JP2014198761A - Polycarbonate resin molded product - Google Patents

Abstract

An object of the present invention is to provide a resin molded product excellent in thin moldability, impact resistance, surface hardness, heat and humidity resistance, and low optical distortion. A resin containing a polycarbonate resin having a structural unit (a) derived from a dihydroxy compound having a structure represented by the following general formula (1) and a structural unit (b) derived from another dihydroxy compound. A molded article molded using the composition, and the structural unit (a) in the polycarbonate resin occupies 70 mol% or more of the structural units derived from all dihydroxy compounds constituting the polycarbonate resin. A molded product characterized in that it is a resin, the reduced viscosity of the polycarbonate resin is 0.45 dL / g or less, and the thickness of the molded product is from 0.1 mm to 1 mm. (However, the case where the structure represented by the general formula (1) is a part of —CH 2 —O—H) [Selection] None

Description

  The present invention relates to a molded article molded using a polycarbonate resin composition. More specifically, the present invention relates to a resin molded product having excellent thin-wall moldability, impact resistance, surface hardness and moist heat resistance and low optical distortion.

Polycarbonate resins are generally composed of bisphenols as monomer components, taking advantage of transparency, heat resistance, mechanical strength, etc., and electrical / electronic parts, automotive parts, medical parts, building materials, films, sheets, bottles It is widely used as so-called engineering plastics in the fields of optical recording media and lenses.
However, conventional polycarbonate resins are limited in use outdoors or in the vicinity of lighting devices, because their hue, transparency, and mechanical strength deteriorate when used in places exposed to ultraviolet rays or visible light for a long time. .

In order to solve such problems, a method of adding a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, or a benzoxazine ultraviolet absorber to a polycarbonate resin is widely known (for example, Non-Patent Document 1).
However, when such an ultraviolet absorber is added, although the hue after UV irradiation is improved, the hue, heat resistance and transparency of the resin are deteriorated in the first place. There were problems such as contamination of the mold.

  Since the bisphenol compound used in the conventional polycarbonate resin has a benzene ring structure, it absorbs a large amount of ultraviolet rays. This causes a deterioration in the light resistance of the polycarbonate resin. Therefore, an aliphatic dihydroxy compound having no benzene ring structure in the molecular skeleton. If a cyclic dihydroxy compound monomer unit having an ether bond in the molecule, such as a compound, an alicyclic dihydroxy compound, or isosorbide, is used, it is expected that light resistance is improved in principle. Among them, a polycarbonate resin using isosorbide obtained from biomass resources as a monomer is excellent in heat resistance and mechanical strength, so that many studies have been made in recent years (for example, Patent Documents 1 to 6). .

  However, cyclic dihydroxy compounds having an ether bond in the molecule, such as the above aliphatic dihydroxy compounds, alicyclic dihydroxy compounds, and isosorbide, do not have phenolic hydroxyl groups, and thus are widely known as methods for producing polycarbonate resins using bisphenol A as a raw material. It is difficult to polymerize by the conventional interface method, and it is usually produced by a method called a transesterification method or a melting method. In this method, the dihydroxy compound and a carbonic acid diester such as diphenyl carbonate are transesterified at a high temperature of 200 ° C. or higher in the presence of a basic catalyst, and the polymerization proceeds by removing by-product phenol and the like out of the system, A polycarbonate resin is obtained. However, a polycarbonate resin obtained using a monomer having no phenolic hydroxyl group as described above is inferior in thermal stability to a polycarbonate resin obtained using a monomer having a phenolic hydroxyl group such as bisphenol A. In addition, there is a problem that coloring occurs during polymerization or molding that is exposed to high temperatures, and as a result, ultraviolet light and visible light are absorbed, resulting in deterioration of light resistance. Among these, when a monomer having an ether bond in the molecule, such as isosorbide, is used, the hue is remarkably deteriorated, and it is difficult to solve the improvement in brightness. Furthermore, when it is used as various molded products, it is melt-molded at a high temperature. At that time, a material having good thermal stability and excellent moldability and mold release properties has been demanded.

  Patent Document 7 proposes a large-sized resin molded product made of a polycarbonate resin using a biomass resource excellent in heat resistance, thermal stability and mechanical properties as a raw material, but has insufficient mechanical properties. It was. Furthermore, Patent Document 8 describes that an optical sheet having a high light transmittance and a method for producing the same, and forming a concavo-convex pattern on the surface of the optical sheet, which can be easily processed into a molded body such as a light guide plate having a thin wall and a large screen. A molded body and a method for producing the molded body are provided, and although the optical distortion is low, the processing temperature is high due to the use of aromatic polycarbonate, and the shape of the molded product is due to extrusion molding. There was a problem of being limited.

  Patent Document 9 proposes a resin molded product having not only excellent low optical distortion properties but also excellent light resistance, hue, transparency, thermal stability, and mechanical strength. The heat and humidity resistance was not considered. In this document, a molded product mainly composed of a plate-shaped portion, and a molded product characterized in that the thickness of the plate-shaped portion of the molded product is 0.5 mm or more and 5 mm or less is proposed. In the examples, molded products having a thickness of 3 mm and 5 mm are only exemplified, and problems (for example, deterioration of moldability and increase in optical distortion) caused by thinning the molded product are not considered. Furthermore, Patent Document 10 proposes a surface protective film or sheet made of a polycarbonate resin using biomass resources as a raw material, but since the manufacturing method is a solution casting method or a melt film forming method, the shape of the molded product is There was a problem of being limited.

  On the other hand, in recent years, demands for further weight reduction and thinning of smartphones, tablet terminal type personal computers, notebook computers, displays, etc. are increasing, and there is a strong demand for weight reduction and thinning of members constituting these products. Therefore, new problems (such as thinner formability than before) are becoming more prominent due to weight reduction and thinning.

International Publication No. 04/111106 Pamphlet Japanese Patent Laid-Open No. 2006-232897 JP 2006-28441 A JP 2008-24919 A JP 2009-91404 A JP 2009-91417 A JP 2009-102537 A JP 2009-242752 A JP 2012-67287 A JP 2009-79190 A

Polycarbonate resin handbook (issued by Seiichi Honma, published by Nikkan Kogyo Shimbun, August 28, 1992)

  An object of the present invention is to solve the above-mentioned conventional problems, and to provide a resin molded product which is excellent in thin-wall moldability, impact resistance, surface hardness and moist heat resistance and has low optical distortion.

  As a result of intensive studies to solve the above problems, the present inventor contains a polycarbonate resin having a structural unit (a) derived from a specific dihydroxy compound and a structural unit (b) derived from another dihydroxy compound. 70 mol% of structural units derived from all dihydroxy compounds constituting the polycarbonate resin, wherein the proportion of the structural unit (a) in the polycarbonate resin is a molded product molded using the resin composition It is a polycarbonate resin that occupies the above, and the reduced viscosity of the polycarbonate resin is 0.45 dL / g or less, and it is suitable for molding a thin molded product having a thickness of the molded product of 0.1 mm or more and 1 mm or less. Furthermore, it has low optical distortion, excellent heat and humidity resistance, surface hardness, transparency, and necessary and sufficient impact resistance. Out, and we arrived at the present invention.

（但し、上記一般式（１）で表される構造が−ＣＨ₂−Ｏ−Ｈの一部である場合を除く。）

［２］ 前記ポリカーボネート樹脂中の構造単位（ｂ）が、脂肪族ジヒドロキシ化合物及び脂環式ジヒドロキシ化合物からなる群より選ばれる少なくとも１種の化合物に由来する構成単位である前記［１］に記載の成形品。
［３］ 一般式（１）で表される構造を有するジヒドロキシ化合物が、下記一般式（２）で表される化合物である前記［１］または［２］のいずれかに記載の成形品。

［４］ 前記成形品が射出成形法により成形されたものである前記［１］乃至［３］のいずれかに記載の成形品。
［５］ 前記成形品の少なくとも片面に、ハードコート処理がなされている前記［１］乃至［４］のいずれかに記載の成形品。
［６］ 前記成形品の少なくとも片面に、金型内加飾フィルムが積層されている前記［１］乃至［５］のいずれかに記載の成形品。
［７］ 前記［１］乃至［６］のいずれかに記載の成形品と筐体が二色成形されてなる樹脂一体成形品。
［８］ 前記［１］乃至［６］のいずれかに記載の成形品からなるフラットパネルディスプレイの前面板。
［９］ 前記［１］乃至［６］のいずれかに記載の成形品からなるタブレット型パーソナルコンピュータの前面板。 That is, the present invention relates to the following inventions.
[1] A resin composition containing a polycarbonate resin having a structural unit (a) derived from a dihydroxy compound having a structure represented by the following general formula (1) and a structural unit (b) derived from another dihydroxy compound And the proportion of the structural unit (a) in the polycarbonate resin accounts for 70 mol% or more of the structural units derived from all dihydroxy compounds constituting the polycarbonate resin. A molded product which is a polycarbonate resin, the reduced viscosity of the polycarbonate resin is 0.45 dL / g or less, and the thickness of the molded product is 0.1 mm or more and 1 mm or less.

(However, the case where the structure represented by the general formula (1) is a part of —CH ₂ —O—H is excluded.)

[2] The structural unit (b) in the polycarbonate resin is a structural unit derived from at least one compound selected from the group consisting of an aliphatic dihydroxy compound and an alicyclic dihydroxy compound. Molding.
[3] The molded article according to any one of [1] or [2], wherein the dihydroxy compound having a structure represented by the general formula (1) is a compound represented by the following general formula (2).

[4] The molded product according to any one of [1] to [3], wherein the molded product is molded by an injection molding method.
[5] The molded product according to any one of [1] to [4], wherein at least one surface of the molded product is subjected to a hard coat treatment.
[6] The molded product according to any one of [1] to [5], wherein an in-mold decorative film is laminated on at least one surface of the molded product.
[7] A resin integrated molded product obtained by two-color molding of the molded product according to any one of [1] to [6] and a housing.
[8] A front panel of a flat panel display comprising the molded product according to any one of [1] to [6].
[9] A front plate of a tablet personal computer comprising the molded product according to any one of [1] to [6].

  According to the present invention, a resin molded product having not only low optical distortion but also excellent thin-wall moldability, impact resistance, surface hardness, and heat-and-moisture resistance can be obtained, and injection of electrical / electronic parts, automotive parts, etc. It becomes possible to provide resin molded products that can be applied to a wide range of fields such as molding applications, camera lenses, finder lenses, lenses such as CCD and CMOS lenses, and optical applications such as optical disks, optical materials, and optical components.

  Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the invention.

（但し、上記一般式（１）で表される構造が−ＣＨ₂−Ｏ−Ｈの一部である場合を除く。） The present invention is a resin containing a polycarbonate resin having a structural unit (a) derived from a dihydroxy compound having a structure represented by the following general formula (1) and a structural unit (b) derived from another dihydroxy compound. A molded product molded using the composition, and the proportion of the structural unit (a) in the polycarbonate resin is 70 mol% or more of the structural units derived from all dihydroxy compounds constituting the polycarbonate resin. The present invention relates to a molded article characterized in that the polycarbonate resin is occupied, the reduced viscosity of the polycarbonate resin is 0.45 dL / g or less, and the thickness of the molded article is 0.1 mm or more and 1 mm or less. By adopting such a configuration, the molded product can be made into a resin molded product having not only low optical distortion but also excellent thin-wall moldability, impact resistance, surface hardness, and wet heat resistance.

(However, the case where the structure represented by the general formula (1) is a part of —CH ₂ —O—H is excluded.)

(1) Polycarbonate resin and resin composition based thereon Polycarbonate resin for obtaining the molded article of the present invention and a resin composition based thereon are described in detail below.

[Polycarbonate resin]
<Raw material>
(Dihydroxy compound)
The polycarbonate resin used in the present invention (hereinafter sometimes referred to as “resin used in the present invention”) is a dihydroxy compound having a structure represented by the following general formula (1) as a part of the structure (hereinafter referred to as “ At least the structural unit (a) derived from “dihydroxy compound used in the present invention”. That is, the dihydroxy compound used in the present invention includes two hydroxyl groups and at least a structure represented by the following general formula (1) in a part of the structure.

（但し、上記一般式（１）で表される構造が−ＣＨ₂−Ｏ−Ｈの一部である場合を除く。）

(However, the case where the structure represented by the general formula (1) is a part of —CH ₂ —O—H is excluded.)

The dihydroxy compound used in the present invention is not particularly limited as long as it has a structure represented by the above general formula (1) in a part of the structure, but specifically, diethylene glycol, triethylene glycol Oxyalkylene glycols such as tetraethylene glycol, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) fluorene 9,9-bis (4- (2-hydroxyethoxy) -3-isopropylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-isobutylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-tert-butylphenyl) fluorene, 9,9-bis (4 (2-hydroxyethoxy) -3-cyclohexylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3,5-dimethylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-tert-butyl-6-methylphenyl) fluorene 9,9-bis (4- (3-hydroxy- 2,2-dimethylpropoxy) phenyl) fluorene and the like, compounds having an aromatic group in the side chain and an ether group bonded to the aromatic group in the main chain, and dihydroxy compounds represented by the following general formula (2) Although the compound which has cyclic ether structures, such as the anhydrosugar alcohol represented and the spiroglycol represented by following General formula (3), is mentioned, From the viewpoints of ease of handling, handling, reactivity during polymerization, and hue of the polycarbonate resin obtained, diethylene glycol and triethylene glycol are preferred. From the viewpoint of heat resistance, anhydrous sugar alcohols and compounds having a cyclic ether structure are preferred. preferable.
These may be used alone or in combination of two or more depending on the required performance of the resin to be obtained.

Examples of the dihydroxy compound represented by the general formula (2) include isosorbide, isomannide and isoidet which are in a stereoisomeric relationship, and these may be used alone or in combination of two or more. It may be used.
Of these dihydroxy compounds, it is preferable to use a dihydroxy compound having no aromatic ring structure from the viewpoint of the light resistance of the resin. Among them, it is produced from various starches that are abundant as plant-derived resources and are easily available. Isosorbide obtained by dehydrating and condensing sorbitol is most preferable from the viewpoints of availability and production, light resistance, optical properties, moldability, heat resistance, and carbon neutral.

  The resin used in the present invention may contain a structural unit (b) derived from a dihydroxy compound other than the dihydroxy compound used in the present invention (hereinafter sometimes referred to as “other dihydroxy compound”). Examples of the dihydroxy compound include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-heptanediol, Aliphatic dihydroxy compounds such as 1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, pentacyclopentadecane dimethanol, 2,6-decalin dimethanol, 1,5-decalin Methanol, 2,3-decalin methanol, 2,3-norbornane methanol, 2,5-norbornane methanol, 1,3-adamantane dimethanol, dihydroxy compound alicyclic hydrocarbon and the like and the like.

  2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as “bisphenol A”), 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2- Bis (4-hydroxy-3,5-diethylphenyl) propane, 2,2-bis (4-hydroxy- (3,5-diphenyl) phenyl) propane, 2,2-bis (4-hydroxy-3,5- Dibromophenyl) propane, 2,2-bis (4-hydroxyphenyl) pentane, 2,4′-dihydroxy-diphenylmethane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-5-nitrophenyl) methane, 1 , 1-bis (4-hydroxyphenyl) ethane, 3,3-bis (4-hydroxyphenyl) pentane, 1,1-bis (4-hydroxy) Enyl) cyclohexane, bis (4-hydroxyphenyl) sulfone, 2,4′-dihydroxydiphenylsulfone, bis (4-hydroxyphenyl) sulfide, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3 ′ -Dichlorodiphenyl ether, 9,9-bis (4- (2-hydroxyethoxy-2-methyl) phenyl) fluorene, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-2) Aromatic bisphenols such as -methylphenyl) fluorene can also be used.

  The structural unit (b) in the polycarbonate resin is preferably a structural unit derived from at least one compound selected from the group consisting of an aliphatic dihydroxy compound and an alicyclic dihydroxy compound. That is, from the viewpoint of the light resistance of the resin, at least one compound selected from the group consisting of an aliphatic dihydroxy compound that is a dihydroxy compound having no aromatic ring structure in the molecular structure and an alicyclic hydrocarbon dihydroxy compound is used. As the aliphatic dihydroxy compound, 1,3-propanediol, 1,4-butanediol, and 1,6-hexanediol are particularly preferable. As the alicyclic hydrocarbon dihydroxy compound, 1,4 is particularly preferable. -Cyclohexanedimethanol and tricyclodecanedimethanol are preferred.

  By using these other dihydroxy compounds, it is possible to obtain effects such as improvement in flexibility of the resin, improvement in heat resistance, improvement in moldability, etc., but inclusion of structural units derived from other dihydroxy compounds If the ratio is too large, mechanical properties and heat resistance may be reduced. Therefore, the dihydroxy compound having a structure represented by the general formula (1) as a part of the structure with respect to all dihydroxy compounds. The proportion of the derived structural unit (a) is preferably 70 mol% or more, more preferably 75 mol% or more, and most preferably 85 mol% or more. On the other hand, the upper limit is preferably 95 mol% or less, more preferably 90 mol% or less. If this ratio is too small, the moisture and heat resistance properties tend to decrease, while if too large, the impact resistance tends to deteriorate.

  One of the characteristics of the resin molded product of the present invention is that, as described above, a structural unit derived from a dihydroxy compound having a structure represented by the general formula (1) as a part of the structure for all dihydroxy compounds (a ) In the specific range as described above. Thereby, the optical distortion generally expressed by the birefringence or phase difference of the resin can be made lower than that of a molded product using a conventional polycarbonate resin.

  The dihydroxy compound used in the present invention may contain a stabilizer such as a reducing agent, antioxidant, oxygen scavenger, light stabilizer, antacid, pH stabilizer, heat stabilizer, etc. Since the dihydroxy compound used in the invention is easily altered, it is preferable to include a basic stabilizer. Basic stabilizers include Group 1 or Group 2 metal hydroxides, carbonates, phosphates, phosphites, hypophosphites in the Long Periodic Periodic Table (Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005). Salts, borates, fatty acid salts, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, Triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium Basic ammonium compounds such as um hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide, butyltriphenylammonium hydroxide, 4-aminopyridine, 2-aminopyridine, N, N -Dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2-dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole And amine compounds such as aminoquinoline. Of these, sodium or potassium phosphates and phosphites are preferred, and disodium hydrogen phosphate and disodium hydrogen phosphite are particularly preferred because of their effects and ease of distillation removal described below.

  Although there is no restriction | limiting in particular in content in the dihydroxy compound used for this invention of these basic stabilizers, if there is too little, there exists a possibility that the effect which prevents the quality change of the dihydroxy compound used for this invention may not be acquired, and too much. Since it may cause modification of the dihydroxy compound used in the present invention, it is usually 0.0001% by weight to 1% by weight, preferably 0.001% by weight to 0.1% by weight, based on the dihydroxy compound used in the present invention. It is.

  Further, when the dihydroxy compound used in the present invention containing these basic stabilizers is used as a raw material for producing polycarbonate resin, the basic stabilizer itself becomes a polymerization catalyst, and it becomes difficult to control the polymerization rate and quality. It is preferable to remove the basic stabilizer by ion exchange or distillation before using it as a raw material for producing the resin in order to deteriorate the initial hue and consequently deteriorate the light resistance of the molded product.

  When the dihydroxy compound used in the present invention has a cyclic ether structure such as isosorbide, it is easily oxidized by oxygen. Therefore, during storage and production, in order to prevent decomposition by oxygen, water should not be mixed, It is important to use an oxygen scavenger or handle under a nitrogen atmosphere. When isosorbide is oxidized, decomposition products such as formic acid may be generated. For example, when isosorbide containing these decomposition products is used as a raw material for the production of polycarbonate resin, the resulting resin may be colored, and not only the physical properties may be significantly degraded, but also the polymerization reaction may be affected. This is not preferable because a high molecular weight polymer may not be obtained.

  The dihydroxy compound used in the present invention is preferably subjected to distillation purification in order to remove the oxidative decomposition product and the above-mentioned basic stabilizer. The distillation in this case may be simple distillation or continuous distillation, and is not particularly limited. As distillation conditions, it is preferable to carry out distillation under reduced pressure in an inert gas atmosphere such as argon or nitrogen. In order to suppress thermal denaturation, it is 250 ° C. or lower, preferably 200 ° C. or lower, particularly 180 °. It is preferable to carry out under the conditions of ℃ or less.

  By such distillation purification, the dihydroxy compound used in the present invention is made to have a formic acid content in the dihydroxy compound used in the present invention of 20 ppm by weight or less, preferably 10 ppm by weight or less, particularly preferably 5 ppm by weight or less. When a dihydroxy compound containing is used as a resin production raw material, it is possible to produce a resin excellent in hue and thermal stability without impairing polymerization reactivity. The formic acid content is measured by ion chromatography.

(Carbonated diester)
The polycarbonate resin used in the present invention can be obtained by polycondensation by a transesterification reaction using the dihydroxy compound containing the dihydroxy compound used in the present invention and the carbonic acid diester as raw materials.
As a carbonic acid diester used, what is normally represented by following General formula (4) is mentioned. These carbonic acid diesters may be used alone or in combination of two or more.

(In General Formula (4), A ¹ and A ² are each independently a substituted or unsubstituted aliphatic group having 1 to 18 carbon atoms or a substituted or unsubstituted aromatic group; ¹ and A ² may be the same or different.)
Examples of the carbonic acid diester represented by the general formula (4) include substituted diphenyl carbonates such as diphenyl carbonate and ditolyl carbonate, dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate. Diphenyl carbonate and substituted difel carbonate are preferable, and diphenyl carbonate is particularly preferable. Carbonic acid diesters may contain impurities such as chloride ions, which may hinder the polymerization reaction or worsen the hue of the resulting resin. It is preferable to use one.
The resin used in the present invention is a polycarbonate resin having the specific structural unit (a), and the resin may be used as a polycarbonate resin composition by adding other additives within a range not impairing the gist of the present invention. Good.

<Transesterification reaction catalyst>
The resin used in the present invention can be produced by transesterifying the dihydroxy compound containing the dihydroxy compound used in the present invention with a carbonic acid diester as described above. More specifically, it can be obtained by transesterification and removing by-product monohydroxy compounds and the like out of the system. In this case, polycondensation is usually carried out by transesterification in the presence of a transesterification catalyst.

The transesterification reaction catalyst (hereinafter sometimes simply referred to as “catalyst” or “polymerization catalyst”) that can be used in the production of the resin used in the present invention affects the light transmittance at a wavelength of 350 nm and the yellow index value. Can give.
The catalyst used is not limited as long as the light resistance can be satisfied, that is, the light transmittance at a wavelength of 350 nm or the yellow index can be set to a predetermined value. Basic compounds such as metal compounds of Group 2 (hereinafter simply referred to as “Group 1” and “Group 2”), basic boron compounds, basic phosphorus compounds, basic ammonium compounds, amine compounds, and the like. It is done. Preferably, Group 1 metal compounds and / or Group 2 metal compounds are used.

It is possible to use a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, and an amine compound in combination with the Group 1 metal compound and / or the Group 2 metal compound. It is particularly preferred to use only Group 1 metal compounds and / or Group 2 metal compounds.
In addition, the group 1 metal compound and / or the group 2 metal compound are usually used in the form of a hydroxide or a salt such as a carbonate, a carboxylate, or a phenol salt. From the viewpoint of easiness, a hydroxide, carbonate, and acetate are preferable, and acetate is preferable from the viewpoint of hue and polymerization activity.

  Examples of the Group 1 metal compound include sodium hydroxide, sodium hydrogen carbonate, sodium carbonate, sodium acetate, sodium stearate, sodium borohydride, sodium phenyl borohydride, sodium benzoate, disodium hydrogen phosphate, phenyl phosphoric acid. Disodium, sodium alcoholate or phenolate, sodium compounds such as disodium salt of bisphenol A, potassium hydroxide, potassium bicarbonate, potassium carbonate, potassium acetate, potassium stearate, potassium borohydride, potassium borohydride, Potassium compounds such as potassium benzoate, dipotassium hydrogen phosphate, dipotassium phenyl phosphate, potassium alcoholate or phenolate, dipotassium salt of bisphenol A, lithium hydroxide, hydrogen carbonate Lithium, lithium carbonate, lithium acetate, lithium stearate, lithium borohydride, lithium phenyl borohydride, lithium benzoate, dilithium hydrogen phosphate, dilithium phenyl phosphate, lithium alcoholate or phenolate, bisphenol A 2 Lithium compounds such as lithium salts, cesium hydroxide, cesium bicarbonate, cesium carbonate, cesium acetate, cesium stearate, cesium borohydride, cesium phenyl borohydride, cesium benzoate, 2 cesium hydrogen phosphate, 2 cesium phenyl phosphate Cesium compounds such as alcoholate or phenolate of cesium, dicesium salt of bisphenol A, and the like, among which lithium compounds are preferable.

  Examples of the Group 2 metal compound include calcium compounds such as calcium hydroxide, calcium bicarbonate, calcium carbonate, calcium acetate, and calcium stearate, and barium such as barium hydroxide, barium bicarbonate, barium carbonate, barium acetate, and barium stearate. Compounds, magnesium compounds such as magnesium hydroxide, magnesium hydrogen carbonate, magnesium carbonate, magnesium acetate, magnesium stearate, strontium hydroxide, strontium hydrogen carbonate, strontium carbonate, strontium acetate, strontium stearate, etc. Of these, magnesium compounds, calcium compounds and barium compounds are preferred. From the viewpoint of polymerization activity and the hue of the obtained polycarbonate resin, magnesium compounds are preferred. And at least one metal compound is more preferably selected from the group consisting of calcium compound, most preferably a calcium compound.

  Examples of basic boron compounds include tetramethylboron, tetraethylboron, tetrapropylboron, tetrabutylboron, trimethylethylboron, trimethylbenzylboron, trimethylphenylboron, triethylmethylboron, triethylbenzylboron, triethylphenylboron, tributylbenzyl. Examples include sodium, potassium, lithium, calcium, barium, magnesium, or strontium salts such as boron, tributylphenylboron, tetraphenylboron, benzyltriphenylboron, methyltriphenylboron, butyltriphenylboron, etc. It is done.

Examples of the basic phosphorus compound include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, and quaternary phosphonium salts.
Examples of the basic ammonium compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, Triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide Sid, butyl triphenyl ammonium hydroxide, and the like.

  Examples of the amine compound include 4-aminopyridine, 2-aminopyridine, N, N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2 -Dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, aminoquinoline and the like.

  The amount of the polymerization catalyst used is preferably 0.1 μmol to 300 μmol, preferably 0.5 μmol to 100 μmol per 1 mol of all dihydroxy compounds used in the polymerization. Among these, from lithium and a metal of Group 2 of the long-period periodic table When using at least one metal compound selected from the group consisting of, in particular, when using at least one metal compound selected from the group consisting of a magnesium compound and a calcium compound, the amount of metal per 1 mol of the total dihydroxy compound used, Usually, it is 0.1 μmol or more, preferably 0.5 μmol or more, particularly preferably 0.7 μmol or more. Further, the upper limit is usually 20 μmol, preferably 10 μmol, more preferably 3 μmol, particularly preferably 1.5 μmol, and most preferably 1.0 μmol.

  If the amount of the catalyst is too small, the polymerization rate will slow down. As a result, when trying to obtain a resin with the desired molecular weight, the polymerization temperature will have to be increased, and the hue and light resistance of the resulting resin will deteriorate. The unreacted raw material volatilizes during the polymerization, and the molar ratio of the dihydroxy compound containing the dihydroxy compound used in the present invention to the carbonic acid diester represented by the general formula (4) may collapse, and may not reach the desired molecular weight. is there. On the other hand, when the amount of the polymerization catalyst used is too large, the hue of the resulting resin is deteriorated, and the light resistance of the resin may be deteriorated.

Further, Group 1 metals, especially lithium, sodium, potassium and cesium, especially sodium, potassium and cesium, may have a bad influence on the hue when contained in the resin in large quantities, and the metal is only from the catalyst used. However, the total amount of these compounds in the resin is usually 20 ppm by weight or less, preferably 2 ppm by weight or less, more preferably 1.5 wt. ppm or less, more preferably 1.2 ppm by weight or less, particularly preferably 0.8 ppm by weight or less, and most preferably 0.7 ppm by weight or less.
The amount of metal in the resin can be measured using a method such as atomic emission, atomic absorption, Inductively Coupled Plasma (ICP) after recovering the metal in the resin by a method such as wet ashing.

<Manufacturing method>
The polycarbonate resin used in the present invention is obtained by polycondensation of a dihydroxy compound containing the dihydroxy compound used in the present invention and a carbonic acid diester by a transesterification reaction. The raw material dihydroxy compound and the carbonic acid diester are converted before the transesterification reaction. It is preferable to mix uniformly in the raw material preparation tank. Moreover, the raw material uniformly mixed in the raw material preparation tank or the like may be subjected to a transesterification reaction after being stored in the raw material storage tank or the like.

  The mixing temperature is usually 80 ° C. or higher, preferably 90 ° C. or higher, and the upper limit is usually 250 ° C. or lower, preferably 200 ° C. or lower, more preferably 150 ° C. or lower. Among these, 100 ° C. or higher and 120 ° C. or lower is preferable. If the mixing temperature is too low, the dissolution rate may be slow or the solubility may be insufficient, often causing problems such as solidification, and if the mixing temperature is too high, the dihydroxy compound may be thermally deteriorated. The hue of the polycarbonate resin thus obtained may deteriorate, which may adversely affect light resistance.

  The operation of mixing the dihydroxy compound containing the dihydroxy compound used in the present invention, which is the raw material of the resin used in the present invention, and the carbonic acid diester is an oxygen concentration of 10 vol% or less, more preferably 0.0001 vol% to 10 vol%, and more preferably 0.0001 vol% to It is preferable to carry out in an atmosphere of 5 vol%, particularly 0.0001 vol% to 1 vol%, from the viewpoint of preventing hue deterioration.

In order to obtain the polycarbonate resin used in the present invention, the carbonic acid diester represented by the general formula (4) is 0.90 to the total dihydroxy compound (including the dihydroxy compound used in the present invention) used in the reaction. The molar ratio is preferably 1.20, more preferably 0.95 to 1.10.
When this molar ratio is reduced, the amount of terminal hydroxyl groups of the produced resin increases, the thermal stability of the polymer deteriorates, coloring occurs during molding, the rate of transesterification reaction decreases, the desired high molecular weight The body may not be obtained.

Moreover, when this molar ratio becomes large, the rate of the transesterification reaction may decrease or it may be difficult to produce a resin having a desired molecular weight. The decrease in the transesterification reaction rate may increase the thermal history during the polymerization reaction, and may deteriorate the hue and light resistance of the resulting resin.
Furthermore, when the molar ratio of the carbonic acid diester represented by the general formula (4) is increased with respect to all the dihydroxy compounds including the dihydroxy compound used in the present invention, the amount of residual carbonic acid diester in the resulting resin increases. These may be unfavorable because they may absorb ultraviolet rays and deteriorate the light resistance of the resin. The concentration of the carbonic acid diester represented by the general formula (4) remaining in the resin used in the present invention is preferably 60 ppm by weight or less, more preferably 50 ppm by weight or less, and particularly preferably 40 ppm by weight or less. . In reality, the resin may contain unreacted carbonic acid diester, and the lower limit of the concentration is usually 1 ppm by weight.

In the present invention, the method of polycondensing a dihydroxy compound and a carbonic acid diester is usually carried out in multiple stages using a plurality of reactors in the presence of the above-mentioned catalyst. The type of reaction may be any of batch type, continuous type, or a combination of batch type and continuous type.
In the initial stage of polymerization, it is preferable to obtain a prepolymer at a relatively low temperature and low vacuum, and in the latter stage of polymerization, it is preferable to increase the molecular weight to a predetermined value at a relatively high temperature and high vacuum, but the jacket temperature at each molecular weight stage. Appropriate selection of the internal temperature and pressure in the reaction system is important from the viewpoints of hue and light resistance. For example, if either the temperature or the pressure is changed too quickly before the polymerization reaction reaches a predetermined value, the unreacted monomer will be distilled, causing the molar ratio of the dihydroxy compound and the carbonic acid diester to change, resulting in a decrease in the polymerization rate. Or a polymer having a predetermined molecular weight or terminal group cannot be obtained, and as a result, the object of the present invention may not be achieved.

  Furthermore, it is effective to use a reflux condenser for the polymerization reactor in order to suppress the amount of the monomer to be distilled off, and the effect is particularly great in a reactor at the initial stage of polymerization where there are many unreacted monomer components. The temperature of the refrigerant introduced into the reflux condenser can be appropriately selected according to the monomer used, but the temperature of the refrigerant introduced into the reflux condenser is usually 45 to 180 ° C. at the inlet of the reflux condenser. Yes, preferably 80 to 150 ° C, particularly preferably 100 to 130 ° C. If the temperature of the refrigerant is too high, the amount of reflux decreases and the effect is reduced. On the other hand, if the temperature is too low, the distillation efficiency of the monohydroxy compound that should be distilled off tends to decrease. As the refrigerant, hot water, steam, heat medium oil or the like is used, and steam or heat medium oil is preferable.

In order to maintain the polymerization rate appropriately and suppress the distillation of the monomer, while keeping the hue, thermal stability, light resistance, etc. of the finally obtained polycarbonate resin, The selection of the quantity is important.
The resin used in the present invention is preferably produced by polymerizing in a plurality of stages using a plurality of reactors using a catalyst, but the reason for carrying out the polymerization in a plurality of reactors is that at the initial stage of the polymerization reaction, Since there are many monomers contained in the reaction solution, it is important to suppress the volatilization of the monomers while maintaining the necessary polymerization rate. In the late stage of the polymerization reaction, in order to shift the equilibrium to the polymerization side, This is because it is important to sufficiently distill off the produced monohydroxy compound. Thus, in order to set different polymerization reaction conditions, it is preferable from the viewpoint of production efficiency to use a plurality of polymerization reactors arranged in series.

The reactor used in the production of the polycarbonate resin used in the present invention may be at least two or more as described above, but from the viewpoint of production efficiency, three or more, preferably 3 to 5, particularly preferably. Are four groups.
If there are two or more reactors, a plurality of reaction stages with different conditions may be set in the reactor, or the temperature and pressure may be continuously changed.

The polymerization catalyst can be added to the raw material preparation tank, the raw material storage tank, or directly to the polymerization tank. From the viewpoint of supply stability and control of the polymerization reaction, the raw material line supplied to the polymerization tank is used. It is preferable to install and supply a catalyst supply line in the middle. The state of the polymerization catalyst to be supplied includes a solid and a liquid. From the viewpoint of quantitative supply, a liquid is preferable.
If the temperature of the polymerization reaction is too low, the productivity decreases due to a decrease in the reaction rate or the reaction time, and if it is too high, not only the evaporation of the monomer is caused but also the decomposition and coloring of the resin may be promoted. .

  Specifically, the reaction in the first stage is performed at 140 to 270 ° C., preferably 180 to 240 ° C., more preferably 200 to 230 ° C. as the maximum internal temperature of the polymerization reactor. The monohydroxy compound generated is removed from the reaction system at a pressure of 1 kPa, preferably 70 kPa to 5 kPa, more preferably 30 kPa to 10 kPa (absolute pressure) for 0.1 hours to 10 hours, preferably 0.5 hours to 3 hours. Carried out while distilling.

  In the second and subsequent stages, the pressure in the reaction system is gradually reduced from the pressure in the first stage, and the monohydroxy compound that is subsequently generated is removed from the reaction system. 200 Pa or less, maximum internal temperature of 210 ° C. to 270 ° C., preferably 220 ° C. to 250 ° C., usually 0.1 hour to 10 hours, preferably 1 hour to 6 hours, particularly preferably 0.5 hour. Perform for ~ 3 hours.

In particular, in order to suppress resin coloring and thermal deterioration and obtain a resin having good hue and light resistance, the maximum internal temperature in all reaction stages is preferably less than 250 ° C., particularly 225 ° C. to 245 ° C.
In order to suppress the decrease in the polymerization rate in the latter half of the polymerization reaction and minimize degradation due to thermal history, it is necessary to use a horizontal reactor with excellent plug flow and interface renewability at the final stage of polymerization. preferable.

If the polymerization temperature is increased and the polymerization time is excessively long in order to obtain a resin having a predetermined molecular weight, the ultraviolet transmittance of the obtained resin decreases and the yellow index (YI) value tends to increase.
The monohydroxy compound produced as a by-product is preferably reused as a raw material for diphenyl carbonate, bisphenol A, etc. after purification as necessary from the viewpoint of effective utilization of resources.
The polycarbonate resin obtained as described above is usually cooled and solidified after polycondensation and pelletized with a rotary cutter or the like.

  The method of pelletization is not limited, but it is extracted from the final polymerization reactor in a molten state, cooled and solidified in the form of a strand, and pelletized, or from the final polymerization reactor in a molten state, uniaxial or biaxial extrusion. The resin is supplied to the machine, melt-extruded, cooled and solidified into pellets, or extracted from the final polymerization reactor in a molten state, cooled and solidified in the form of strands, once pelletized, and then uniaxially again Alternatively, a method may be mentioned in which resin is supplied to a biaxial extruder, melt-extruded, cooled and solidified, and pelletized.

At that time, in the extruder, the residual monomer under reduced pressure devolatilization, and generally known heat stabilizers, neutralizers, UV absorbers, mold release agents, colorants, antistatic agents, lubricants, lubricants, A plasticizer, a compatibilizer, a flame retardant, etc. can be added and kneaded.
The melt kneading temperature in the extruder depends on the glass transition temperature and molecular weight of the resin, but is usually 150 ° C to 300 ° C, preferably 200 ° C to 270 ° C, and more preferably 230 ° C to 260 ° C. When the melt kneading temperature is lower than 150 ° C., the melt viscosity of the resin is high, the load on the extruder is increased, and the productivity is lowered. When the temperature is higher than 300 ° C., the resin is severely thermally deteriorated, resulting in a decrease in mechanical strength due to a decrease in molecular weight, coloring, and gas generation.

  When producing the polycarbonate resin used in the present invention, it is desirable to install a filter in the extruder in order to prevent foreign substances from entering. The filter installation position is preferably on the downstream side of the extruder, and the foreign matter removal size (opening) of the filter is preferably 100 μm or less as the filtration accuracy for 99% removal. In particular, in the case of disagreeing with the entry of minute foreign matters for film use etc., it is preferably 40 μm or less, more preferably 10 μm or less.

Extrusion of the resin used in the present invention is preferably carried out in a clean room having a higher degree of cleanliness than Class 6 as defined in JIS B 9920 (2002), and more preferably in a clean room in order to prevent foreign matter from being mixed after extrusion. It is desirable.
Further, when cooling the extruded resin into chips, it is preferable to use a cooling method such as air cooling or water cooling. As the air used for air cooling, it is desirable to use air from which foreign substances in the air have been removed in advance with a hepa filter or the like to prevent reattachment of foreign substances in the air. When water cooling is used, it is desirable to use water from which metal in water has been removed with an ion exchange resin or the like, and foreign matter in water has been removed with a filter. The opening of the filter to be used is preferably 10 μm to 0.45 μm as 99% removal filtration accuracy.

The molecular weight of the resin used in the present invention thus obtained can be represented by a reduced viscosity, and the lower limit of the reduced viscosity is 0.10 dL / g or more, preferably 0.20 dL / g or more, and More preferably, it is 30 dL / g or more. The upper limit of the reduced viscosity is more preferably 0.45 dL / g or less and 0.40 dL / g or less.
If the reduced viscosity of the resin is too low, the mechanical strength of the molded product may be small, and if it is too large, the fluidity at the time of molding tends to decrease, and the productivity and moldability tend to decrease.

The reduced viscosity is measured using a Ubbelohde viscometer at a temperature of 20.0 ° C. ± 0.1 ° C., using methylene chloride as a solvent and precisely preparing a resin concentration of 0.6 g / dL.
Furthermore, the lower limit of the concentration of the terminal group represented by the following general formula (5) (referred to as “terminal phenyl group concentration”) of the resin used in the present invention is preferably 20 μeq / g, more preferably 40 μeq / g, particularly preferably Is 50 μeq / g, while the upper limit is preferably 160 μeq / g, more preferably 140 μeq / g, particularly preferably 100 μeq / g.

If the concentration of the terminal group represented by the following general formula (5) is too high, even if the hue at the time of polymerization or at the time of molding is good, the hue after UV exposure may be deteriorated. Thermal stability may be reduced.
In order to control the concentration of the terminal group represented by the following general formula (5), the molar ratio of the dihydroxy compound containing the dihydroxy compound used in the present invention as the raw material and the carbonic acid diester represented by the general formula (4) is set. In addition to controlling, a method for controlling the kind and amount of the catalyst at the time of the transesterification reaction, the polymerization pressure and the polymerization temperature can be used.

  When using the substituted diphenyl carbonate such as diphenyl carbonate and ditolyl carbonate as the carbonic acid diester represented by the general formula (4) to produce the resin used in the present invention, phenol and substituted phenol are by-produced in the resin. Although it cannot be avoided, phenol and substituted phenols also have an aromatic ring, which absorbs ultraviolet rays and may cause deterioration of light resistance, and may also cause odor during molding. . The resin contains an aromatic monohydroxy compound having an aromatic ring such as by-product phenol of 1000 ppm by weight or more after a normal batch reaction, but from the viewpoint of light resistance and odor reduction, it is devolatilized. It is preferably 700 ppm by weight or less, more preferably 500 ppm by weight or less, and particularly preferably 300 ppm by weight or less using a horizontal reactor having excellent performance or an extruder with a vacuum vent. However, it is difficult to remove completely industrially, and the lower limit of the content of the aromatic monohydroxy compound is usually 1 ppm by weight.

These aromatic monohydroxy compounds may have a substituent depending on the raw material used, and may have, for example, an alkyl group having 5 or less carbon atoms.
When the equivalent number of hydrogen atoms (H) bonded to the aromatic ring of the resin used in the present invention is (A) and the equivalent number of hydrogen atoms (H) bonded to other than the aromatic ring is (B), the aromatic ring The ratio of the number of equivalents of hydrogen atoms (H) bonded to the number of equivalents of all hydrogen atoms (H) is represented by A / (A + B), but the light resistance has an ultraviolet absorbing ability as described above. Since the aromatic ring may influence, the value of A / (A + B) is preferably 0.05 or less, more preferably 0.03 or less, particularly preferably 0.02 or less, suitably 0.01 or less. A / (A + B) can be quantified by ¹ H-NMR.

[Other additives]
As described above, the polycarbonate resin used in the present invention is generally used as a polycarbonate resin composition by adding other additives to the extent that the gist of the present invention is not impaired.
Examples of such additives include antioxidants, acidic compounds, ultraviolet absorbers, light stabilizers, inorganic fillers, and the like.
The antioxidant is preferably at least one selected from the group consisting of phenolic antioxidants, phosphite antioxidants and sulfur antioxidants, and phenolic antioxidants and / or phosphites. More preferred are system antioxidants.

  Examples of the phenolic antioxidant include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), glycerol-3-stearylthiopropionate, triethylene glycol-bis [ 3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] , Pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1 , 3,5-trimethyl-2 4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 4,4′-biphenylenediphosphinic acid tetrakis ( 2,4-di-tert-butylphenyl), 3,9-bis {1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} And compounds such as -2,4,8,10-tetraoxaspiro (5,5) undecane.

  Among these compounds, an aromatic monohydroxy compound substituted with one or more alkyl groups having 5 or more carbon atoms is preferable. Specifically, octadecyl-3- (3,5-di-tert-butyl-4- Hydroxyphenyl) propionate, pentaerythrityl-tetrakis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate}, 1,6-hexanediol-bis [3- (3,5-di- tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene and the like, preferably pentaerythris Lithyl-tetrakis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate} is more preferred.

  Examples of the phosphite antioxidant include triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) 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, bis (2,6-di-) tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaeri Li diphosphite, bis (2,4-di -tert- butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, and the like.

  Among these, trisnonylphenyl phosphite, trimethyl phosphate, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis ( 2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is preferred, and tris (2,4-di-tert-butylphenyl) phosphite is more preferred.

  Examples of the sulfur-based antioxidant include dilauryl-3,3′-thiodipropionate, ditridecyl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, diester Stearyl-3,3′-thiodipropionate, laurylstearyl-3,3′-thiodipropionate, pentaerythritol tetrakis (3-laurylthiopropionate), bis [2-methyl-4- (3 -Laurylthiopropionyloxy) -5-tert-butylphenyl] sulfide, octadecyl disulfide, mercaptobenzimidazole, 2-mercapto-6-methylbenzimidazole, 1,1′-thiobis (2-naphthol) and the like. Among the above, pentaerythritol tetrakis (3-lauryl thiopropionate) is preferable.

  The content of the antioxidant is preferably 0.001 parts by weight or more, more preferably 0.01 parts by weight or more, particularly preferably 0.05 parts by weight or more, on the other hand, preferably 100 parts by weight of the polycarbonate resin. 1 part by weight or less, more preferably 0.7 part by weight or less, particularly preferably 0.5 part by weight or less. If the content of the antioxidant is excessively small, the coloring suppression effect during molding may be insufficient. Also, if the content of the antioxidant is excessively large, the amount of deposits on the mold during injection molding increases or the number of deposits on the roll increases when forming a film by extrusion. The surface appearance of the product may be damaged.

  Examples of acidic compounds include hydrochloric acid, nitric acid, boric acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, adipic acid, ascorbic acid, aspartic acid, azelaic acid, adenosine phosphoric acid, benzoic acid Acid, formic acid, valeric acid, citric acid, glycolic acid, glutamic acid, glutaric acid, cinnamic acid, succinic acid, acetic acid, tartaric acid, oxalic acid, p-toluenesulfinic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, nicotinic acid , Bronsted acids such as picric acid, picolinic acid, phthalic acid, terephthalic acid, propionic acid, benzenesulfinic acid, benzenesulfonic acid, malonic acid, maleic acid, and esters thereof.

Among these acidic compounds or derivatives thereof, sulfonic acids or esters thereof are preferable, and p-toluenesulfonic acid, methyl p-toluenesulfonate, and butyl p-toluenesulfonate are particularly preferable.
These acidic compounds can be added in the production process of the resin composition as compounds that neutralize the basic transesterification catalyst used in the above-described resin polycondensation reaction.

  The compounding amount of the acidic compound is 0.00001 part by weight or more and 0.1 part by weight or less, preferably 0.0001 part by weight or more and 0.01 part by weight or less, based on 100 parts by weight of the resin. Preferably they are 0.0002 weight part or more and 0.001 weight part or less. If the blending amount of the acidic compound is excessively small, it may not be possible to sufficiently suppress coloring when the residence time of the resin composition in the injection molding machine becomes long during injection molding. Moreover, when there are too many compounding quantities of an acidic compound, the hydrolysis resistance of a resin composition may fall remarkably.

  The content in the case of using an ultraviolet absorber or a light stabilizer is preferably 0.01 to 2 parts by weight with respect to 100 parts by weight of the resin.

  Examples of the inorganic filler include glass fiber, glass milled fiber, glass flake, glass bead, carbon fiber, silica, alumina, titanium oxide, calcium sulfate powder, gypsum, gypsum whisker, barium sulfate, talc, mica, and wallast. Calcium silicate such as knight; carbon black, graphite, iron powder, copper powder, molybdenum disulfide, silicon carbide, silicon carbide fiber, silicon nitride, silicon nitride fiber, brass fiber, stainless steel fiber, potassium titanate fiber, whisker, etc. It is done. Among these, glass fiber filler, glass powder filler, glass flake filler; carbon fiber filler, carbon powder filler, carbon flake filler; various whiskers, mica Talc is preferred. More preferably, glass fiber, glass flake, glass milled fiber, carbon fiber, wollastonite, mica and talc are mentioned.

The compounding amount of the inorganic filler is usually 1 part by weight or more and 100 parts by weight or less, preferably 3 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the resin. When the blending amount of the inorganic filler is excessively small, the reinforcing effect is small, and when it is excessively large, the appearance tends to deteriorate.
The resin composition used in the present invention includes, for example, aromatic polycarbonate, aromatic polyester, aliphatic polyester, polyamide, polystyrene, polyolefin, acrylic, amorphous polyolefin, ABS, AS and other synthetic resins, polylactic acid, polybutylene succin It can also be used as a polymer alloy by kneading with one or more of biodegradable resins such as nate and rubber.

In order to produce the above resin composition, the above components are mixed simultaneously or in any order with a mixer such as a tumbler, V-type blender, nauter mixer, Banbury mixer, kneading roll, extruder, etc. be able to. Furthermore, a nucleating agent, a flame retardant, an inorganic filler, an impact modifier, a foaming agent, a dye / pigment and the like that are usually used in the resin composition may be contained within a range not impairing the object of the present invention.
The resin composition preferably contains at least one metal compound selected from the group consisting of a lithium compound and a metal of Group 2 of the long-period periodic table, and the content of the metal compound is the amount of metal. Is preferably 0.1 ppm by weight or more, more preferably 0.5 ppm by weight or more, and particularly preferably 0.7 ppm by weight or more. Further, the upper limit is preferably 20 ppm by weight, more preferably 10 ppm by weight, particularly preferably 3 ppm by weight, most preferably 1.5 ppm by weight, and most preferably 1.0 ppm by weight.

[Resin molded product]
<Physical properties / characteristics>
The resin molded product of the present invention can be obtained by molding the resin composition used in the present invention according to a conventional method, and a preferred molding method is an injection molding method.

  The molded product of the present invention can be used for liquid crystal display devices such as televisions, computer monitors, various touch panels, flat panel displays, and tablet personal computers. In such applications, planar members are used. Often used as In this case, the plate-like portion in the present invention can be used as the entire surface of the molded product. The molded product of the present invention can also be used as a front plate of a liquid crystal display device such as a television, a computer monitor, various touch panels, a flat panel display, and a tablet personal computer. In particular, the molded product of the present invention is suitable for a flat panel display and a front panel of a tablet personal computer because of its excellent thin moldability, impact resistance, surface hardness, wet heat resistance, and low optical distortion.

  Further, for example, in a molded product in which such a flat plate and a frame (bezel) are combined, or a molded product in which the housing and the flat plate are integrally formed by two-color molding or the like, the plate-like portion The term “planar part” excluding the frame and the case, that is, the part of the flat plate of the molded product that is not covered by the frame or the like.

  Further, for example, when used in a liquid crystal display device such as a television, a computer monitor, and various touch panels, it may be used as a curved curved member instead of a flat surface from the viewpoint of visibility and design. In this case, the upper part of the plate in the present invention shows a curved curved part.

<Manufacturing method>
The molded article of the present invention can be produced by various methods.
In general, the extrusion molding method is generally used in the production of resin molded products, but the shape of the obtained molded product is limited, and it may be difficult to produce a molded product having a complicated shape.

  The production of the molded article of the present invention is preferably performed by an injection molding method. In particular, it is preferably performed by injection press molding from the viewpoint of reducing the optical distortion of the molded product. In the case of injection molding, a resin molded product having a complicated shape can be manufactured by using a mold corresponding to the shape of the molded product. Injection molding is performed by an injection molding machine, and suitable molding conditions are appropriately set according to the resin composition to be used and the product shape. The molding conditions include cylinder temperature, mold temperature, injection pressure, holding pressure, screw rotation speed, cushion amount, injection speed, injection time, pressure holding time, cooling time, and the like.

  In the production of the molded article of the present invention by the injection molding method, the cylinder temperature is preferably 200 ° C. to 300 ° C., more preferably 210 ° C. to 280 ° C., particularly preferably 220 ° C. to 270 ° C., most preferably 230 ° C. to 260 ° C. If the cylinder temperature is too high, the resin composition tends to thermally decompose and the resin molded product tends to be colored. On the other hand, if the cylinder temperature is too low, the melt viscosity of the resin composition increases, resulting in molding defects and increased optical distortion. It tends to be.

  The mold temperature is preferably 40 ° C to 120 ° C, more preferably 50 ° C to 100 ° C, and particularly preferably 60 ° C to 80 ° C. If the mold temperature is too high, the productivity of the molded product tends to decrease, while if too low, the optical distortion tends to increase.

  As a means for obtaining the molded product of the present invention, as described above, the ratio of the structural unit (a) derived from the dihydroxy compound to the total dihydroxy compound is within a specific range, and the cylinder temperature and the mold temperature are set as described above. It is mentioned to be a specific range. The molded article of the present invention can be produced by combining these means alone or in an appropriate combination.

  By the above manufacturing method, the molded product of the present invention is molded as a molded product having a thickness of 0.1 mm to 1 mm. When the thickness is within this range, it can be easily used as a molded product having a thickness suitable for optical applications. The thickness of the molded product is preferably 0.2 mm or more and 0.9 mm or less, more preferably 0.3 mm or more and 0.8 mm or less. If the thickness of the molded product is too thin, the moldability may deteriorate, the impact resistance may decrease, or the optical distortion may increase. On the other hand, when the thickness of the molded product is too thick, the molded product becomes heavy, and the transparency of the molded product may be lowered.

  The molded article of the present invention is preferably hard-coated on at least one side. By performing the hard coat treatment and providing the hard coat treatment layer on the molded product, the surface hardness can be particularly improved, and the durability is improved from the point of being hardly damaged. The hard coating agent may be a conventionally known one and is not particularly limited. For example, acryl-based, polyester-based, urethane-based, rubber-based, silicone-based, vinyl-based compositions and the like can be mentioned. The composition may be a mixture of two or more of the composition groups. Further, it may be an energy ray curable composition or a thermosetting composition. Moreover, the particle | grains of an organic compound and an inorganic compound may be included. The hard coat treatment method may be a conventionally known one and is not particularly limited. Examples of the method for applying the hard coat layer coating liquid include a line coating method and a wet coating method, and the wet coating method is preferable from the viewpoint of productivity or cost. The wet coating method may be a known one, such as a roll coating method, a spin coating method, or a dip coating method. The coating liquid for hard coat layer is cured by irradiating active energy rays such as ultraviolet rays after coating. Moreover, in order to further improve the adhesion between the transparent substrate and the hard coat layer, a pretreatment such as corona discharge can be applied to the surface of the transparent substrate as necessary. In particular, it is effective to provide a hard coat treatment layer when used in applications where scratch resistance is required, such as flat panel displays and tablet personal computers.

  The molded product of the present invention preferably has an in-mold decorative film laminated on at least one surface thereof. By providing the in-mold decorative film layer, there are excellent effects such as improving the appearance of the molded product and improving the scratch resistance. Lamination | stacking of the decoration film in a metal mold | die can be performed by a conventionally well-known film insert molding. In particular, from the viewpoint of scratch resistance, it is preferable to perform a hard coat treatment.

  ADVANTAGE OF THE INVENTION According to this invention, the molded article shape | molded using the polycarbonate resin composition which is excellent in thin moldability, impact resistance, surface hardness, and moist heat resistance, and has low optical distortion can be provided. This molded product can be used for many purposes as described above, and is particularly suitable for optical applications.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by a following example, unless the summary is exceeded.
In the following, the physical properties and characteristics of polycarbonate resins, polycarbonate resin compositions, and molded articles were evaluated by the following methods.

(1) Measurement of reduced viscosity A sample of a polycarbonate resin composition was dissolved using methylene chloride as a solvent to prepare a polycarbonate solution having a concentration of 0.6 g / dL. Measured at a temperature of 20.0 ° C. ± 0.1 ° C. using an Ubbelohde viscometer manufactured by Moriyu Rika Kogyo Co., Ltd., and the relative viscosity ηrel is obtained from the following equation from the solvent passage time t ₀ and the solution passage time t. From the relative viscosity, the specific viscosity ηsp was determined from the following formula.
ηrel = t / t ₀
ηsp = (η−η ₀ ) / η ₀ = ηrel−1

  The reduced viscosity ηsp / c was determined by dividing the specific viscosity by the concentration c (g / dL). The higher this value, the higher the molecular weight.

(2) Measurement of the structural unit ratio derived from each dihydroxy compound in the polycarbonate resin composition The structural unit ratio derived from each dihydroxy compound in the polycarbonate resin composition was obtained by weighing 30 mg of the polycarbonate resin composition, It was dissolved in 0.7 mL, and the solution, which was placed in a NMR tube having an inner diameter of 5 mm, was analyzed by ¹ H NMR spectrum at room temperature using a Nippon Denshi JNM-AL400 (resonance frequency 400 MHz). The structural unit ratio derived from each dihydroxy compound was determined from the signal intensity ratio based on the structural unit derived from each dihydroxy compound.

(3) Evaluation of formability (thickness 1 mm) An injection molding machine with a clamping force of 200 tons made by Meiki Seisakusho Co., Ltd. has a width of 100 mm, a length of 100 mm, a wall thickness of 1.0 mm, a gate width of 40 mm, A mold having a fan gate gate with a gate thickness of 0.8 mm is mounted, mold temperature is 80 ° C., injection pressure is 180 to 250 MPa, holding pressure is 60 to 80 MPa, holding pressure is 2 seconds, cooling time is 30 seconds. The plate was formed with. The cylinder temperature was set according to the properties of the resin to be molded. The moldability of the resin that could be molded under the above molding conditions was rated as ◯, and the moldability of the resin that was short shot, that is, the mold could not be filled, was rated as x.

(4) Evaluation of formability (thickness 0.7 mm) An injection molding machine with a clamping force of 200 tons manufactured by Meiki Seisakusho Co., Ltd. has a width of 100 mm, a length of 100 mm, a wall thickness of 0.7 mm, and a gate width. A mold having a fan gate of 40 mm and a gate thickness of 0.5 mm is mounted, mold temperature is 80 ° C., injection pressure is 200 to 250 MPa, holding pressure is 60 to 80 MPa, holding pressure is 2 seconds, and cooling time is 30. Plates were molded in seconds. The cylinder temperature was set according to the properties of the resin to be molded. The moldability of the resin that could be molded under the above molding conditions was rated as ◯, and the moldability of the resin that became a short shot, that is, the mold could not be filled, was rated as x.

(5) Impact resistance Metal plate having a longitudinal width of 200 mm, a lateral width of 200 mm, and a thickness of 10 mm provided with a through hole of 60 mmΦ at the center of the resin plate obtained in the above (4) evaluation of formability (thickness 0.7 mm). Placed on the plate. At this time, the center of the plate was set on the center of the through hole. Next, a metal plate having a longitudinal width of 200 mm, a lateral width of 200 mm, and a thickness of 10 mm, which was similarly provided with a through hole of 60 mmΦ at the center, was overlaid thereon. Each of the two metal plates is provided with bolt holes for positioning and fixing at the four corners. The resin plate was fixed by passing a bolt through this bolt hole and tightening with the nut on the opposite side. Next, an iron ball having a weight of 150 g was dropped from a predetermined height at the center of the resin plate to evaluate the impact resistance. The falling ball test from a predetermined height was performed five times for one resin while the resin plate was replaced with an unused one each time. In addition, the test was performed so that the iron ball bounced after hitting the resin plate would not hit again.

In the above test, the impact resistance of the resin that did not break even after a 50cm height drop ball test was evaluated as ○, and the 50cm height drop ball test failed, but the 30cm height drop ball test failed once. The impact resistance of the resin that did not occur was Δ, and the impact resistance of the resin that failed in the falling ball test with a height of 30 cm was ×.
On the other hand, the impact resistance was not evaluated for the resin in which the resin plate was not obtained due to the short shot in the evaluation of the moldability (4) (thickness 0.7 mm).

(6) Pencil Hardness Pencil hardness was measured at a load of 750 g, a measurement speed of 30 mm / min, and a measurement distance of 7 mm in accordance with JIS-K5600 using a test piece having a thickness of 3 mm. The pencil hardness is preferably F or higher, and more preferably H or higher. When the pencil hardness is HB or less, the obtained molded product is likely to be damaged and the appearance may be easily damaged. The pencil hardness is expressed in the order of 4H, 3H, 2H, H, F, HB, B, 2B, 3B, and 4B from the hardest. The surface hardness was evaluated by measuring the pencil hardness of the molded products according to the examples and comparative examples.

(7) Moisture and heat resistance After leaving the resin plate obtained in the above (4) moldability evaluation (thickness 0.7 mm) in a constant temperature and humidity apparatus adjusted to a temperature of 80 ° C. and a humidity of 90% for 300 hours. The product was taken out and checked for changes in shape. In addition, the resin plate was installed in the sample shelf which consists of a net-like metal in a constant temperature and humidity apparatus.
The moisture and heat resistance of the resin that does not change its shape is ○, and the resin plate that has undergone a deformation that the end of the resin plate floats up to 1 mm or more and less than 5 mm when the resin plate after the wet heat test is installed horizontally on a flat surface Δ, when the resin plate after the wet heat test was placed horizontally on a flat surface, the end of the resin plate was lifted by 5 mm or more, or the resin plate was deformed and the original shape was not retained, and x . On the other hand, with respect to the resin that could not be obtained as a short shot in the above (4) moldability evaluation (thickness 0.7 mm), the resin plate obtained in the above (3) moldability evaluation (thickness 1.0 mm) Was used to evaluate the heat and moisture resistance.

(8) Optical distortion The resin plate obtained in the above (4) evaluation of moldability (thickness 0.7 mm) is sandwiched between two polarizers that are in a crossed Nicol state, and on the observation table from behind. The color unevenness that appears under the condition of being irradiated with white light was observed. The optical distortion of the resin where color unevenness is seen only in the vicinity of the gate is ○, the optical distortion of the resin is found even when the color unevenness is 25 mm or more away from the gate, and even when the color unevenness is 50 mm or more away from the gate The optical distortion of the resin that was seen was marked with x. On the other hand, with respect to the resin that could not be obtained as a short shot in the above (4) moldability evaluation (thickness 0.7 mm), the resin plate obtained in the above (3) moldability evaluation (thickness 1.0 mm) Was used to evaluate the heat and moisture resistance.

The abbreviations of the compounds used in the description of the following examples are as follows.
(Dihydroxy compound)
・ ISB: Isosorbide (Rocket Fleure, trade name: POLYSORB)
CHDM: 1,4-cyclohexanedimethanol (manufactured by Shin Nippon Rika Co., Ltd., trade name: SKY CHDM)
TCDDM: TCDDM: Tricyclodecane dimethanol (carbonic acid diester)
・ DPC: Diphenyl carbonate (Mitsubishi Chemical Corporation)
(Heat stabilizer)
AS2112: Compound name, tris (2,4-di-t-butylphenyl) phosphite (manufactured by ADEKA)
(Antioxidant)
IRGANOX 1010: Compound name, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (manufactured by BASF Japan Ltd.)
(Release agent)
E-275: Compound name, ethylene glycol distearate (manufactured by NOF Corporation)
(Bisphenol A polycarbonate: BPA PC)
NOVAREX 7022R: aromatic polycarbonate resin having a structure derived only from 2,2-bis- (4-hydroxyphenyl) propane, viscosity average molecular weight 22,000 (manufactured by Mitsubishi Engineering Plastics)
(PMMA)
・ Acrypet VH: Polymethyl methacrylate resin (Mitsubishi Rayon Co., Ltd.)

[Example 1]
In a polymerization reactor equipped with a stirring blade and a reflux condenser controlled at 100 ° C., ISB and CHDM, DPC and calcium acetate monohydrate having a chloride ion concentration of 10 ppb or less by purification by distillation, in a molar ratio. ISB / CHDM / DPC / calcium acetate monohydrate = 0.70 / 0.30 / 1.00 / 1.3 × 10 ⁻⁶ , and sufficiently purged with nitrogen (oxygen concentration 0.0005 vol% -0.001 vol%). Subsequently, heating was performed with a heating medium, and stirring was started when the internal temperature reached 100 ° C., and the contents were melted and made uniform while controlling the internal temperature to be 100 ° C. After that, temperature increase was started, the internal temperature was adjusted to 210 ° C. in 40 minutes, and when the internal temperature reached 210 ° C., control was performed so as to maintain this temperature, and at the same time, pressure reduction was started and the temperature reached 210 ° C. After 90 minutes, the pressure was changed to 13.3 kPa (absolute pressure, the same applies hereinafter), and the pressure was maintained for another 60 minutes. The phenol vapor produced as a by-product with the polymerization reaction is led to a reflux condenser using a steam controlled at 100 ° C. as the inlet temperature to the reflux condenser, and a monomer component contained in the phenol vapor in a slight amount is introduced into the polymerization reactor. Then, the phenol vapor that did not condense was recovered by guiding it to a condenser using 45 ° C. warm water as a refrigerant.

  The content thus oligomerized is once restored to atmospheric pressure, and then transferred to another polymerization reaction apparatus equipped with a stirring blade and a reflux condenser controlled in the same manner as described above. The internal temperature was set to 220 ° C. and the pressure was set to 200 Pa in 60 minutes. Thereafter, the internal temperature was set at 228 ° C. and the pressure at 133 Pa or less over 20 minutes, and when the predetermined stirring power was reached, the pressure was restored, and a molten polycarbonate resin was obtained from the outlet of the polymerization reactor.

  Further, the melted polycarbonate resin was continuously supplied to a twin-screw extruder provided with 3 vents and water injection equipment, and “Irganox 1010” and “AS2112” were used as antioxidants so as to have the compositions shown in Table 1. In addition to continuously adding “E-275” as a mold release agent at a predetermined ratio, low-molecular weight substances such as phenol are devolatilized under reduced pressure at each vent section provided in the twin-screw extruder, and then a pelletizer is used. Pelletization was performed to obtain polycarbonate resin composition pellets.

  Table 1 shows various evaluation results of the obtained resin composition.

[Example 2]
In Example 1, except that the charge composition was changed to ISB / CHDM / DPC / calcium acetate monohydrate = 0.80 / 0.20 / 1.00 / 1.3 × 10 ⁻⁶ In the same manner as in Example 1, pellets of a carbonate copolymer resin composition were obtained. Table 1 shows various evaluation results of the obtained resin composition.

[Example 3]
In Example 1, except that the charged composition was changed so that ISB / CHDM / DPC / calcium acetate monohydrate = 0.90 / 0.10 / 1.00 / 1.3 × 10 ⁻⁶ In the same manner as in Example 1, pellets of a carbonate copolymer resin composition were obtained. Table 1 shows various evaluation results of the obtained resin composition.

[Example 4]
In Example 1, except that the charged composition was changed to ISB / TCDDM / DPC / calcium acetate monohydrate = 0.70 / 0.30 / 1.00 / 1.3 × 10 ⁻⁶ In the same manner as in Example 1, pellets of a carbonate copolymer resin composition were obtained. Table 1 shows various evaluation results of the obtained resin composition.

[Example 5]
In Example 1, except that the charged composition was changed so that ISB / TCDDM / DPC / calcium acetate monohydrate = 0.80 / 0.20 / 1.00 / 1.3 × 10 ⁻⁶ In the same manner as in Example 1, pellets of a carbonate copolymer resin composition were obtained. Table 1 shows various evaluation results of the obtained resin composition.

[Comparative Example 1]
In Example 1, carbonate was changed in the same manner as in Example 1 except that the charged composition was changed to ISB / DPC / calcium acetate monohydrate = 0.10 / 1.00 / 1.3 × 10 ^−6. Polymer resin composition pellets were obtained. Table 1 shows various evaluation results of the obtained resin composition.

[Comparative Example 2]
In Example 1, except that the charged composition was changed to ISB / CHDM / DPC / calcium acetate monohydrate = 0.50 / 0.50 / 1.00 / 1.3 × 10 ⁻⁶ In the same manner as in Example 1, pellets of a carbonate copolymer resin composition were obtained. Table 1 shows various evaluation results of the obtained resin composition.

[Comparative Example 3]
In Example 1, the pellets of the carbonate copolymer resin composition were the same as in Example 1 except that the predetermined stirring power when returning to atmospheric pressure was changed and the reduced viscosity was 0.47 dL / g. Got. Table 1 shows various evaluation results of the obtained resin composition.

[Comparative Example 4]
In Example 2, the pellets of the carbonate copolymer resin composition were the same as in Example 1 except that the predetermined stirring power when returning to atmospheric pressure was changed and the reduced viscosity was 0.46 dL / g. Got. Table 1 shows various evaluation results of the obtained resin composition.

[Comparative Example 5]
Table 1 shows various evaluation results of commercially available bisphenol A polycarbonate, NOVAREX 7022R (manufactured by Mitsubishi Engineering Plastics Co., Ltd.).

[Comparative Example 6]
Table 1 shows various evaluation results of commercially available PMMA and Acrypet VH (manufactured by Mitsubishi Rayon Co., Ltd.).

  The molded products of the inventions shown in Examples 1 to 5 were superior to the molded products shown in the comparative examples when the evaluation items such as moldability, impact resistance, surface hardness, moist heat resistance, and optical distortion were combined. Among them, Examples 2 to 5 were particularly excellent in wet heat resistance, and Examples 1, 2, 4, and 5 were particularly excellent in impact resistance.

  On the other hand, Comparative Example 1 was a molded product having a structure derived only from the structural unit (a), and was very brittle and insufficient in impact resistance. In Comparative Example 2, the proportion of the structural unit (a) is 50%, the surface hardness is insufficient (HB), and the heat and humidity resistance is insufficient.

  In Comparative Example 3, the proportion of the structural unit (a) is 70 mol%, but the reduced viscosity is 0.47 dL / g. If the reduced viscosity is too high, the shear stress generated during molding becomes strong and the polymer is oriented. It is easy, and since the polymer once oriented is difficult to relax, the stress remaining in the molded product is larger than that of the molded product of the present invention, which is considered to cause a larger deformation than in Example 1 in the wet heat test. Further, in Comparative Example 4, the proportion of the structural unit (a) is 80 mol%, but the reduced viscosity is 0.46 dL / g, and the glass transition point is higher with the increase in the structural unit (a) than in Comparative Example 3. Therefore, it is considered that the thin-wall moldability was insufficient because the melt viscosity did not reach a level suitable for the thin-wall moldability at the molding temperature (220 ° C. to 260 ° C.). On the other hand, if the molding temperature is set higher than 260 ° C., there is a risk of poor appearance such as silver streak.

  Comparative Example 5 is a molded article using a commercially available bisphenol A-based polycarbonate, but it has poor moldability (0.7 mm) and is under observation of crossed Nicols due to the high optical distortion characteristic of bisphenol A-based polycarbonate. Color unevenness was observed. Furthermore, the pencil hardness is 2B, and the molded product may be easily damaged. The lack of surface hardness is considered to be a defect that applies to all bisphenol A polycarbonates. Comparative Example 6 is a molded product using commercially available PMMA. However, although the moldability and surface hardness are good, the impact resistance is insufficient, and there is also a problem with the wet heat resistance.

  The molded product molded using the polycarbonate resin composition of the present invention is excellent in thin-wall moldability, impact resistance, surface hardness and wet heat resistance, and has low optical distortion. It can be used for a resin molded product for a purpose.

Claims (9)

A resin composition containing a polycarbonate resin having a structural unit (a) derived from a dihydroxy compound having a structure represented by the following general formula (1) and a structural unit (b) derived from another dihydroxy compound is used. And a polycarbonate resin in which the proportion of the structural unit (a) in the polycarbonate resin accounts for 70 mol% or more of the structural units derived from all dihydroxy compounds constituting the polycarbonate resin. And a reduced viscosity of the polycarbonate resin is 0.45 dL / g or less, and a thickness of the molded product is 0.1 mm or more and 1 mm or less.

(However, the case where the structure represented by the general formula (1) is a part of —CH ₂ —O—H is excluded.)
  The structural unit (b) in the polycarbonate resin is a structural unit derived from at least one compound selected from the group consisting of an aliphatic dihydroxy compound and an alicyclic dihydroxy compound. Molded products. 3. The molded article according to claim 1, wherein the dihydroxy compound having a structure represented by the general formula (1) is a compound represented by the following general formula (2).

  The molded article according to any one of claims 1 to 3, wherein the molded article is molded by an injection molding method.   The molded product according to any one of claims 1 to 4, wherein at least one surface of the molded product is subjected to a hard coat treatment.   The molded product according to any one of claims 1 to 5, wherein an in-mold decorative film is laminated on at least one surface of the molded product.   A resin integrated molded product, wherein the molded product according to any one of claims 1 to 6 and the casing are molded in two colors.   A front panel of a flat panel display, comprising the molded product according to any one of claims 1 to 6.   A front plate of a tablet-type personal computer comprising the molded product according to any one of claims 1 to 6.