JP4839285B2 - Plastic molded product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin molded article comprising a polycarbonate resin of a biomass resourced material which is excellent in transparency, mechanical properties and surface properties. <P>SOLUTION: The resin molded article has a total light transmittance of 75% or higher, when measured according to the JIS K 7105 on a smooth tabular molded article of a 1 mm thickness obtained by injection-molding a polycarbonate resin (compound (A)) at a cylinder temperature range of 220-270&deg;C wherein the compound (A) is composed of a carbonate unit expressed by the following formula (1), and has a melt viscosity range of 0.2&times;10<SP>3</SP>-4.0&times;10<SP>3</SP>Pa s measured at a shear rate of 600 sec<SP>-1</SP>with a capillary rheometer at 250&deg;C. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a resin molded article made of a specific polycarbonate resin. More specifically, the present invention relates to a resin molded product excellent in transparency, mechanical properties, and heat resistance obtained by molding a specific polycarbonate resin under specific injection molding conditions.

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

  A representative example of biomass plastics is polylactic acid, which has relatively high heat resistance and mechanical properties among biomass plastics, so its application is expanding to tableware, packaging materials, sundries, etc. Therefore, the possibility of various industrial uses including automobile parts has been studied (Patent Document 1).

  However, for applications that require transparency, polylactic acid is a crystalline resin, so a molded product with high transparency cannot be obtained. Since the transition temperature is low, its heat resistance is insufficient.

Polycarbonate resin-based polymers are expected as materials having high transparency and excellent performance in heat resistance and mechanical properties.
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 carbohydrate has been studied.

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

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

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

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

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

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

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

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

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

  So far, among the above-mentioned ether diols, in particular, incorporation into polycarbonate using isosorbide as a monomer has been studied. In particular, isosorbide homopolycarbonates are described in Patent Documents 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 view of the development of the above, there are problems in obtaining a molded product by injection molding or the like because the glass transition temperature is high, the molding processing temperature is high, and the decomposition of the polymer is promoted.

  In other words, it is a polycarbonate resin material using biomass raw material that can be applied to transparent members for vehicles, has melt flow characteristics and heat stability suitable for injection molding, and has excellent transparency, mechanical characteristics, heat resistance, etc. A product that can provide a resin molded product to be exhibited has not yet been obtained.

Japanese Patent No. 3583097 British Patent Application No. 1079686 International Publication No. 2007/013463 Pamphlet “Journal of Applied Polymer Science”, 2002, Vol. 86, p. 872-880 “Macromolecules”, 1996, Vol. 29, p. 8077-8082

  Therefore, a main object of the present invention is to provide a resin molded article made of a polycarbonate resin using a biomass resource excellent in transparency, mechanical properties, and surface properties as a raw material.

  As a result of diligent research to achieve the above object, the present inventors have made a resin molding excellent in transparency, mechanical properties, and surface properties when a polycarbonate resin having a specific structure and melt flow properties is injection-molded under specific conditions. As a result, the present invention was completed.

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

４．全光線透過率が８０％以上である前項１〜３のいずれか１項に記載の樹脂成形品、
５．上記樹脂成形品は、その厚みが１〜５ｍｍである前項１〜４のいずれか１項に記載の樹脂成形品、
６．上記樹脂成形品は、（ｉ）ＪＩＳ Ｋ５４００に従って測定された手かき法による鉛筆引っかき値がＨＢ以上で、且つ（ｉｉ）ＡＳＴＭ Ｄ７９０に従って測定された曲げ弾性率の値が３，０００ＭＰａ以上である前項１〜５のいずれか１項に記載の樹脂成形品、
７．上記樹脂成形品は、その表面にハードコート処理がなされている前項１〜６のいずれか１項に記載の樹脂成形品、および
８．上記樹脂成形品は、車輌用透明部材である前項１〜７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. It consists of a carbonate structural unit represented by the following formula (1), and the melt viscosity measured by a capillary rheometer at 250 ° C. is 0.2 × 10 ^{3 to} 4.0 × 10 ³ Pa under the condition of a shear rate of 600 sec ^-1. The total light transmittance of a 1 mm-thick smooth plate-like molded article, measured according to JIS K7105, obtained by injection molding a polycarbonate resin (component A) in the range of s in a cylinder temperature range of 220 to 270 ° C. Resin molded product characterized by being 75% or more,

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

4). The resin molded product according to any one of items 1 to 3, wherein the total light transmittance is 80% or more,
5). The resin molded product according to any one of items 1 to 4, wherein the resin molded product has a thickness of 1 to 5 mm,
6). The above-mentioned resin molded product has (i) a pencil scratch value measured according to JIS K5400 by a hand scratch method of HB or more, and (ii) a flexural modulus value measured according to ASTM D790 of 3,000 MPa or more. The resin molded product according to any one of 1 to 5,
7). 7. The resin molded product according to any one of items 1 to 6, wherein the resin molded product has a hard coat treatment on the surface thereof; The resin molded product according to any one of items 1 to 7, which is a transparent member for a vehicle,
Is provided.

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

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

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

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

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

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

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

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

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

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

  These saccharide-derived ether diols are substances obtained from natural biomass and are one of so-called renewable resources. Isosorbide is obtained by hydrogenating D-glucose obtained from starch and then dehydrating it. 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 a monohydroxy compound during polymerization. As the monohydroxy compound, a hydroxy compound represented by the following formula (2) or (3) is preferably used.

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

  The 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 (component B) used in the present invention is 0.001 to 1.0 part by weight, preferably 0.01 to 0.5 part by weight, based on 100 parts by weight of the polycarbonate resin. 0.5 part by weight is more preferable, 0.03 to 0.3 part by weight is further preferable, and 0.03 to 0.2 part by weight is particularly preferable. When the release agent is within this range, it is possible to achieve improvement in releasability while suppressing opacity.

  In addition, in order to use the resin molded product of the present invention as a transparent member for vehicles, good weather resistance is often required, and therefore the polycarbonate resin forming the resin molded product may further contain an ultraviolet absorber. preferable.

  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 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.

  Of these, benzotriazole and hydroxyphenyltriazine are preferred. 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.

  The polycarbonate resin forming the resin molded product of the present invention includes bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (1,2,2,6,6-pentamethyl-4-piperidyl). ) Sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4- Piperidyl) -1,2,3,4-butanetetracarboxylate, poly {[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethylpiperidyl) imino] hexamethylene [(2,2,6,6-tetramethylpiperidyl) imino]}, and polymethylpropyl 3-oxy- [4- 2,2,6,6-tetramethyl) piperidinyl] hindered amine light stabilizer typified by siloxane can also be included. Furthermore, the combined use of a hindered amine light stabilizer and a benzotriazole-based and / or triazine-based ultraviolet absorber effectively improves the weather resistance. In such a combination, the weight ratio (light stabilizer / ultraviolet absorber) of both is preferably in the range of 95/5 to 5/95, more preferably in the range of 80/20 to 20/80.

  You may use the said light stabilizer individually or in mixture of 2 or more types. The amount of the light stabilizer 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. -0.5 part by weight is particularly preferred.

  The polycarbonate resin forming the resin molded product of the present invention preferably further comprises 0.05 to 3 ppm (weight ratio) of a blueing agent in the polycarbonate resin. This is effective for eliminating the yellow color of the polycarbonate resin molded product. In particular, in the case of molded products with weather resistance, since a certain amount of UV absorber is used, there is a reality that resin products tend to be yellowish due to the `` action and color of the UV absorber ''. The use of a bluing agent is very effective for imparting natural transparency.

  Here, the bluing agent refers to a colorant that exhibits a blue or purple color by absorbing light of orange or yellow color, and a dye is particularly preferable. The polycarbonate resin of the present invention achieves a better hue by blending the bluing agent. The important point here is the blending amount of the bluing agent. In the resin composition, if the bluing agent is less than 0.05 ppm, the hue improving effect may be insufficient. On the other hand, if it exceeds 3 ppm, the light transmittance is not suitable. A more preferable blending amount of the bluing agent is in the range of 0.5 to 2.5 ppm, more preferably 0.5 to 2 ppm in the polycarbonate resin.

  Representative examples of the bluing agent include Macrolex Violet B and Macrolex Blue RR from Bayer, Terrasol Blue RLS from Sand, and Plast Blue 8580 from Arimoto Chemical Industry.

  In the polycarbonate resin that forms the resin molded product of the present invention, various dyes and pigments can be used in addition to the bluing agent as long as the object of the invention is not impaired. In particular, a dye is preferable from the viewpoint of maintaining transparency. Preferred dyes include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as bitumen, perinone dyes, quinoline dyes, quinacridone dyes, dioxazine dyes, isoindo Examples thereof include linone dyes and phthalocyanine dyes. Furthermore, fluorescent whitening agents such as bisbenzoxazolyl-stilbene derivatives, bisbenzoxazolyl-naphthalene derivatives, bisbenzoxazolyl-thiophene derivatives, and coumarin derivatives can be used. The amount of these dyes and fluorescent whitening agent used is preferably 0.0001 to 1 part by weight, more preferably 0.0005 to 0.5 part by weight per 100 parts by weight of the polycarbonate resin.

  The resin molded product of the present invention may be required to have antistatic performance, and in such a case, it is preferably formed from a polycarbonate resin containing an antistatic agent. Examples of the antistatic agent include (i) an organic sulfonic acid phosphonium salt such as an aryl sulfonic acid phosphonium salt typified by dodecylbenzenesulfonic acid phosphonium salt and an alkyl sulfonic acid phosphonium salt. The phosphonium salt has a composition ratio of 5 parts by weight or less per 100 parts by weight of the polycarbonate resin, preferably 0.05 to 5 parts by weight, more preferably 1 to 3.5 parts by weight, and 1.5 to 3 parts by weight. A range of parts is more preferred.

  Examples of the antistatic agent include (ii) lithium organic sulfonate, organic sodium sulfonate, organic potassium sulfonate, cesium organic sulfonate, rubidium organic sulfonate, calcium organic sulfonate, magnesium organic sulfonate, and barium organic sulfonate. Organic sulfonate alkali (earth) metal salts of Specifically, for example, metal salts of dodecylbenzenesulfonic acid, metal salts of perfluoroalkanesulfonic acid, and the like are exemplified. The organic sulfonate alkali (earth) metal salt has an appropriate composition ratio of 0.5 parts by weight or less per 100 parts by weight of the polycarbonate resin, preferably 0.001 to 0.3 parts by weight, and 0.005 to 0.005. 2 parts by weight is more preferred. In particular, alkali metal salts such as potassium, cesium, and rubidium are preferable.

  Examples of the antistatic agent include (iii) organic sulfonic acid ammonium salts such as alkyl sulfonic acid ammonium salt and aryl sulfonic acid ammonium salt. The composition ratio of the ammonium salt is 0.05 parts by weight or less per 100 parts by weight of the polycarbonate resin. Examples of the antistatic agent include (iv) glycerin derivative esters such as glycerin monostearate, maleic anhydride monoglyceride, and maleic anhydride diglyceride. The ester has a composition ratio of 0.5 parts by weight or less per 100 parts by weight of the polycarbonate resin. Examples of the antistatic agent include (v) a polymer containing a poly (oxyalkylene) glycol component such as polyether ester amide as a constituent component. The polymer is suitably 5 parts by weight or less per 100 parts by weight of the polycarbonate resin. Examples of other antistatic agents include (vi) non-organic compounds such as carbon black, carbon fiber, carbon nanotube, graphite, metal powder, and metal oxide powder. The composition ratio of the non-organic compound is 0.05 parts by weight or less per 100 parts by weight of the polycarbonate resin. In addition to the antistatic performance, the non-organic compounds exemplified in (vi) may be blended as a heat ray absorbent.

  For the polycarbonate resin forming the resin molded article of the present invention, a compound having a heat ray absorbing ability in an amount that does not impair the object of the present invention can be used. Preferred examples of the compound include phthalocyanine-based near infrared absorbers and carbon fillers. As such a phthalocyanine-based near infrared absorber, for example, MIR-362 manufactured by Mitsui Chemicals, Inc. is commercially available and easily available. Examples of the carbon filler include carbon black, graphite (including both natural and artificial, and whisker), carbon fiber (including those produced by vapor phase growth), carbon nanotubes, and fullerenes, preferably carbon black. And graphite. These can be used alone or in combination of two or more. The phthalocyanine-based near infrared absorber is preferably 0.005 to 0.2 parts by weight, more preferably 0.008 to 0.1 parts by weight, and 0.01 to 0.07 parts by weight with respect to 100 parts by weight of the polycarbonate resin. Is more preferable. The carbon filler is preferably in the range of 0.1 to 200 ppm (weight ratio) in the resin of the present invention, more preferably in the range of 0.5 to 100 ppm, and still more preferably in the range of 1 to 50 ppm.

  A flame retardant in an amount that does not impair the object of the present invention can be used for the polycarbonate resin that forms the resin molded product of the present invention. Flame retardants include brominated epoxy resins, brominated polystyrenes, brominated polycarbonates, brominated polyacrylates, halogenated flame retardants such as chlorinated polyethylene, phosphate ester flame retardants such as monophosphate compounds and phosphate oligomer compounds, Organic phosphorus flame retardants other than phosphate ester flame retardants such as phosphinate compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, phosphonic acid amide compounds, organic sulfonate alkali (earth) metal salts, borate metal salt flame retardants And organic metal salt flame retardants such as metal stannate flame retardants, silicone flame retardants, ammonium polyphosphate flame retardants, and triazine flame retardants. Separately, a flame retardant aid (for example, sodium antimonate, antimony trioxide, etc.), an anti-drip agent (polytetrafluoroethylene having fibril-forming ability, etc.), etc. may be blended and used together with the flame retardant.

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

  In the resin composition constituting the 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 the amount is less than 0.05 parts by weight, sufficient flame retardancy is not exhibited. If the amount exceeds 50 parts by weight, the strength and heat resistance of the molded product are impaired.

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

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

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

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

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

  Examples of the phosphite compound include triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl Monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, tris (diethylphenyl) phos Phyto, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite Ito, and tris (2,6-di -tert- butylphenyl) phosphite and the like.

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

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

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

  Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.

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

Other resins and elastomers can be appropriately blended according to the purpose in the polycarbonate resin forming the resin molded product of the present invention.
Examples of such other resins include other polycarbonate resins such as aromatic polycarbonate resins, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, and polyphenylene ether resins. , Polyphenylene sulfide resin, polysulfone resin, polyolefin resin such as polyethylene, polypropylene, polystyrene resin, acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), polymethacrylate resin, phenol resin, Resins such as epoxy resins can be used.

  As the elastomer, for example, isobutylene / isoprene rubber, styrene / butadiene rubber, ethylene / propylene rubber, acrylic elastomer, polyester elastomer, polyamide elastomer, MBS (methyl methacrylate / sterene / butadiene) which is a core-shell type elastomer. Examples thereof include rubber and MAS (methyl methacrylate / acrylonitrile / styrene) rubber.

  For the aromatic polycarbonate resin forming the resin molded product of the present invention, various release agents, inorganic fillers, flow modifiers, antibacterial agents, photocatalytic antifouling agents, metallic agents, photochromic agents, etc. Can be blended as long as the effects of the present invention are not impaired.

<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 used in the present invention increases.

  The resin molded product of the present invention can be usually produced by injection molding the pellets produced as described above. In such injection molding, not only ordinary molding methods but also injection compression molding, injection press molding, gas assist injection molding, insert molding, in-mold coating molding, heat insulating mold molding, rapid heating and cooling mold, depending on the purpose as appropriate. Molded articles can be obtained using injection molding methods such as mold molding, two-color molding, sandwich molding, and ultra-high speed injection molding. The advantages of these various molding methods are already widely known. In addition, either a cold runner method or a hot runner method can be selected for molding.

  The resin molded product obtained as described above is manufactured under a wide range of molding processing conditions having no practical problem, and has a good surface hardness and a good rigidity. More specifically, (i) the pencil scratch value measured according to JIS K5400 is not less than HB, and (ii) the value of the flexural modulus measured according to ASTM D790 is A resin molded product characterized in that it is 3,000 MPa or more is obtained, and such a resin molded product has a higher industrial value. Conventionally, in order to improve the flexural modulus of a resin molded product, it was common to add a reinforcing material on fiber or an inorganic filler, but in that case, the surface roughness was significantly reduced, This is because a product that can achieve the above balance has not been obtained.

  The pencil scratch value is more preferably F or more, and the upper limit is 6H. The value of the flexural modulus is more preferably 3,300 MPa or more, and further preferably 3,500 MPa or more. On the other hand, the upper limit is suitably 8,000 MPa, preferably 7,000 MPa, and more preferably 6,000 MPa.

  The resin molded article of the present invention has a total light transmittance of 75% or more and 80% or more measured in accordance with JIS K7105 in a 1 mm-thick smooth flat molded article formed from the resin composition. It is more preferable. A composition satisfying such conditions makes it possible to provide a resin molded product having better light transmittance. Furthermore, the resin molded product of the present invention preferably has a thickness of 1 to 5 mm. The resin molded product of the present invention has good light transmittance even at such a thickness, and provides a transparent resin molded product having such a thickness. The smooth flat plate-like molded product referred to here preferably has an arithmetic mean roughness Ra of 0.1 μm or less, more preferably 0.08 μm or less, more preferably 0, as measured on the surface according to JIS B0601. .05 μm or less. The lower limit is largely due to the mold for molding, but about 0.001 μm is appropriate.

  The resin molded product of the present invention can be subjected to various surface treatments. As the surface treatment, various surface treatments such as a hard coat, a water / oil repellent coat, a hydrophilic coat, an antistatic coat, an ultraviolet absorption coat, an infrared absorption coat, and metalizing (evaporation) can be performed. Examples of the surface treatment method include liquid deposition, vapor deposition, thermal spraying, and plating. As the vapor deposition method, either a physical vapor deposition method or a chemical vapor deposition method can be used. Examples of physical vapor deposition include vacuum vapor deposition, sputtering, and ion plating. Examples of the chemical vapor deposition (CVD) method include a thermal CVD method, a plasma CVD method, and a photo CVD method. For example, by metallizing, a molded product suitable for applications such as a mirror and a reflector is provided.

  The resin molded product of the present invention has a good surface hardness, but is further suitable for a transparent member for vehicles by applying a hard coat. That is, since the base molded article has a good surface hardness, the characteristics of the hard coat layer can be expressed more effectively. Furthermore, since the linear expansion coefficient of the resin molded product of the present invention is also reduced, the adhesiveness is also reduced due to the difference in expansion coefficient from the hard coat layer.

  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 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 alcohol generated during the condensation reaction (in the case of a partially hydrolyzed condensate of alkoxysilane), etc., 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 hard coat agents, silicone resin hard coat agents with excellent long-term durability and relatively high surface hardness, or UV curable acrylics that can be processed with a relatively simple and good hard coat layer. A resin or a polyfunctional acrylic resin is preferred. The silicone resin hard coat agent can be selected from a so-called two-coat type composed of a primer layer and a top layer and a so-called one-coat type formed from only one layer.

  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. Various polyfunctional acrylic resins such as acrylate, phosphazene acrylate, melamine acrylate, amino acrylate and the like can be mentioned, and these can be used alone or in combination of two or more. Among these, an acrylic resin and a polyfunctional acrylic resin preferably include 50% by weight, more preferably 60% by weight or more, and those composed of an acrylic resin and a 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 hard coat layer includes the above-mentioned light stabilizer and ultraviolet absorber, catalyst, thermal / photopolymerization initiator, polymerization inhibitor, silicone antifoaming agent, leveling agent, thickener, precipitation prevention. Agents, sag-preventing agents, flame retardants, various additives of organic / inorganic pigments / dyes, and auxiliary additives can be included.

  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 resin molded product of the present invention is excellent in transparency, surface smoothness, and surface hardness. Further, the resin molded product of the present invention can greatly improve the bending rigidity without increasing the weight of the molded product, and such characteristics contribute to the weight reduction of the product. A further feature is that the resin composition constituting the resin molded product of the present invention is excellent in thermal stability and can be applied to a large injection molded product. From these characteristics, the resin molded product of the present invention is suitable for various transparent members. Examples of such transparent members include transparent members for various vehicles (head lamp lens, winker lamp lens, tail lamp lens, resin window glass, meter cover, sunroof, moon roof, detachable top, window reflector, winker lamp lens, room lamp lens. , And display display front plate, etc.), lighting cover, resin window glass (for construction, etc.), solar cell cover or solar cell substrate, display device lens, touch panel, mirror, and parts for pachinko machines, etc. (Circuit cover, chassis, pachinko ball conveyance guide, etc.). Furthermore, among these, a molded product that is subjected to a hard coat treatment is particularly suitable for the resin molded product of the present invention.

  The present invention is a molded product obtained from a polycarbonate resin made from biomass resources, and has good transparency, heat resistance, mechanical properties, and environmental resistance properties, and in addition, resin molding with reduced environmental impact Since it is a product, it is useful for use in transparent parts centering on vehicles, and its industrial effect is exceptional.

Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to these.
A polycarbonate resin was produced by the method shown in the following production example. Moreover, each value in an Example was calculated | required with the following method.
(1) Melt viscosity Obtained as a result of measurement using a capillary rheometer (Capillograph Model 1D) manufactured by Toyo Seiki Co., Ltd. with a capillary length of 10.0 mm, a capillary diameter of 1.0 mm, and a measurement temperature of 250 ° C. The melt viscosity at 600 sec ⁻¹ was read from the obtained Shear Rate / Viscosity curve.
(2) Glass transition temperature The glass transition temperature was measured by DSC (model DSC2910) manufactured by TA Instruments.
(3) 5% weight loss temperature Measured with TGA (model TGA2950) manufactured by TA Instruments.

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

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

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

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

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

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

<Adjustment of hard coat composition>
(1) Coating composition (i-1)
A flask equipped with a reflux condenser and a stirrer and substituted with nitrogen in a flask with 70 parts of methyl methacrylate (hereinafter abbreviated as MMA), 39 parts of 2-hydroxyethyl methacrylate (hereinafter abbreviated as HEMA), 0.18 parts (abbreviated as AIBN) and 200 parts of 1,2-dimethoxyethane were added, 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 90 parts of a copolymer (acrylic resin (I)) having a composition ratio of MMA / HEMA of 70/30 (molar ratio). The weight average molecular weight of the copolymer was 80,000 in terms of polystyrene based on GPC measurement (column; Shodex GPCA-804, eluent: THF).

  Next, as the composition for the hard coat first layer, 8 parts of the acrylic resin (I) is mixed with 40 parts of methyl ethyl ketone, 20 parts of methyl isobutyl ketone, 5.2 parts of ethanol, 14 parts of isopropanol and 10 parts of 2-ethoxyethanol. Then, 10 parts of methyltrimethoxysilane hydrolysis condensate solution (X) was added to this solution and stirred at 25 ° C. for 5 minutes. To this solution was added melamine resin (Cymel 303, Mitsui Cytec Co., Ltd.). ) 1 part was added and stirred at 25 ° C. for 5 minutes to prepare a coating composition (i-1).

(2) Coating composition (ii-1)
Using the same apparatus as above, 142 parts of methyltrimethoxysilane, 72 parts of distilled water and 20 parts of acetic acid were mixed with cooling with ice water, and the mixture was stirred at 25 ° C. for 1 hour and diluted with 116 parts of isopropanol. Thus, 350 parts of methyltrimethoxysilane hydrolysis condensate solution (X) was obtained. On the other hand, 208 parts of tetraethoxysilane and 81 parts of 0.01N hydrochloric acid were mixed with cooling with ice water, the mixture was stirred at 25 ° C. for 3 hours, diluted with 11 parts of isopropanol, and the tetraethoxysilane hydrolyzed condensate solution ( Y) 300 parts were obtained.

  Furthermore, as a composition for the hard coat second layer, 12 parts of distilled water and 20 parts of acetic acid are added to 100 parts of a water-dispersed colloidal silica dispersion (Snowtex 30 solid content concentration: 30% by weight, manufactured by Nissan Chemical Industries, Ltd.). The mixture was stirred, and 134 parts of methyltrimethoxysilane was added to the dispersion while cooling in an ice-water bath. To this reaction liquid obtained by stirring this mixed liquid at 25 ° C. for 1 hour, 20 parts of tetraethoxysilane hydrolysis condensate solution (Y) and 1 part of sodium acetate as a curing catalyst were added and diluted with 200 parts of isopropanol to coat. A composition for use (ii-1) was prepared.

Molded articles were produced by the methods shown in the following examples and comparative examples. The evaluation of the molded product was obtained by the following method.
(1) Total light transmittance, haze Using a haze meter HR-100 (manufactured by Murakami Color Research Laboratory Co., Ltd.), the resin molded product (smooth square plate molded product having a thickness of 1 mm) was measured according to JIS K7105.
(2) Heat resistance According to ISO75-1 and 2, the deflection temperature under load was measured under the condition of load: 1.80 MPa.
(3) Flexural modulus The flexural modulus was measured according to ISO178 (test piece shape: length 80 mm × width 10 mm × thickness 4 mm).
(4) Pencil Scratch Value According to the method defined in JIS K5400, the pencil scratch value was measured by a hand scratch method using a 1 mm thick smooth square plate molded product.
(5) Hard Coat Adhesive Nichiban adhesive tape (product name) by making 100 grids at 1 mm intervals on the hard coat layer with a cutter knife in the center of the resin molded product (smooth square plate molded product with a thickness of 1 mm) “Cello tape (registered trademark)”) was pressure-bonded and peeled strongly vertically to observe whether or not all remained on the resin molded product. Among the 10 resin molded products, the number n of molded products that did not remain was determined.

<Examples 1-9, Comparative Examples 1-5>
Polycarbonate resin and other components having the composition shown in Table 1 are supplied to a vent type twin screw extruder [TEX30XSST manufactured by Nippon Steel Works, Ltd.] having a diameter of 30 mmφ, cylinder temperature 250 ° C., screw rotation speed 150 rpm, discharge amount 20 kg. / H, and melt-extruded at a reduced pressure of 3 kPa for pelletization.

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

  The obtained pellets were dried with a hot air circulation dryer at 100 ° C. for 12 hours. After drying, a test piece for evaluating the deflection temperature under load is molded by an injection molding machine (JSWJ-75EIII, manufactured by Nippon Steel) with a cylinder temperature, a mold temperature of 90 ° C. and a molding cycle of 180 seconds. did.

  In addition, using the dried pellets, a 150 mm square × 1 mm thick smooth square plate molded product and a bending test piece were subjected to a cylinder temperature of 250 ° C. and a mold temperature of 80 using an injection molding machine (Toshiba Machine Co., Ltd .: IS-150EN). Molding was performed at a temperature of 40 ° C. for 40 seconds.

  Further, after the smooth square plate molded product was annealed at 120 ° C. for 2 hours, the coating composition (i-1) was applied by dip coating, left at 25 ° C. for 20 minutes, and then at 120 ° C. for 30 minutes. Heat cured. Next, the coating composition (ii-1) was further applied to the resin molded article by a dip coating method, allowed to stand at 25 ° C. for 20 minutes, and then thermally cured at 120 ° C. for 2 hours to perform a hard coat treatment. Observation of the obtained resin molded product revealed no occurrence of cracks.

Each characteristic was measured using these molded articles. Their injection moldability and measurement results are shown in Tables 1 and 2. In addition, each symbol in Table 1 represents the following.
(B-1) Mold release agent: stearic acid monoglyceride (Rikenmar S-100A manufactured by Riken Vitamin Co., Ltd.)
(B-2) Release agent: Pentaerythritol tetrastearyl ester (VPG-861 manufactured by Cognis Japan KK)
(PO) Antioxidant: Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (manufactured by Adeka Adeka Stub PEP-36)
(UVA) UV absorber (manufactured by Ciba Specialty Chemicals: Tinuvin 1577)
(HP) Hindered phenolic antioxidant (Ciba Specialty Chemicals: Irganox 1076)
(IR) phthalocyanine-based near infrared absorber (Mitsui Chemicals, Inc .: MIR-362, TGA 5% weight loss temperature 282 ° C.)
(CB) Carbon black (Mitsubishi Chemical Corporation: Furnace Black MA-100, pH = 3.5)
(FR) Perylene red fluorescent dye (BASF: Lumogen F Red 300)
(OB) Coumarin-based fluorescent brightening agent (Hackol Chemical Co., Ltd .: Hackol PSR)

  As is apparent from the results of Tables 1 and 2, the polycarbonate resin of the present invention having a specific melt viscosity and glass transition temperature can obtain a good molded product when injection molded in a specific temperature range. It turns out that it is excellent in transparency, heat resistance, mechanical properties, and the like. Furthermore, it can be seen that the same good characteristics can be maintained even in the composition provided with various functional additives, and various functions required for the transparent member can be imparted without problems.

Claims (8)

It consists of a carbonate structural unit represented by the following formula (1), and the melt viscosity measured by a capillary rheometer at 250 ° C. is 0.2 × 10 ^{3 to} 4.0 × 10 ³ Pa under the condition of a shear rate of 600 sec ^-1. The total light transmittance of a 1 mm-thick smooth plate-like molded article, measured according to JIS K7105, obtained by injection molding a polycarbonate resin (component A) in the range of s in a cylinder temperature range of 220 to 270 ° C. A resin molded product characterized by being 75% or more.

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

  The resin molded product according to any one of claims 1 to 3, wherein the total light transmittance is 80% or more.   The resin molded product according to any one of claims 1 to 4, wherein the resin molded product has a thickness of 1 to 5 mm.   The resin molded product has (i) a pencil scratch value measured according to JIS K5400 by a hand-scratch method of HB or more, and (ii) a flexural modulus value measured according to ASTM D790 of 3,000 MPa or more. Item 6. The resin molded product according to any one of Items 1 to 5.   The resin molded product according to any one of claims 1 to 6, wherein the resin molded product is subjected to a hard coat treatment on a surface thereof.   The resin molded product according to any one of claims 1 to 7, wherein the resin molded product is a vehicle transparent member.