon atoms. A kill group is preferred. n is an integer of 1 to 4, an integer of 1 to 3 is preferable, and 2 is particularly preferable.

When the structure represented by the above formula (6) is represented as a “—X ¹ ” group, the hindered phenol antioxidant used in the present invention is represented by the following formulas (7), (8) and (9). Preferred is at least one compound selected from the group consisting of the following compounds.

In the above formula (7), R ²⁴ is a hydrocarbon group that may contain an oxygen atom having 8 to 30 carbon atoms, more preferably a hydrocarbon group that may contain an oxygen atom having 12 to 25 carbon atoms. A hydrocarbon group which may contain an oxygen atom having 15 to 25 carbon atoms is preferred.

In the above formula (8), R ²⁵ is a hydrogen atom or an alkyl group having 1 to 25 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, particularly an alkyl having 1 to 18 carbon atoms. Groups are preferred. m is an integer of 1 to 4, an integer of 1 to 3 is preferable, and 2 is particularly preferable. k is an integer of 1-4, 3-4 are preferable, and 4 is especially preferable.

In the above formula (9), R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, A methyl group is particularly preferable. l is an integer of 1 to 4, an integer of 1 to 3 is preferable, and 2 is particularly preferable.

  Preferred specific examples of the above formula (7) include octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, benzenepropanoic acid 3,5-bis (1,1-dimethylethyl)- 4-hydroxyalkyl ester (alkyl has 7 to 9 carbon atoms and has a side chain), ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylene Bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate is mentioned.

  A preferred specific example of the above formula (8) is pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate].

  As a preferred specific example of the above formula (9), 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane.

Among these, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate, 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10- Tetraoxaspiro [5,5] undecane is particularly preferred.
Such a hindered phenolic antioxidant may be one kind or a mixture of two or more kinds.

The antioxidant used in the present invention is 0.001 to 1 part by weight, preferably 0.01 to 0.5 part by weight, more preferably 0.01 to 0.00 part by weight per 100 parts by weight of the polycarbonate resin (component A). 3 parts by weight is blended.
The resin molded product of the present invention may be composed of a resin composition obtained by adding the following various components to the above-described polycarbonate resin composition.

<Release agent>
The polycarbonate resin forming the resin molded article of the present invention preferably contains a release agent. Known release agents can be used. For example, fatty acid ester, polyolefin wax (polyethylene wax, 1-alkene polymer, etc., which can be modified with a functional group-containing compound such as acid modification), silicone compound (especially alkyl such as phenyl group and methyl group) And a fluorine oil (represented by polyfluoroalkyl ether), paraffin wax, beeswax and the like.

  Of these, fatty acid esters and silicone compounds are preferred, and fatty acid esters are particularly preferred from the viewpoints of releasability, transparency of molded products, adhesion to the hard coat layer, and the like. The fatty acid ester is an ester of an alcohol and a fatty acid. Among them, an ester of a monohydric alcohol and a fatty acid, a partial ester or a total ester of a polyhydric alcohol and a fatty acid is preferable. Furthermore, esters of monohydric alcohols having 1 to 20 carbon atoms and saturated fatty acids having 10 to 30 carbon atoms and partial esters of polyhydric alcohols having 1 to 25 carbon atoms and saturated fatty acids having 10 to 30 carbon atoms Alternatively, at least one mold release agent selected from the group consisting of all esters is preferably used.

  Specific examples of the ester of a monohydric alcohol and a saturated fatty acid include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate and the like.

  Specific examples of partial esters or total esters of polyhydric alcohols and saturated fatty acids include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol diester. Dipentaerythritol such as stearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexyl stearate, dipentaerythritol hexastearate Examples include total esters or partial esters of Toll.

  Among these esters, stearic acid monoglyceride, stearic acid diglyceride, stearic acid monosorbate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol distearate, propylene glycol monostearate, sorbitan monostearate, etc. Esters are preferred, stearic acid monoglyceride, stearic acid monosorbate, pentaerythritol monostearate and pentaerythritol distearate are more preferred, and stearic acid monoglyceride is particularly preferred. Such a release agent may be one kind or a mixture of two or more kinds.

  Although the esterification rate of these partial esters is not particularly limited, the esterification rate is preferably 20% or more, more preferably 20 to 80%, still more preferably 20 to 50%. When the esterification rate is within the above range, the total light transmittance of the resin composition of the present invention is high and the haze is kept low. Further, a fatty acid ester having a low esterification rate and a high hydroxyl value tends to deteriorate the polycarbonate resin, and the molded product is liable to crack.

  The amount of the release agent used in the present invention is preferably 0.001 to 1.0 part by weight, more preferably 0.01 to 0.5 part by weight, and 0.03 to 0.5 part per 100 parts by weight of the polycarbonate resin. Part by weight is more preferred, 0.03 to 0.3 part by weight is particularly preferred, and 0.03 to 0.2 part by weight is most preferred. When the release agent is within this range, it is possible to achieve improvement in releasability while suppressing opacity.

<Ultraviolet absorber>
When the resin molded product of the present invention is used as a window glass, good weather resistance is often required. Therefore, the polycarbonate resin forming the resin molded product preferably further contains an ultraviolet absorber.

  As the ultraviolet absorber, in the benzophenone series, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 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 Eniru) methane, 2-hydroxy -4-n-dodecyloxy benzoin phenone, and 2-hydroxy-4-methoxy-2'-carboxy benzophenone may be exemplified.

  In the benzotriazole series, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3, 5-Dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2′-methylenebis [4- (1,1,3 , 3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazole, 2- (2- Hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5 Di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole, 2- ( 2-hydroxy-4-octoxyphenyl) benzotriazole, 2,2'-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis (1,3-benzoxazine-4 -One), and 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole, and 2- (2'-hydroxy-5-methacryloxy) Copolymerization of ethylphenyl) -2H-benzotriazole with vinyl monomer copolymerizable with the monomer And 2- (2′-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole and a copolymer of vinyl monomer copolymerizable with the monomer, 2-hydroxyphenyl-2H-benzotriazole skeleton A polymer having

  In the benzoxazine series, for example, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2′-m-phenylenebis (3,1-benzoxazin-4-one) And 2,2′-p, p′-diphenylenebis (3,1-benzoxazin-4-one) and the like.

  In the hydroxyphenyl triazine series, for example, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol, 2- (4,6-diphenyl-1,3,5) -Triazin-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-ethyloxyphenol, 2- (4,6-diphenyl) -1,3,5-triazin-2-yl) -5-propyloxyphenol and 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-butyloxyphenol Illustrated. Further, the phenyl group is a 2,4-dimethylphenyl group such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol. Some compounds are exemplified.

  You may use the said ultraviolet absorber individually or in mixture of 2 or more types. The amount of the ultraviolet absorber used is preferably 0.0005 to 3 parts by weight, more preferably 0.01 to 2 parts by weight, still more preferably 0.02 to 1 part by weight, based on 100 parts by weight of the polycarbonate resin. 05 to 0.5 parts by weight are particularly preferred.

<Fluorescent brightener>
If desired, an optical brightener is used in the polycarbonate resin forming the resin molded product of the present invention. Here, the fluorescent whitening agent has an action of absorbing energy in the ultraviolet part of the light and radiating this energy to the visible part.

  Examples of the fluorescent brightening agent include stilbene, benzimidazole, benzoxazole, naphthalimide, rhodamine, coumarin, and oxazine compounds. Of these, benzoxazole compounds and coumarin compounds are preferred. These fluorescent brighteners can be used alone or in combination of two or more. Specifically, Kayalite OS (CI Fluorescent Brightener 219: 1, benzoxazole-based compound) manufactured by Nippon Kayaku Co., Ltd., Hakkol PSR (coumarin-based compound) manufactured by Hakkol Chemical Co., Ltd., EASTOBRITE OB manufactured by Eastman Chemical Co., Ltd. -1, etc.

  The blending ratio of the optical brightener is 0.0001 to 3 parts by weight, preferably 0.0002 to 0.5 parts by weight, more preferably 0.0003 to 0.1 parts by weight based on 100 parts by weight of the polycarbonate resin. Parts by weight, particularly preferably 0.0005 to 0.05 parts by weight.

<Inorganic filler>
In the component A polycarbonate resin constituting the resin molded product of the present invention, when a filler is further blended, a part having excellent mechanical characteristics, dimensional characteristics and the like can be obtained. As the filler, an inorganic filler and / or an organic filler can be used.

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

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

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

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

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

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

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

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

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

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

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

  The blending amount of these inorganic fillers is preferably 0.3 to 200 parts by weight, more preferably 1.0 to 100 parts by weight, and most preferably 3 to 50 parts by weight per 100 parts by weight of the polycarbonate resin (component A). When the blending amount is 0.3 parts by weight or more, the reinforcing effect on the mechanical properties of the molded article of the present invention is sufficient, and when it is 200 parts by weight or less, the moldability and hue are good.

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

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

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

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

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

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

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

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

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

<Elastic polymer>
In the polycarbonate resin of component A constituting the resin molded product of the present invention, when an elastic polymer is further blended, it is possible to obtain a part that is given impact resistance and has improved safety against collision.

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

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

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

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

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

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

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

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

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

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

Among the above-mentioned flame retardants, compounds that do not contain chlorine and bromine atoms have reduced features that are undesirable when performing incineration and thermal recycling. It is more suitable as a flame retardant in the molded article of the present invention.
Furthermore, the phosphate ester flame retardant is particularly preferable because a good hue can be obtained and an effect of improving molding processability is also exhibited.

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

<Other additives>
The resin composition constituting the resin molded article of the present invention includes other thermoplastic resins (for example, other polycarbonate resins, aromatic polyester resins, aliphatic polyester resins, polyarylates) within the range where the effects of the present invention are exhibited. Resin, liquid crystalline polyester resin, polyamide resin, polyimide resin, polyetherimide resin, polyurethane resin, silicone resin, polyphenylene ether resin, polyphenylene sulfide resin, polysulfone resin, polyolefin resin such as polyethylene and polypropylene, polystyrene resin, acrylonitrile / styrene co-polymer Polymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), polystyrene resin, high impact polystyrene resin, syndiotactic polystyrene resin, polymethacrylate Oils, phenoxy or epoxy resins, etc.), light stabilizers (HALS, etc.), flow modifiers (polycaprolactone, etc.), colorants (carbon black, titanium dioxide, various organic dyes, metallic pigments, etc.), light diffusion Agents (acrylic crosslinked particles, silicone crosslinked particles, etc.), phosphorescent pigments, fluorescent dyes, antistatic agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents (fine particle titanium oxide, fine particle zinc oxide, etc.), infrared absorbers, and You may mix | blend a photochromic agent ultraviolet absorber. These various additives can be used in known blending amounts when blended with a thermoplastic resin such as bisphenol A polycarbonate.

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

<About the manufacturing method of molded products>
The resin molded product of the present invention is manufactured by injection molding the pellets of the resin composition manufactured as described above. Here, as the injection molding method, not only a normal injection molding method but also injection compression molding, injection press molding, heat insulating mold molding, rapid heating / cooling mold molding, ultra-high speed injection molding, and the like can be used. Among these, injection press molding is preferable for the following reasons. In addition, either a cold runner method or a hot runner method can be selected for molding. Furthermore, use of a flow mold method, an SVG method, or the like is also possible.

  In the present invention, injection press molding means that a molten thermoplastic resin is supplied into a mold cavity having a capacity larger than the target molded article capacity at least when the supply is completed, and the mold cavity capacity is reduced after the supply is completed. This is a molding method in which the molded product is reduced to a target molded product capacity and the molded product is taken out after being cooled to a temperature below which the molded product in the mold cavity can be taken out. The reduction of the mold cavity capacity may be started before or after the completion of the resin supply, but is preferably started before the completion of the supply. That is, a mode in which the step of reducing the cavity capacity and the step of filling the resin overlap is preferable.

  In injection press molding, the need to fill the resin at high pressure is reduced, so that distortion in the molded product is reduced. Such distortion reduction is important in the uniformity of transmitted light. Furthermore, the reduction of the distortion enables the application of a hard coat agent with higher adhesion.

  From the viewpoint of reducing distortion on the surface of the molded product, it is also preferable to combine heat insulating mold forming and rapid heating / cooling mold forming (halogen lamp irradiation, induction heating, high-speed switching of heat medium, ultrasonic mold, etc.) It is.

  In addition, as is generally known, injection press molding enables molding at an extremely low pressure, so that the level of clamping pressure of the injection molding machine can be greatly reduced. In particular, this is a large molded product having a long flow length, so that the quality of the product can be improved and the cost of the equipment can be reduced. In another aspect, injection press molding is a molding method capable of reducing the molding temperature. However, since the molded article of the present invention is large-sized, there is a limit in reducing the thermal load. Examples of the heat load due to the large size include extremely long flow paths, large-capacity resins, and injection filling with a large flow rate per unit time while having a long injection time.

  In the above-described injection press molding, particularly injection press molding of a large molded product, it is important to maintain the parallelism between the molds in the intermediate clamping state and the intermediate clamping state to the final clamping state. Injection press molding is often performed by providing a molding machine with a small clamping force as described above with a high-weight mold close to the upper limit. Therefore, it is difficult to maintain parallelism in the mold clamping mechanism of the molding machine due to the weight of the mold. Also, an offset load is generated by the pressure at the time of resin filling, and it is difficult to maintain the parallelism of the mold. Misalignment of parallelism causes mold galling and makes mass production difficult. Furthermore, maintaining parallelism between molds achieves a more uniform pressure load on the resin within the mold. As a result, the pressure applied to the resin achieves a low pressure as a whole, and it is possible to provide a molded product with less distortion. When the parallelism between the molds is not sufficient, a difference occurs in the pressure applied due to the difference in the location of the resin molded product, and this may be a factor in generating one distortion.

  As a method for maintaining the parallelism between the molds, (i) a plurality of mold mounting plates, preferably four corners, are adjusted between the molds while adjusting the parallelism between the molds by a mold clamping mechanism at four positions. Method of maintaining parallelism, and (ii) Adjusting the parallelism between molds by applying correction force to multiple locations, preferably 4 corners, on the mold mounting plate (mold mounting surface) A method for maintaining the parallelism between the molds is preferably exemplified. The method (i) is a method for maintaining parallelism by a mold clamping mechanism, and the method (ii) is a method for maintaining parallelism by a correction force applying mechanism provided separately. As a molding machine that realizes the method (i), for example, the MDIP series manufactured by Meiki Seisakusho Co., Ltd., which is a large molding machine capable of injection press molding provided with a 4-axis parallel control mechanism of a platen can be exemplified. As the mold clamping mechanism and the correction force applying mechanism, a normal hydraulic cylinder is preferably used, but other combinations such as a pneumatic cylinder, a combination of a ball screw and a screw, and a combination of a rack gear and a pinion gear are exemplified.

Furthermore, the molding conditions in the injection press molding will be briefly described. The magnification ratio of the mold capacity in the intermediate clamping state of the injection press molding is preferably in the range of 1.02 to 5 times the target molded product capacity of the target molded product capacity. The lower limit is more preferably 1.03 times, still more preferably 1.05 times, and particularly preferably 1.1 times. The upper limit is more preferably 4 times, still more preferably 3.5 times, and particularly preferably 3 times. However, this range is based on the premise that the following compression stroke amount is in an appropriate range. In such a range, an injection molded product with less distortion can be obtained even in a large injection molded product.

  Furthermore, the magnification of the mold capacity at the completion of the resin supply is preferably in the range of 1.002 to 4.5 times the target molded article capacity. The lower limit is more preferably 1.03 times, still more preferably 1.05 times, and particularly preferably 1.1 times. The upper limit is more preferably 3.5 times, still more preferably 3 times, and particularly preferably 2.7 times.

  The final clamping state of the injection press molding is preferably a state where the parting surfaces of the movable side mold and the fixed side mold do not contact each other. In such a state, it is possible to uniformly transmit the pressure to the resin, and an injection molded product with less distortion can be obtained. The molding in such a state is stably performed while maintaining the parallelism between the molds. Therefore, the maintenance of the parallelism between the molds is important in injection press molding from this point. The distance between the parting surfaces of the movable mold and the fixed mold in the final mold clamping state is preferably in the range of 0.05 to 3 mm, and more preferably 1 to 2 mm.

  The amount of movement of the mold from the intermediate clamping state to the final clamping state of injection press molding (hereinafter sometimes referred to as a compression stroke) is preferably in the range of 1 to 10 mm, more preferably in the range of 1 to 6 mm. A range of 2 to 5 mm is more preferable. A retreat amount in such a range achieves both a low clamping force, which is an advantage of the injection press molding method, and good molding efficiency and appearance of the molded product. The thickness of the molded product is not particularly limited, but is preferably in the range of 0.5 to 10 mm, more preferably in the range of 1 to 7 mm.

  Furthermore, the moving speed when the mold is moved from the intermediate clamping state to the final clamping state is preferably 0.5 mm / sec or more, more preferably 1 mm / sec or more, and further preferably 10 mm / sec or more. A molded article having a higher L / D requires a higher mold capacity enlargement ratio and requires a higher moving speed. This is because in order to reduce the distortion of the molded product, it is important to end the compression process up to a predetermined final clamping state while the change in the thermal distribution of the molten resin inside the mold is small. The higher the moving speed, the larger the compression stroke can be handled. Therefore, it is preferable that the moving speed is as high as possible, but at present, about 40 mm / sec is a practical limit. If the level is 35 mm / sec, sufficiently precise speed control is possible. The moving speed is obtained by dividing the compression stroke from the intermediate clamping state to the final clamping state by the time required for compression, and does not necessarily have to be a constant speed. In addition, as the compression stroke is larger and the moving speed of the mold is larger as described above, the galling of the mold is more likely to occur. Therefore, maintaining the parallelism between the molds is an important and essential condition.

  More preferably, the injection molded product of the present invention has only one gate on the side surface of the molded product. This is because such an injection molded product can particularly effectively utilize the advantages of injection press molding. In this case, one gate means that there is one gate for the molded product body. Therefore, a plurality of flow paths from the resin discharge port of the injection molding machine to the gate may exist. For example, a structure having a plurality of hot runner inlets with respect to the fan gate may be used. Further, by using the SVG method in such a structure, it is possible to control the resin to flow into the molded product body almost simultaneously over the entire gate gate of the fan gate, which is a preferable technique for obtaining a molded product with less distortion. is there.

<About molded products>
The resin molded product of the present invention has a maximum projected area of 500 to 50,000 cm ² . Such a lower limit is preferably 5,000 cm ² , more preferably 10.000 cm ² . Such an upper limit is preferably 40,000 cm ² , more preferably 35,000 cm ² . The advantage of the polycarbonate resin composition in the present invention becomes more prominent as the molded article is larger. That is, the larger the size, the higher the heat load during molding, and the thermal stability of the resin composition of the present invention is advantageously exhibited.

  Furthermore, the flow length during molding of the resin composition is preferably 30 cm or more, more preferably 35 cm or more. On the other hand, 200 cm or less is appropriate as the upper limit of the flow length, and 180 cm or less is more appropriate.

As a more preferable molded product shape, the ratio L / D of the distance (L (mm)) from the gate portion to the flow end with respect to the thickness (D (mm)) of the molded product is preferably 75 or more. The above is more preferable, 130 or more is further preferable, and 150 or more is particularly preferable. On the other hand, the upper limit is suitably 1,000 or less, preferably 800 or less, and more preferably 600 or less.
Therefore, according to the present invention, there is provided a large injection-molded product, particularly an injection press-molded product comprising the above resin composition and having such a maximum projected area.

<About surface modification>
The resin molded product in the present invention can be further provided with other functions by surface modification. “Surface modification” as used herein means the surface layer of a resin molded product by means of vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot dipping, etc.), painting, coating, and printing. This means that a new layer is formed on the surface, and a surface modification method used for ordinary resin molded products can be applied. Further, as the surface modification method, any one of (i) a method of directly applying to the molded product of the present invention and (ii) a method of laminating a resin film subjected to such treatment on the molded product of the present invention can be applied. is there.

  Examples of the method for laminating a metal layer or metal oxide layer on the surface of a resin molded product (including the resin film in the case of (ii) above) include physical vapor deposition, chemical vapor deposition, thermal spraying, and plating. It is done. Examples of physical vapor deposition include vacuum vapor deposition, sputtering, and ion plating, and examples of chemical vapor deposition (CVD) include thermal CVD, plasma CVD, and photo CVD. By such a method, it is possible to form a hard film such as diamond-like carbon. Examples of the thermal spraying method include an atmospheric pressure plasma spraying method and a low pressure plasma spraying method. Examples of the plating method include an electroless plating (chemical plating) method, a hot dipping method, and an electroplating method. In the electroplating method, a laser plating method can be used.

  Among the above methods, the vapor deposition method and the plating method are preferable for forming the metal layer on the molded article of the present invention, and the vapor deposition method is preferable for forming the metal oxide layer. Surface modification with metal oxides typified by ATO, ITO, tin oxide and the like has a relatively good light transmittance, a relatively good hue of transmitted light, and cuts heat rays. Such surface modification by the metal oxide may be performed on any surface of the molded product.

The molded article of the present invention is particularly suitable for outdoor use by applying a hard coat.
Next, the hard coat layer of the present invention will be described. In the present invention, various hard coat agents can be used as the hard coat treatment, and examples of the hard coat agent used in the present invention include a silicone resin hard coat agent and an organic resin hard coat agent. The hardness of the hard coat layer is not particularly limited as long as it is higher than the hardness of polycarbonate.

  The silicone resin hard coat agent forms a cured resin layer having a siloxane bond. For example, partial hydrolysis of a compound mainly composed of a compound corresponding to a trifunctional siloxane unit (trialkoxysilane compound, etc.). Condensates, preferably partially hydrolyzed condensates further containing compounds corresponding to tetrafunctional siloxane units (tetraalkoxysilane compounds etc.), and further partially hydrolyzed condensates filled with metal oxide fine particles such as colloidal silica Is mentioned. The silicone resin hard coat agent may further contain a bifunctional siloxane unit and a monofunctional siloxane unit. These include alcohols generated during the condensation reaction (in the case of a partially hydrolyzed condensate of alkoxysilane) and the like, but if necessary, may be dissolved or dispersed in any organic solvent, water, or a mixture thereof. Good. Examples of the organic solvent for this purpose include lower fatty acid alcohols, polyhydric alcohols and ethers thereof, and esters. In addition, in order to obtain a smooth surface state, various surfactants such as siloxane-based and alkyl fluoride-based surfactants may be added to the hard coat layer.

  Examples of the organic resin hard coat agent include melamine resin, urethane resin, alkyd resin, acrylic resin, and polyfunctional acrylic resin. Here, examples of the polyfunctional acrylic resin include resins such as polyol acrylate, polyester acrylate, urethane acrylate, epoxy acrylate, and phosphazene acrylate. Among these, an ultraviolet curable hard coat agent is particularly preferable. Furthermore, it is more preferable that such a hard coat agent contains a structural unit obtained by copolymerizing an ultraviolet absorbing monomer and / or a photostable monomer. A more suitable organic resin hard coat agent is one in which a hard coat layer is formed by copolymerizing such a monomer and an alkyl (meth) acrylate monomer. Such an ultraviolet curable hard coat agent is preferable in that its processing is simple, and in addition, it is easy to include a structural unit obtained by copolymerizing an ultraviolet absorbing monomer and / or a light stable monomer. This is preferable in that the light resistance of the product can be greatly improved. As a commercial item of an acrylic hard coat agent, for example, Origin Electric series manufactured by Origin Electric Co., Ltd. and Nippon Shokubai Co., Ltd. Udouble series are exemplified. These can be used by mixing with a crosslinking agent component.

  On the other hand, when a glass-like hardness is required for a molded product, a silicone resin-based hard coat agent having excellent long-term weather resistance and relatively high surface hardness is preferable. In particular, it is preferable to form a primer layer (first layer) made of various resins and then form a top layer (second layer) prepared from a silicone resin hard coat agent thereon.

  Examples of the resin that forms such a primer layer (first layer) include urethane resins, acrylic resins, polyester resins, epoxy resins, melamine resins, amino resins, and polyester acrylates, urethane acrylates, and epoxy resins, which are composed of various blocked isocyanate components and polyol components. Examples include various polyfunctional acrylic resins such as acrylate, phosphazene acrylate, melamine acrylate, amino acrylate, etc., and these can be used alone or in combination of two or more. Among these, the acrylic resin and the polyfunctional acrylic resin are preferably those containing 50% by weight, more preferably 60% by weight or more, and those made of acrylic resin and urethane acrylate are particularly preferable. These can be applied either by applying a predetermined reaction after application of an unreacted material to obtain a cured resin, or by directly applying the reacted resin to form a cured resin layer. In the latter case, the resin is usually dissolved in a solvent to form a solution, which is then applied and then the solvent is removed. In the former case, a solvent is generally used.

  Furthermore, the resin forming the primer layer of the silicone resin hard coat agent of the present invention includes known light stabilizers and ultraviolet absorbers, silicone resin hard coat agent catalysts, thermal / photopolymerization initiators, polymerization inhibitors. , Silicone antifoaming agents, leveling agents, thickeners, suspending agents, anti-sagging agents, flame retardants, various additives of organic / inorganic pigments / dyes, and auxiliary additives.

The hard coat layer of the present invention preferably contains an ultraviolet absorber because it has good durability (especially durability against adhesion). Furthermore, the more suitable aspect of the hard-coat layer of this invention is as follows. That is, a hard coat layer having a configuration in which the first layer is formed on the surface of the molded article of the present invention and the second layer is formed on the surface of the first layer,
The first layer is composed of a crosslinked acrylic copolymer (acrylic copolymer-I) and an ultraviolet absorber, and the second layer is composed of a crosslinked organosiloxane polymer, and the crosslinked acrylic copolymer (acrylic copolymer). Polymer-I) is 50 mol% or more of the following formula (X-1)

（式中Ｒ^３１はメチル基またはエチル基である。）
で表される繰り返し単位、５〜３０モル％の下記式（Ｘ−２）

(Wherein R ³¹ is a methyl group or an ethyl group.)
A repeating unit represented by the formula: 5 to 30 mol% of the following formula (X-2)

（式中Ｒ^３２は炭素数２〜５のアルキレン基である。式（Ｘ−２）で表される繰り返し単位において少なくとも一部のＲ^ａは単結合であり、残りが水素原子である。Ｒ^ａが単結合の場合はウレタン結合を介して、他の式（Ｘ−２）で表される繰り返し単位と結合している。）
で表される繰り返し単位、および０〜３０モル％の下記式（Ｘ−３）

(In the formula, R ³² is an alkylene group having 2 to 5 carbon atoms. In the repeating unit represented by the formula (X-2), at least a part of ^Ra is a single bond, and the remainder is a hydrogen atom. ^{When a} is a single bond, it is bonded to a repeating unit represented by the other formula (X-2) via a urethane bond.)
And a repeating unit represented by formula (X-3) of 0 to 30 mol%

（但し、式中Ｙは水素原子またはメチル基であり、Ｒ^３３は水素原子、炭素数２〜５のアルキル基、紫外線吸収残基からなる群より選ばれる少なくとも一種の基である。但し、Ｙがメチル基であり、かつＲ^１３がメチル基またはエチル基である場合を除く。）で表される繰り返し単位からなり、ウレタン結合と式（Ｘ−１）〜（Ｘ−３）で表される繰り返し単位の合計量とのモル比が４／１００〜３０／１００の範囲にある架橋したアクリル共重合体であり、該架橋したオルガノシロキサン重合体は、下記式（ｐ−４）〜（ｐ−６）

(In the formula, Y is a hydrogen atom or a methyl group, and R ³³ is at least one group selected from the group consisting of a hydrogen atom, an alkyl group having 2 to 5 carbon atoms, and an ultraviolet-absorbing residue. Is a methyl group, and R ¹³ is a methyl group or an ethyl group.), And is represented by a urethane bond and formulas (X-1) to (X-3). It is a crosslinked acrylic copolymer having a molar ratio with the total amount of repeating units in the range of 4/100 to 30/100, and the crosslinked organosiloxane polymer has the following formulas (p-4) to (p- 6)

（式中、Ｑ^１、Ｑ^２は、それぞれ炭素数１〜４のアルキル基、ビニル基、またはメタクリロキシ基、アミノ基、グリシドキシ基および３，４−エポキシシクロヘキシル基からなる群より選ばれる少なくとも一種の基で置換された炭素数１〜３のアルキル基である。）
で表される繰り返し単位からなり、該繰り返し単位の全量を１００モル％としたとき、式（ｐ−４）：８０〜１００モル％、式（ｐ−５）：０〜２０モル％、および式（ｐ−６）：０〜２０モル％である架橋したオルガノシロキサン重合体である、ハードコート層である。

(In the formula, Q ¹ and Q ² are each at least one selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a vinyl group, or a methacryloxy group, an amino group, a glycidoxy group, and a 3,4-epoxycyclohexyl group. A C 1-3 alkyl group substituted with a group.)
When the total amount of the repeating units is 100 mol%, the formula (p-4): 80 to 100 mol%, the formula (p-5): 0 to 20 mol%, and the formula (P-6): It is a hard coat layer which is a crosslinked organosiloxane polymer of 0 to 20 mol%.

  As a coating method, a method such as a bar coating method, a dip coating method, a flow coating method, a spray coating method, a spin coating method, or a roller coating method is appropriately selected depending on the shape of a molded product to be coated. be able to. Of these, the dip coating method, the flow coating method, and the spray coating method, which can easily cope with complicated molded product shapes, are preferable.

  The present invention is a large-sized injection-molded product from a polycarbonate resin composition having improved thermal stability using a biomass resource as a raw material. Such a molded product can bring about a dramatic improvement in productivity and modularization of parts to various molded products in which sheets and bent products thereof have been mainly used. Examples of such molded articles include automobile exterior parts, automobile interior parts, and resin window glass. Examples of the resin window glass include a roof window (including a wind up to a side window and a back window), a back window, a detachable top, a window reflector, and the like, and a dome in a daylighting apparatus for buildings.

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

(1) Melt viscosity Obtained as a result of measurement using a capillary rheometer (Capillograph Model 1D) manufactured by Toyo Seiki Co., Ltd. with a capillary length of 10.0 mm, a capillary diameter of 1.0 mm, and a measurement temperature of 250 ° C. The melt viscosity at 600 sec ⁻¹ was read from the obtained Shear Rate / Viscosity curve.

(2) Glass transition temperature The glass transition temperature was measured by DSC (model DSC2910) manufactured by TA Instruments.

(3) 5% weight loss temperature Measured with TGA (model TGA2950) manufactured by TA Instruments.

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

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

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

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

<Production Example 3: Production of Polycarbonate A-3 Component>
A polymer was obtained in the same manner as in Production Example 1 except that zinc acetate was used as the polymerization catalyst and the reaction was finally carried out at 220 ° C. and 6.66 × 10 ⁻⁵ MPa for 11 hours. The glass transition temperature of this polymer was 158 A polymer having a melt viscosity of 0.59 × 10 ³ Pa · s at a shear rate of 600 sec ⁻¹ and a 5% weight reduction temperature of 291 ° C. was obtained.

In addition, the following were used as raw materials.
B-1: Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (Adeka Stub PEP-36 manufactured by Asahi Denka Kogyo Co., Ltd.)
B-2: Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (IRGANOX 1010 manufactured by Ciba Specialty Chemicals Co., Ltd.)
B-3: 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8, 10-tetraoxaspiro [5,5] undecane (Sumitomo GA-80 manufactured by Sumitomo Chemical Co., Ltd.)

(Other)
CEi-P: 2,2′-p-phenylenebis (3,1-benzoxazin-4-one) (manufactured by Takemoto Yushi Co., Ltd .: “CEi-P” (trade name))
H-PSR: Coumarin-based fluorescent brightener (manufactured by Hackol Chemical Co., Ltd .: “Hackol PSR” (trade name))
KL-OS: fluorescent brightener (manufactured by Nippon Kayaku Co., Ltd .: “Kayalite OS” (trade name))
MR: Stearyl monoglyceride release agent (Riken Vitamin Co., Ltd .: “Riquemar S-100A” (trade name))

<Evaluation of resin composition and molded product>
(1) Thermal stability evaluation by large injection press-molded products (Examples 1-6 and Comparative Examples 1-2)
An automobile roof molded product having a thickness of 5 mm shown in FIG. 1 was molded by an injection press molding method, and the appearance was confirmed. Molding was carried out after 20 purge shots after a sufficient purge shot and evaluated using a total of 10 molded products from the 11th to the 20th shot when molding was stable. Evaluation was performed based on the following criteria as described above.
○: Silver streaks are not observed in any molded product. △: Slight silver streaks are observed in some molded products. ×: Silver streaks are observed in all molded products.

(2) Hard coat adhesion In almost the center of the above molded product, Nichiban adhesive tape (trade name “Sero Tape (registered trademark)”) is pressure-bonded to the hard coat layer by making 100 grids with a cutter knife at intervals of 1 mm. Then, it was strongly peeled off vertically to observe whether or not all the hard coat layer remained on the resin molded product. The test was carried out with 10 resin molded products, and the number of molded products in which all the hard coat layers remained in the resin molded products was determined.

(3) Heat resistance: In accordance with ISO75-1 and 2, the deflection temperature under load was measured under the condition of load: 1.80 MPa using a bending test piece.

(4) Flexural modulus: The flexural modulus was measured according to ISO178 (bending specimen shape: length 80 mm × width 10 mm × thickness 4 mm).

[Examples 1-6 and Comparative Examples 1-2]
(I) Preparation of molding material The raw materials shown in Table 1 were blended in the blending proportions listed in the table and mixed uniformly using a Henschel mixer. The obtained mixture was supplied to a first supply port located at the screw root of the extruder and extruded. As the extruder, a twin-screw extruder with a vent equipped with a screw having a diameter of 30 mmφ (manufactured by Nippon Steel Works: TEX30α (completely meshing, rotating in the same direction, two-thread screw)) was used. A screw configuration having one kneading zone in front of the vent was adopted. Extrusion conditions were a discharge rate of 25 kg / h, a screw rotation speed of 150 rpm, a vent vacuum of 3 kPa, and a cylinder temperature of the extruder from the first supply port: 230 ° C. to the die: 250 ° C. The profile of the cylinder temperature was distributed almost uniformly for each block. The extruded strand was cut into strands to obtain pellets.

(Ii) Production of Large Injection Press Molded Product Large pellet molding machine capable of injection press molding with platen 4-axis parallel control mechanism (made by Meiki Seisakusho: MDIP2100, maximum mold clamping) 1 was produced by injection press molding using a force of 33540 kN). The molding machine is equipped with a hopper dryer facility that can dry the pellets up to a level of about 5 hours at 120 ° C., as described above, and the dried pellets were used for molding. Drying was performed in an atmosphere of 110 ° C.

  Molding is cylinder temperature 250 ° C, hot runner set temperature 230 ° C, fixed mold temperature 110 ° C, movable mold temperature 100 ° C, injection speed 16mm / sec, filling time 31 seconds, intermediate mold clamping position to final mold clamping position The press stroke was 3.0 mm, the cooling time was 230 seconds, and the molding cycle was 310 seconds. Further, the movable mold parting surface was not in contact with the fixed mold parting surface in the final forward position. The runner is a valve gate type hot runner (gate diameter: 7 mmφ) manufactured by Moldmasters. The mold compression starts immediately before the completion of filling, and the valve gate is closed immediately after the filling is completed, so that the molten resin does not flow backward from the gate to the cylinder. Condition.

(Iii) Preparation of molded product for characteristic evaluation Using dried pellets, bending is performed at an injection molding machine (Toshiba Machine Co., Ltd .: IS-150EN) at a cylinder temperature of 250 ° C, a mold temperature of 80 ° C, and a molding cycle of 40 seconds. A test piece was molded.

(Vi) Hard coat treatment The molded article for automobile roof of Examples 1 to 6 was subjected to a hard coat treatment.
(Vi-1) Adjustment of hard coat agent (in the following description, “part” means “part by weight”)
(Vi-1-1) Production of acrylic copolymer (EMA-HEMA (I)) 102.7 parts of ethyl methacrylate (hereinafter abbreviated as EMA) in a flask equipped with a reflux condenser and a stirrer and purged with nitrogen. 13 parts of 2-hydroxyethyl methacrylate (hereinafter abbreviated as HEMA), 0.18 part of azobisisobutyronitrile (hereinafter abbreviated as AIBN) and 200 parts of 1,2-dimethoxyethane were added and mixed and dissolved. Subsequently, it was made to react under stirring at 70 degreeC in nitrogen stream for 6 hours. The obtained reaction solution was added to n-hexane and purified by reprecipitation to obtain 98 parts of a copolymer (EMA-HEMA (I)) having an EMA / HEMA composition ratio of 90/10 (molar ratio). The copolymer had a hydroxyl value of 48.7 mgKOH / g and a weight average molecular weight of 90,000 in terms of polystyrene as measured by GPC (column; Shodex GPCA-804, eluent: THF).

(Vi-1-2) Preparation of first layer acrylic resin composition (HC-1) 10 parts of EMA-HEMA (I) and UV absorber (Ciba Specialty Chemicals Co., Ltd .: “Tinuvin 411L” (product) Name)) 2.00 parts is dissolved in a mixed solvent consisting of 50 parts of methyl isobutyl ketone and 25 parts of 2-butanol, and 1 equivalent of isocyanate group is added to 1 equivalent of hydroxy group of EMA-HEMA (I) in this solution. 2.96 parts of a polyisocyanate compound precursor (Degussa Japan Co., Ltd .: “VESTANATB135 8/100” (trade name)) was added, and 0.005 part of dimethyltindineodecanoate, silane cup Add 1.5 parts of ring agent (Nihon Unicar Co., Ltd .: “APZ-6633 5% ethanol solution” (trade name)) The mixture was stirred at 5 ° C. for 30 minutes to prepare an acrylic resin composition (HC-1) for the first layer.

(Vi-1-3) Preparation of organosiloxane resin composition for second layer (HC-2) Water-dispersed colloidal silica dispersion (manufactured by Catalyst Chemical Industry Co., Ltd .: “Cataloid SN30” (trade name), solid content 100 parts of 30% by weight) 0.1 part of 35% hydrochloric acid was added and stirred, and 136 parts of methyltrimethoxysilane and 20.3 parts of dimethyldimethoxysilane were added to this dispersion while cooling in an ice-water bath. An organosiloxane resin composition is prepared by adding 1 part of a 45% choline methanol solution and 4 parts of acetic acid as a curing catalyst and a pH adjuster to the reaction liquid obtained by stirring this mixed liquid at 25 ° C. for 6 hours, and diluting with 200 parts of isopropanol. A product (HC-2) was prepared.

(Vi-2) Application of hard coat agent The vehicle roof molded article produced above was annealed in a clean oven at 130 ° C for 1 hour. Thereafter, the acrylic resin composition for the first layer (HC-1) prepared as described above was applied on both sides by a dip coating method so as not to be pooled, left at 25 ° C. for 20 minutes, and then in a hot air circulating oven at 130 ° C. for 1 hour. And a cured film having a thickness of 4.0 μm was laminated. Next, the second layer organosiloxane resin composition (HC-2) prepared as described above was applied on both surfaces by the dip coating method on the coating surface of the molded article, left at 25 ° C. for 20 minutes, and then 2 ° C. at 120 ° C. A cured film having a thickness of 4.0 μm was laminated by heat curing in a hot air circulating oven.

The schematic of the motor vehicle roof molded article shape | molded in the Example is shown. As shown in the drawing, the automobile roof molded article has a three-dimensional shape composed of gentle curved surfaces. [1-A] shows a front view (projected on the platen surface during molding), [1-B] shows a side view in the longitudinal direction, and [1-C] shows a side view from the flow end side.

Explanation of symbols

11 Automobile roof molded product main body (main body is 5 mm thick, maximum projected area is about 11,000 cm ² )
12 Portion corresponding to the tip of the hot runner nozzle 13 Gate of the molded product (the gate is a flat plate having a thickness of 5 mm)
14 Molded product gate side length (corresponds to the maximum width of the molded product and is 1000 mm)
15 Length of molded product flow end side (900mm)
16 Length of molded product (1240mm)
17 Total length of the molded product including the gate (1350mm)
18 Height of molded product (90mm)
19 Mounting claw

Claims (4)

A polycarbonate resin composition comprising 0.001 to 1 part by weight of an antioxidant (component B) with respect to 100 parts by weight of a polycarbonate resin (component A) containing a carbonate constituent unit represented by the following formula (1) A resin molded product having a maximum projected area of 500 to 50,000 cm ² obtained by injection molding an object.

  The resin molded article according to claim 1, wherein the resin molded article is obtained by injection press molding a resin composition.   The resin molded product according to claim 1 or 2, wherein the resin molded product has a sheet shape and is subjected to a hard coat treatment on at least one surface thereof. The polycarbonate resin (component A) uses at least one compound selected from the group consisting of a nitrogen-containing basic compound, an alkali metal compound and an alkaline earth metal compound as a polymerization catalyst, and an ether represented by the following formula (a) The diol and the carbonic acid diester are obtained by heat-reacting at normal pressure and then melt polycondensation while heating at a temperature of 180 ° C to 280 ° C under reduced pressure. The resin molded product described in 1.

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