JP2014174271A - Molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a molded article which exhibits high transparency and shock resistance, a low photoelastic coefficient, a uniform slow axis, low birefringence, and high surface hardness.SOLUTION: A molded article comprises a tabular portion made of a polycarbonate resin which contains a carbonate unit (A) represented by a formula below (A) and has specific viscosity of 0.3 to 0.5 as measured in a methylene chloride solution at 20°C. The tabular portion has a thickness of 0.5 mm to 5 mm. No less than 50% of an area of the tabular portion produces phase difference of no more than 80 nm, and no less than 50% of the area thereof has phase retardation values of no greater than 450 nm in a thickness direction of the tabular portion of the molded article.

Description

  The present invention relates to a molded article having high transparency, impact strength, low photoelastic coefficient, uniform slow axis, low birefringence, and high surface hardness.

  Conventionally, a molded article used for a display unit or the like has been required to have a material having high transparency and impact strength, low birefringence, and low photoelastic coefficient. In conventional transparent resins, polycarbonate resins and acrylic resins have been used. However, in polycarbonate resins, visibility has deteriorated due to the occurrence of birefringence, and acrylic resins have a problem in impact strength because they are brittle.

  In addition, since polycarbonate resins and acrylic resins are resins obtained from petroleum resources, in recent years there are concerns about the depletion of petroleum resources in recent years and the problem of an increase in carbon dioxide in the air that causes global warming. Biomass resources that are carbon neutral, which does not increase carbon dioxide even when burned, have attracted a great deal of attention. In the polymer field, biomass plastics produced from biomass resources are actively developed.

A representative example of biomass plastic is polylactic acid, which has relatively high heat resistance and mechanical properties among biomass plastics, so its application is expanding to tableware, packaging materials, general merchandise, etc. Sexuality has also been considered.
However, polylactic acid is insufficient in heat resistance when used as an industrial material, and when a molded product is obtained by injection molding with high productivity, the crystalline polymer has low crystallinity. There is a problem that moldability is inferior.

  As an amorphous polycarbonate resin that uses biomass resources as a raw material and has high heat resistance, a polycarbonate resin using a raw material obtained from an ether diol residue that can be produced from a saccharide has been studied. In particular, it has been investigated to incorporate isosorbide as a monomer mainly in polycarbonate.

  A polycarbonate resin excellent in heat resistance and moldability has been proposed by copolymerizing isosorbide and an aliphatic dihydroxy compound (Patent Documents 1 and 2). Moreover, using as a surface protection film or a front plate is proposed (patent document 3, patent document 4). However, there was no description regarding the optical characteristics, the phase difference during molding was high, and the visibility was very poor.

  Further, a molded product having a low phase difference has been proposed (Patent Document 5). However, there is no description about the retardation in the thickness direction of the molded product, and for example, when used for a display member of a display, the visibility is very poor. Furthermore, when using polarized sunglasses, a phenomenon that the screen darkened occurred, which was a problem.

International Publication No. 2004/111106 Pamphlet JP 2008-24919 A JP 2009-79190 A JP 2009-61762 A JP 2012-67287 A

  An object of the present invention is to provide a molded article having high transparency, impact strength, low photoelastic coefficient, uniform slow axis, low birefringence and high surface hardness.

  As a result of intensive studies, the present inventors have found that a polycarbonate resin containing isosorbide has a low photoelastic coefficient, a high breaking strength, and an excellent surface hardness, thereby completing the present invention.

２．ポリカーボネート樹脂の光弾性係数の絶対値が３０×１０^−１２Ｐａ^−１以下である前項１記載の成形品。
３．ポリカーボネート樹脂のガラス転移温度が７０℃〜１５０℃である前項１記載の成形品。
４．成形品が射出プレス成型により得られることを特徴とする前項１記載の成形品。
５．成形品の少なくとも片面に位相差フィルムを積層することを特徴とする前項１記載の成形品。
６．成形品の少なくとも片面にハードコートをすることを特徴とする前項１記載の成形品。
７．成形品の少なくとも片面に金型内加飾をすることを特徴とする前項１記載の成形品。
８．前項１〜７のいずれか１項に記載の成形品から形成されたディスプレイ前面板。 That is, according to the present invention, the objects of the invention are achieved by the following.
1. A plate-shaped part comprising a carbonate unit (A) represented by the following formula (A) and formed from a polycarbonate resin having a specific viscosity of 0.3 to 0.5 measured with a 20 ° C. methylene chloride solution. Retardation in the thickness direction of the plate-shaped part of the molded product, wherein the thickness of the plate-shaped part is 0.5 mm to 5 mm, and the proportion of the area where the phase difference of the plate-shaped part is 80 nm or less is 50% or more A molded product characterized in that the ratio of the area having a value of 450 nm or less is 50% or more.

2. 2. The molded article according to item 1 above, wherein the absolute value of the photoelastic coefficient of the polycarbonate resin is 30 × 10 ⁻¹² Pa ⁻¹ or less.
3. 2. The molded article according to item 1, wherein the polycarbonate resin has a glass transition temperature of 70 ° C. to 150 ° C.
4). 2. The molded article according to item 1 above, wherein the molded article is obtained by injection press molding.
5. 2. The molded article according to item 1 above, wherein a retardation film is laminated on at least one side of the molded article.
6). 2. The molded product according to item 1 above, wherein at least one surface of the molded product is hard-coated.
7). 2. The molded product according to item 1 above, wherein at least one side of the molded product is decorated in a mold.
8). A display front plate formed from the molded product according to any one of the preceding items 1 to 7.

  Since the molded article of the present invention has high transparency, high impact strength, low photoelastic coefficient, uniform slow axis, low birefringence and high surface hardness, it can be suitably used as a display front plate. The industrial effects that it plays are exceptional.

Hereinafter, the present invention will be described in detail.
<Polycarbonate resin>
The polycarbonate resin used in the present invention contains a carbonate unit (A) represented by the above formula (A). The unit (A) is preferably at least 15 mol%, more preferably at least 30 mol%, even more preferably at least 50 mol%, particularly preferably at least 60 mol%, based on all repeating units.

(Unit (A))
The unit (A) according to the present invention is derived from an aliphatic diol having an ether group, as shown in the formula (A).
The formula (A) is a diol having an ether bond among biomass resources, and is a material having high heat resistance and high pencil hardness.
Examples of the formula (A) include repeating units (A1), (A2) and (A3) represented by the following formulas having a stereoisomer relationship.

  These are saccharide-derived ether diols that are also obtained from natural biomass and are one of the so-called renewable resources. The repeating units (A1), (A2) and (A3) are called isosorbide, isomannide and isoidide, respectively. 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.

Among isosorbide, isomannide, and isoidide, a repeating unit derived from isosorbide (1,4; 3,6-dianhydro-D-sorbitol) is particularly preferable because of ease of production and heat resistance.
The polycarbonate resin of the present invention preferably contains a copolymerization monomer represented by the following formula (B).

(Unit (B-1))
As a preferable embodiment of the polycarbonate resin used in the present invention, the unit (A) and the unit (B-1) are included, and the total of the unit (A) and the unit (B-1) is 70 mol in all repeating units. % Or more, preferably 80 mol% or more, more preferably 90 mol% or more, and particularly preferably 95 mol% or more.
The unit (B-1) is a carbonate unit derived from at least one compound selected from the group consisting of an aliphatic diol compound and an alicyclic diol compound.

The aliphatic diol compound is preferably a linear aliphatic diol compound. Preferably, a linear aliphatic diol compound having 2 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 8 to 12 carbon atoms is used.
As the alicyclic diol compound, an alicyclic diol compound having preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms is used.

  Specific examples of the linear aliphatic diol compound include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1, 7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 2-ethyl-1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,10-decane Examples include diol, 1,12-dodecanediol, hydrogenated dilinoleyl glycol, hydrogenated dioleyl glycol, and the like. Of these, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol are preferable.

  Specific examples of the alicyclic diol compound include cyclohexanediols such as 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, and 2-methyl-1,4-cyclohexanediol. , 2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, cyclohexanedimethanol such as 1,4-cyclohexanedimethanol, norbornanedimethanol such as 2,3-norbornanedimethanol, 2,5-norbornanedimethanol , Tricyclodecane dimethanol, pentacyclopentadecane dimethanol, 1,3-adamantanediol, 2,2-adamantanediol, decalin dimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 3 9- bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-spiro [5.5] undecane. Among these, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5. 5] Undecane is preferred.

  These aliphatic diol compounds and alicyclic diol compounds may be used alone or in combination of two or more. In addition, the diols used in the present invention may be used in combination with an aromatic diol as long as the effects of the present invention are not impaired. As aromatic dihydroxy compounds, α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene (bisphenol M), 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,1- Bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide, bisphenol A, 2 , 2-bis (4-hydroxy-3-methylphenyl) propane (bisphenol C), 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane (bisphenol AF) ) And 1,1-bis (4-hydroxyphenyl) decane.

(composition)
The polycarbonate resin used in the present invention preferably contains the unit (A) and further contains the unit (B-1). The molar ratio (A / B-1) between these units (A) and units (B-1) is preferably 15/85 to 99/1. When the molar ratio (A / B-1) is in the range of 15/85 to 99/1, the heat resistance is high, the melt viscosity is appropriate, the moldability is good, and the impact properties are excellent accordingly. The molar ratio (A / B-1) of the unit (A) to the unit (B-1) is preferably 30/70 to 98/2, more preferably 40/60 to 96/4, still more preferably 50 / 50-95 / 5, particularly preferably 60 / 40-90 / 10. The molar ratio of each repeating unit is measured and calculated by proton NMR of JNM-AL400 manufactured by JEOL Ltd.

(Production method of polycarbonate resin)
The polycarbonate resin used in the present invention is produced by a reaction means known per se for producing an ordinary polycarbonate resin, for example, a method of reacting a diol component with a carbonate precursor such as a carbonic acid diester. Next, basic means for these manufacturing methods will be briefly described.

  The transesterification reaction using a carbonic acid diester as a carbonate precursor is performed by a method in which an aromatic dihydroxy component in a predetermined ratio is stirred with a carbonic acid diester while heating with an inert gas atmosphere to distill the generated alcohol or phenols. . The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 300 ° C. The reaction is completed while distilling off the alcohol or phenol produced under reduced pressure from the beginning. Moreover, you may add a terminal stopper, antioxidant, etc. as needed.

  Examples of the carbonic acid diester used in the transesterification include esters such as an aryl group having 6 to 12 carbon atoms and an aralkyl group which may be substituted. Specific examples include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate and m-cresyl carbonate. Of these, diphenyl carbonate is particularly preferred. The amount of diphenyl carbonate used is preferably 0.97 to 1.10 mol, more preferably 1.00 to 1.06 mol, per 1 mol of the total of dihydroxy compounds.

In the melt polymerization method, a polymerization catalyst can be used to increase the polymerization rate. Examples of the polymerization catalyst include alkali metal compounds, alkaline earth metal compounds, nitrogen-containing compounds, and metal compounds.
As such compounds, organic acid salts, inorganic salts, oxides, hydroxides, hydrides, alkoxides, quaternary ammonium hydroxides, and the like of alkali metals and alkaline earth metals are preferably used. It can be used alone or in combination.

  Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, Sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, phosphorus Examples include dilithium oxyhydrogen, disodium phenylphosphate, disodium salt of bisphenol A, 2 potassium salt, 2 cesium salt, 2 lithium salt, sodium salt of phenol, potassium salt, cesium salt, lithium salt and the like.

  Alkaline earth metal compounds include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, calcium bicarbonate, barium bicarbonate, magnesium bicarbonate, bicarbonate Examples include strontium, magnesium diacetate, calcium diacetate, strontium diacetate, and barium diacetate. 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 nitrogen-containing compounds include quaternary ammonium hydroxides having alkyl, aryl groups, etc., such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzylammonium hydroxide. Can be mentioned. Further, tertiary amines such as triethylamine, dimethylbenzylamine, and triphenylamine, and imidazoles such as 2-methylimidazole, 2-phenylimidazole, and benzimidazole can be used. Moreover, bases or basic salts such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, tetraphenylammonium tetraphenylborate and the like are exemplified.

Examples of metal compounds include zinc aluminum compounds, germanium compounds, organotin compounds, antimony compounds, manganese compounds, titanium compounds, zirconium compounds, and the like. These compounds may be used alone or in combination of two or more.
The amount of these polymerization catalysts used is preferably 1 × 10 ⁻⁹ to 1 × 10 ⁻² equivalent, preferably 1 × 10 ⁻⁸ to 1 × 10 ⁻⁵ equivalent, more preferably 1 × with ^respect to 1 mol of the diol component. It is selected in the range of 10 ⁻⁷ to 1 × 10 ⁻³ equivalents.

  In addition, a catalyst deactivator can be added at a later stage of the reaction. As the catalyst deactivator to be used, a known catalyst deactivator is effectively used. Among them, sulfonic acid ammonium salt and phosphonium salt are preferable. Furthermore, salts of dodecylbenzenesulfonic acid such as tetrabutylphosphonium salt of dodecylbenzenesulfonic acid and salts of paratoluenesulfonic acid such as tetrabutylammonium salt of paratoluenesulfonic acid are preferable.

  Further, as esters of sulfonic acid, methyl benzenesulfonate, ethyl benzenesulfonate, butyl benzenesulfonate, octyl benzenesulfonate, phenyl benzenesulfonate, methyl paratoluenesulfonate, ethyl paratoluenesulfonate, butyl paratoluenesulfonate, Octyl paratoluenesulfonate, phenyl paratoluenesulfonate and the like are preferably used. Among these, dodecylbenzenesulfonic acid tetrabutylphosphonium salt is most preferably used.

  The amount of the catalyst deactivator used is preferably 0.5 to 50 mol per mol of the catalyst when at least one polymerization catalyst selected from alkali metal compounds and / or alkaline earth metal compounds is used. It can be used in a proportion, more preferably in a proportion of 0.5 to 10 mol, still more preferably in a proportion of 0.8 to 5 mol.

(Unit (B-2))
As a preferable embodiment of the polycarbonate resin used in the present invention, a carbonate unit derived from at least one compound selected from the group consisting of the above unit (A) and an aliphatic diol compound and an alicyclic diol compound (B- 2), having a block property, and the total of the units (A) and the units (B-2) is 80 mol% or more, preferably 90 mol% or more in all repeating units Is mentioned. Compounds (for example, oxyalkylene glycols and aromatic dihydroxy compounds) that derive other units other than the unit (A) and the unit (B-2) can also be used.

The aliphatic diol compound may be either a linear aliphatic diol compound or a branched aliphatic diol compound. As the linear aliphatic diol compound, a linear aliphatic diol compound having preferably 2 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, and further preferably 3 to 10 carbon atoms is used. Further, as the branched aliphatic diol compound, a branched aliphatic diol compound having preferably 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, and further preferably 4 to 12 carbon atoms is used.
As the alicyclic diol compound, an alicyclic diol compound having preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms is used.

  Specific examples of the linear aliphatic diol compound include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,7-heptanediol. 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, hydrogenated dilinoleyl glycol, hydrogenated dioleyl glycol and the like. Of these, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and 1,10-decanediol are preferable.

  Specific examples of the branched aliphatic diol compound include 1,3-butylene glycol, 2-methyl-1,3-propanediol, neopentyl glycol, 2-ethyl-1,6-hexanediol, 2,2,4 -Trimethyl-1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-n-butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol 2,4-diethyl-1,5-pentanediol, 1,2-hexane glycol, 1,2-octyl glycol, 2-ethyl-1,3-hexanediol, 2,3-diisobutyl-1,3-propane Examples include diol, 2,2-diisoamyl-1,3-propanediol, and 2-methyl-2-propyl-1,3-propanediol. Among them, 3-methyl-1,5-pentanediol, 2-n-butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,4-diethyl-1 , 5-pentanediol is preferred.

  Specific examples of the alicyclic diol compound include cyclohexanediols such as 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, and 2-methyl-1,4-cyclohexanediol. , 2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, cyclohexanedimethanol such as 1,4-cyclohexanedimethanol, norbornanedimethanol such as 2,3-norbornanedimethanol, 2,5-norbornanedimethanol , Tricyclodecane dimethanol, pentacyclopentadecane dimethanol, 1,3-adamantanediol, 2,2-adamantanediol, decalin dimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 3 9- bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-spiro [5.5] undecane. Among these, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5. 5] Undecane is preferred. These aliphatic diol compounds and alicyclic diol compounds may be used alone or in combination of two or more.

  The polycarbonate copolymer has a block property of the unit (B-2). The average number of repeating units (n) of the unit (B-2) in the block portion is preferably 2 to 100, more preferably 2.2 to 50, still more preferably 2.3 to 30, particularly preferably 2.5 to 10. It is. The number average molecular weight of the unit (B-2) in the block portion is preferably 250 to 5000, more preferably 300 to 3000, still more preferably 300 to 2000, and particularly preferably 350 to 1500. When the average number of repeating units (n) and the number average molecular weight of the unit (B-2) in the block part are within the above ranges, the desired water absorption, heat resistance and pencil hardness are improved, and phase separation hardly occurs. preferable.

The block property of the unit (B-2) in the polycarbonate copolymer can be calculated from carbon of carbonate measured by ¹³ C-NMR by dissolving the polycarbonate copolymer in CDCl ₃ . There are three signals of [unit (A) -unit (A)] at 153 to 154 ppm (since there are three stereoisomers), and the signal of [unit (A) -unit (B-2)] is usually 154 There are two at 155 ppm (when there is no stereoisomerism of the copolymerized diol, there are two types of stereoisomers with isosorbide), and the signal of [unit (B-2) -unit (B-2)] is usually Measured at 155-156 ppm. The average number of repeating units of the unit (B-2) can be calculated from the integrated value of this signal. The average number of repeating units of the unit (B-2) is determined by the following formula. Further, the number average molecular weight of the unit (B-2) in the block portion is calculated by multiplying the average number of repeating units by the molecular weight of the repeating unit.

  The molar ratio (A / B-1) of the unit (A) to the unit (B-2) is preferably in the range of 60/40 to 95/5, more preferably in the range of 65/35 to 93/7, 70 The range of / 30 to 90/10 is more preferable. Within the above range, it is preferable because of excellent balance of heat resistance, weather resistance, low water absorption, surface hardness and low temperature impact characteristics. The molar ratio (A / B-2) can be measured and calculated by proton NMR of JNM-AL400 manufactured by JEOL Ltd.

  The method for producing the polycarbonate copolymer containing the unit (A) and the unit (B-2) and having the block property of the unit (B-2) is selected from the group consisting of an aliphatic diol compound and an alicyclic diol compound in advance. A polycarbonate oligomer represented by a repeating unit (B-2) is obtained from at least one kind of compound, and then the obtained polycarbonate oligomer, a monomer (for example, isosorbide) for deriving the unit (A), and a carbonate precursor are reacted. Thus, a method for producing a polycarbonate copolymer is preferred.

(I) Polycarbonate oligomer production method Polycarbonate oligomer is a known reaction means for producing an ordinary polycarbonate resin, for example, a method in which a diol compound is reacted with a carbonate precursor such as a carbonic acid diester, or a known method for producing a polycarbonate diol. Manufactured by. Next, basic means for these manufacturing methods will be briefly described.

The transesterification reaction using a carbonic acid diester as a carbonate precursor is carried out by a method in which a predetermined proportion of a diol compound is stirred with a carbonic acid diester while heating under an inert gas atmosphere to distill the alcohol or phenols produced. The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 300 ° C. The reaction is carried out while distilling off the alcohol or phenol produced under reduced pressure from the beginning. Moreover, you may add antioxidant etc. as needed.
As the carbonic acid diester used in the transesterification reaction, the same carbonic acid diesters as described above can be used.
As the catalyst that can be used, the same catalyst as the above-mentioned catalyst (transesterification catalyst) can be used.

The method for producing a polycarbonate oligomer can be carried out in the presence or absence of a catalyst, but is preferably carried out in the presence of a catalyst from the viewpoint of reaction efficiency.
The reaction temperature in the method for producing a polycarbonate oligomer is preferably 90 to 230 ° C, more preferably 100 to 220 ° C, and further preferably 120 to 210 ° C. When reaction temperature exceeds 230 degreeC, the obtained polycarbonate oligomer may color or an ether structure may produce | generate.

  At the beginning of the reaction of the production method of polycarbonate oligomer, the amount of by-produced alcohol and phenol is relatively small. Therefore, in order to suppress the distillation of the carbonic acid diester, the ester exchange reaction is performed at 10 kPa to normal pressure, and the end of the ester exchange reaction. For example, the transesterification is preferably performed at a reduced pressure of 0.1 to 10 kPa, more preferably 0.1 to 1 kPa after the transesterification has proceeded preferably at least 50%, more preferably at least 70%. Is preferred.

  The number average molecular weight of the polycarbonate oligomer is preferably 250 to 5000, more preferably 300 to 3000, still more preferably 400 to 2000, and particularly preferably 400 to 1500. When the number average molecular weight is less than 250, the intended water absorption, heat resistance, and pencil hardness may be deteriorated. On the other hand, when the number average molecular weight exceeds 5000, the block property becomes too high and phase separation is likely to occur. The number average molecular weight of the polycarbonate oligomer can be calculated by measuring proton NMR. The terminal hydroxyl group and the terminal phenyl group were calculated with respect to the repeating unit by proton NMR, and the number average molecular weight was calculated by the following formula.

The ratio of the terminal hydroxyl group and terminal phenyl group of the polycarbonate oligomer is not particularly limited, and any ratio may be used.
The production of the polycarbonate oligomer may be carried out in the same reaction vessel as the production of the polycarbonate copolymer, or a separate reaction vessel may be used. Alternatively, it may be used after being taken out from the reaction vessel and stored. Further, the polycarbonate oligomer may be purified by a filter or reprecipitation.

(Ii) Production method of polycarbonate copolymer The polycarbonate copolymer comprising the unit (A) and the unit (B-2) and having the block property of the unit (B-2) is a polycarbonate oligomer obtained by the above method, It is produced by reacting a monomer (for example, isosorbide) for deriving the unit (A) and a carbonate precursor by a reaction means known per se for producing an ordinary polycarbonate resin. Next, basic means for these manufacturing methods will be briefly described.

  The transesterification reaction using a carbonic acid diester as a carbonate precursor is carried out by a method in which a predetermined proportion of a diol component is stirred with a carbonic acid diester under heating in an inert gas atmosphere to distill the resulting alcohol or phenol. The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 300 ° C. The reaction is completed while distilling off the alcohol or phenol produced under reduced pressure from the beginning. Moreover, you may add a terminal stopper, antioxidant, etc. as needed.

  As the carbonic acid diester used in the transesterification reaction, the same carbonic acid diesters as described above can be used. Of these, diphenyl carbonate is particularly preferred. The amount of diphenyl carbonate used is preferably 0.97 to 1.10 mol, more preferably 1.00 to 1.06 mol, per 1 mol of the total of dihydroxy compounds.

In the melt polymerization method, a polymerization catalyst can be used in order to increase the polymerization rate. As the polymerization catalyst, the same catalyst as described above (transesterification catalyst) can be used.
The amount of the polymerization catalyst, preferably with respect to the diol component per mol of 1 × ¹⁰ -9 ~1 × ^{10 -2} equivalents, preferably 1 × ¹⁰ -8 ~1 × ^{10 -5} equivalent, more preferably 1 × 10 ^- It is selected in the range of ⁷ to 1 × 10 ⁻³ equivalents.
In addition, a catalyst deactivator can be added at a later stage of the reaction. The catalyst deactivator mentioned above can be used as the catalyst deactivator to be used.

  The amount of the catalyst deactivator used is preferably 0.5 to 50 mol per mol of the catalyst when at least one polymerization catalyst selected from alkali metal compounds and / or alkaline earth metal compounds is used. It can be used in a proportion, more preferably in a proportion of 0.5 to 10 mol, still more preferably in a proportion of 0.8 to 5 mol.

(Unit (B-3))
As a preferable embodiment of the polycarbonate resin used in the present invention, the unit (A) and the unit (B-3) represented by the following formula (B-3) are included. A copolymer polycarbonate resin having a total of 80 mol% or more, preferably 90 mol% or more, with the unit (B-3) can be mentioned.

（式中Ｘは、炭素数３〜２０のアルキレン基または炭素数３〜２０のシクロアルキレン基を表し、Ｒは炭素数１〜２０のアルキル基または炭素数３〜２０のシクロアルキル基を表し、ｍは１〜１０の整数を示す。）

(In the formula, X represents an alkylene group having 3 to 20 carbon atoms or a cycloalkylene group having 3 to 20 carbon atoms, R represents an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms, m represents an integer of 1 to 10.)

The unit (B-3) is a unit derived from an aliphatic diol having a side chain alkyl group or a side chain cycloalkyl group.
The unit (B-3) preferably has a total carbon number in the range of 4 to 12, more preferably in the range of 5 to 10. Within such a range, the HDT (deflection temperature under load) of the polycarbonate resin is kept high.

In the unit (B-3), the total number of carbon atoms of X (main chain carbon number) and R carbon atoms (side chain carbon number) preferably satisfies the following formula (i). It is more preferable to satisfy (ia), and it is more preferable to satisfy the following formula (ib). When the following formula (i) is satisfied, the boiling water resistance is excellent and the water absorption rate can be greatly reduced, which is preferable.
0.3 ≦ (number of carbons in main chain) / (number of carbons in side chain) ≦ 8 (i)
0.4 ≦ (number of carbons in main chain) / (number of carbons in side chain) ≦ 5 (ia)
0.5 ≦ (number of carbons in main chain) / (number of carbons in side chain) ≦ 2 (ib)

(X in the unit (B-3))
In the formula (B-3), X represents an alkylene group having 3 to 20 carbon atoms or a cycloalkylene group having 3 to 20 carbon atoms.
X is preferably an alkylene group having 3 to 12 carbon atoms, more preferably an alkylene group having 3 to 8 carbon atoms, and still more preferably an alkylene group having 2 to 6 carbon atoms. Examples of the alkylene group include a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, and an octylene group.
X is preferably a cycloalkylene group having 3 to 12 carbon atoms, more preferably a cycloalkylene group having 3 to 8 carbon atoms, and further preferably a cycloalkylene group having 3 to 6 carbon atoms. Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, and a cyclooctylene group.

(R in unit (B-3))
In the formula (B-3), R represents an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms.
R is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group.
R is preferably a cycloalkyl group having 3 to 12 carbon atoms, more preferably a cycloalkyl group having 3 to 8 carbon atoms. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

(M in unit (B-3))
In the formula (B-3), m represents an integer of 1 to 10, preferably an integer of 2 to 8, more preferably an integer of 2 to 5.

(When X in the unit (B-3) is an alkylene group having 3 to 20 carbon atoms)
In the unit (B-3), X is preferably an alkylene group having 3 to 20 carbon atoms, R is an alkyl group having 1 to 4 carbon atoms, and m is an integer of 2 to 8. It is preferable that X in the unit (B) is an alkylene group having 3 to 5 carbon atoms, R is an alkyl group having 1 to 4 carbon atoms, and m is an integer of 1 to 2.
It is preferable that -X {-(R) _m }-in the unit (B-3) is a unit (Ba) represented by the following formula.

n is an integer of 2-6, preferably an integer of 3-5. n R _{a s} are each independently selected from a hydrogen atom and an alkyl group having 1 to 4 carbon atoms. n R _{b s} are each independently selected from a hydrogen atom and an alkyl group having 1 to 4 carbon atoms. Of n R _a and n R _b , one or two is an alkyl group having 1 to 4 carbon atoms, and the other is preferably a hydrogen atom.
-X {-(R) _m }-in the unit (B-3) is 2-n-butyl-2-ethyl-1,3-propanediyl group, 2,4-diethyl-1,5-pentanediyl The group is preferably a 3-methyl-1,5-pentanediyl group.

(When X in the unit (B-3) is a cycloalkylene group having 3 to 20 carbon atoms)
In the formula (B-3), X is preferably a cycloalkylene group having 4 to 5 carbon atoms, R is an alkyl group having 1 to 10 carbon atoms, and m is preferably an integer of 3 to 12.
The unit (B-3) is preferably a unit (Bb) represented by the following formula.

R ₁ , R ₂ , R ₃ and R ₄ are each an alkyl group which may be the same or different, and the total number of carbon atoms of R _{1 to} R ₄ is 4 to 10, and R ₁ and R ₂ , R ₃ and R ₄ may combine to form a carbocycle. R ₁ , R ₂ , R ₃ and R ₄ in the unit (Bb) are preferably each independently a methyl group, an ethyl group or a propyl group.
The unit (B-3) is preferably a unit (Bb-i) represented by the following formula.

  The unit (B-3) is derived from an aliphatic diol having a side chain alkyl group or a side chain cycloalkyl group. Examples of the aliphatic diol having a side chain alkyl group or a side chain cycloalkyl group include 1,3-butylene glycol, 2-methyl-1,3-propanediol, neopentyl glycol, and 3-methyl-1,5-pentanediol. 2-n-butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexane glycol 1,2-octyl glycol, 2-ethyl-1,6-hexanediol, 2,3-diisobutyl-1,3-propanediol, 1,12-octadecanediol, 2,2-diisoamyl-1,3-propane Diol, 2-methyl-2-propyl-1,3-propanediol, 2-cyclohexyl-1,3-propanediol, 2- Chill-1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol and the like.

  Among them, 3-methyl-1,5-pentanediol, 2-n-butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,4-diethyl-1 , 5-pentanediol is preferred, and 2-n-butyl-2-ethyl-1,3-propanediol and 2,4-diethyl-1,5-pentanediol are particularly preferred. Two or more of these may be used in combination.

  The molar ratio (A / B-3) of the unit (A) to the unit (B-3) is preferably in the range of 50/50 to 95/5, more preferably in the range of 60/40 to 93/7, 70 The range of / 30 to 90/10 is more preferable. Within the above range, it is preferable because of excellent balance of heat resistance, weather resistance, low water absorption, surface hardness and low temperature impact characteristics. The molar ratio (A / B-3) can be measured and calculated by proton NMR of JNM-AL400 manufactured by JEOL.

Examples of the diol compound for deriving other units other than the unit (A) and the unit (B-3) include the monomer compounds for deriving the unit (B-1) and the unit (B-2), and other fats. Any of an aromatic diol compound, an alicyclic diol compound, and an aromatic dihydroxy compound may be used. Specific examples include diol compounds and oxyalkylene glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, and polyethylene glycol described in International Publication No. 2004/111106 pamphlet and International Publication No. 2011/021720 pamphlet.
Examples of the aliphatic dihydroxy compound, the alicyclic dihydroxy compound, and the aromatic dihydroxy compound include those described above.

  The copolymer polycarbonate resin containing the unit (A) and the unit (B-3) is obtained by a reaction means known per se for producing an ordinary polycarbonate resin, for example, a method of reacting a diol component with a carbonate precursor such as a carbonic acid diester. Manufactured. The basic means for these production methods is the same as the means for the copolymer polycarbonate resin containing the unit (A) and the unit (B-1) described above.

(Unit (B-4))
Another aspect of the polycarbonate resin used in the present invention includes the above unit (A) and a carbonate unit (B-4) derived from a polyester diol. Among all repeating units, the unit (A) and the unit (B -4) is a total of 80 mol% or more, preferably 90 mol% or more.
The unit (B-4) is a carbonate unit derived from a polyester diol (B4) containing a dicarboxylic acid component and a diol component as constituent components.

  Suitable dicarboxylic acids are aliphatic carboxylic acids, aromatic carboxylic acids or aromatic aliphatic carboxylic acids having 4 to 20 carbon atoms. Preferably, 2,2-dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, suberic acid, azelaic acid, 1,4-cyclohexanedicarboxylic acid, orthophthalic acid, phthalic anhydride, naphthalic acid, At least one dicarboxylic acid selected from the group consisting of biphenyldicarboxylic acid, hexahydrophthalic acid, 5-methylisophthalic acid, terephthalic acid and isophthalic acid, particularly preferably adipic acid, sebacic acid, 1,4-cyclohexanedicarboxylic acid It is at least one dicarboxylic acid selected from the group consisting of acids, terephthalic acid and isophthalic acid. These dicarboxylic acid components may be used alone or in combination of two or more.

Suitable diol components include linear aliphatic diol compounds, branched aliphatic diol compounds, and alicyclic diol compounds.
Specific examples of the linear aliphatic diol compound include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,7-heptanediol. 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, hydrogenated dilinoleyl glycol, hydrogenated dioleyl glycol and the like. Of these, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and 1,10-decanediol are preferable.

  Specific examples of the branched aliphatic diol compound include 1,3-butylene glycol, 2-methyl-1,3-propanediol, neopentyl glycol, 2-ethyl-1,6-hexanediol, 2,2,4 -Trimethyl-1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-n-butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol 2,4-diethyl-1,5-pentanediol, 1,2-hexane glycol, 1,2-octyl glycol, 2-ethyl-1,3-hexanediol, 2,3-diisobutyl-1,3-propane Diol, 2,2-diisoamyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, glycerin, trimethylo Trimethylolpropane, pentaerythritol, and the like. Among them, 3-methyl-1,5-pentanediol, 2-n-butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,4-diethyl-1 , 5-pentanediol is preferred.

Specific examples of the alicyclic diol compound include cyclohexanediols such as 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, and 2-methyl-1,4-cyclohexanediol. , 2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, cyclohexanedimethanol such as 1,4-cyclohexanedimethanol, norbornanedimethanol such as 2,3-norbornanedimethanol, 2,5-norbornanedimethanol , Tricyclodecane dimethanol, pentacyclopentadecane dimethanol, 1,3-adamantanediol, 2,2-adamantanediol, decalin dimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 3 9- bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-spiro [5.5] undecane. Among these, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5. 5] Undecane is preferred.
These diol compounds may be used alone or in combination of two or more.

A suitable polyester diol (B4) is represented by the following formula.

In the formula, R represents a hydrocarbon group that may contain an aromatic group having 1 to 12 carbon atoms, specifically, the above-mentioned linear aliphatic diol compound, branched aliphatic diol compound, alicyclic diol compound. Is an aliphatic or alicyclic moiety.
W represents a hydrocarbon group which may contain an aromatic group having 1 to 12 carbon atoms. Specifically, the aliphatic carboxylic acid, aromatic carboxylic acid or aromatic aliphatic carboxylic acid described above, Is an aliphatic or aromatic aliphatic moiety.
n represents the average number of repeating units. As will be described later, the weight average molecular weight of the polyester diol (B1) is preferably in the range of 100 to 3000, and the average number of repeating units n is preferably set so as to be the weight average molecular weight.

The polyester diol can be produced according to a known polyester diol production method.
Examples of the metal catalyst used in the method for producing the polyester diol include Lewis acids, alkali metal and alkaline earth metal carboxylates, proton acids, activated clays, acid clays, and ion exchange resins. More specifically, tetrabutoxy titanate, dibutyltin oxide, manganese acetate, cobalt acetate, zinc acetate, zinc benzoate, lithium acetate, sodium acetate, magnesium acetate, calcium acetate, acid value antimony, acid value germanium, phosphoric acid, boron Examples include acid, sulfuric acid, p-toluenesulfonic acid, metasulfonic acid, and Amberlyst E15. The usage-amount of these catalysts is 10-5000 micrograms with respect to raw material polyalkylene terephthalate, Preferably it is 50-1000 micrograms.

  In the method for producing a polyester diol, the reaction temperature for carrying out the transesterification reaction is usually in the range of 150 to 300 ° C, preferably in the range of 200 to 250 ° C. The pressure may be any, but is usually normal pressure to 1 MPa. In addition, the reaction time for the transesterification reaction is not particularly limited, but is usually in the range of 0.5 to 5 hours. The transesterification reaction may be carried out by any of batch, semi-batch and continuous methods.

  The glycol component by-produced by the transesterification reaction is distilled off as necessary. As a result, the hydroxyl value and viscosity of the polyester diol can be controlled within a predetermined range. There is no particular limitation on the distillation of the glycol component, but it is usually carried out under heating and reduced pressure. Also, the glycol component may be distilled off while reacting in the presence of a transesterification reaction catalyst, or it may be distilled off after completion of the reaction, but the reaction can be controlled because the ratio of the acid component and glycol component during the reaction can be controlled. It is sometimes preferred to distill off. The temperature for distilling off the glycol is usually in the range of 150 to 300 ° C, preferably in the range of 200 to 250 ° C. The pressure is usually 0.5 to 0.0001 MPa, preferably 0.1 to 0.001 MPa.

  The obtained polyester diol may remove impurities such as metal. In particular, it is preferable to treat metal components such as antimony and germanium using an adsorbent or the like. Furthermore, if the catalyst used for the transesterification remains in the diol, the hydrolyzability and thermal stability deteriorate, so it may be removed with an adsorbent, or water such as tetrabutoxy titanate. A compound that is decomposed to become an insoluble compound in the diol may be removed by adding water to hydrolyze the catalyst to precipitate it, and then separating it by filtration.

  Although it does not restrict | limit especially about the weight average molecular weight of polyester diol, 100-3000 are preferable, 200-2500 are more preferable, 300-2000 are more preferable, 400-1500 are especially preferable, 450-1000 are the most preferable. When the weight average molecular weight of the polyester diol is less than 100, the acid value tends to increase, which may affect the polymerization reaction and deteriorate the productivity. On the other hand, when the weight average molecular weight of the polyester diol exceeds 3000, phase separation tends to occur.

The acid value of the polyester diol is preferably 1 mgKOH / g or less, more preferably 0.3 mgKOH / g or less. If it exceeds 1 mgKOH / g, the polymerization reaction may be affected, and productivity may deteriorate.
The molar ratio (A / B-4) of the unit (A) to the unit (B-4) is preferably in the range of 50/50 to 99/1, more preferably in the range of 70/30 to 98/2, 90 A range of / 10 to 97.5 / 2.5 is more preferable. It is preferable that it is in the above-mentioned range because of excellent balance of heat resistance, weather resistance, low water absorption, surface hardness and low temperature impact resistance. The molar ratio (A / B-4) can be measured and calculated by proton NMR of JNM-AL400 manufactured by JEOL.

  The polyester carbonate resin is obtained by reacting the polyester diol obtained by the above-described method, the monomer (for example, isosorbide) derived from the unit (A) and the carbonate precursor by a reaction means known per se for producing a normal polycarbonate resin. Manufactured. The basic means for these production methods is the same as the means for the copolymer polycarbonate resin containing the unit (A) and the unit (B-1) described above.

(Specific viscosity: η _SP )
The specific viscosity (η _SP ) of the polycarbonate resin used in the present invention is 0.3 to 0.5, preferably 0.31 to 0.47, more preferably 0.32 to 0.45, and 33 to 0.42 is more preferable, 0.34 to 0.40 is particularly preferable, and 0.35 to 0.38 is most preferable. When the specific viscosity of the polycarbonate resin is smaller than 0.3, the strength is lowered, and when it is larger than 0.5, the moldability is deteriorated.

The specific viscosity referred to in the present invention was determined using an Ostwald viscometer from a solution obtained by dissolving 0.7 g of a polycarbonate resin in 100 ml of methylene chloride at 20 ° C.
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]
In addition, as a specific measurement of specific viscosity, it can carry out in the following way, for example. First, the polycarbonate resin is dissolved in 20 to 30 times the weight of methylene chloride, and the soluble component is collected by celite filtration, and then the solution is removed and dried sufficiently to obtain a solid component soluble in methylene chloride. Using a Ostwald viscometer, the specific viscosity at 20 ° C. is determined from a solution of 0.7 g of the solid dissolved in 100 ml of methylene chloride.

(Glass transition temperature: Tg)
The glass transition temperature (Tg) of the polycarbonate resin used in the present invention is preferably 70 to 150 ° C, more preferably 90 to 140 ° C, still more preferably 100 to 135 ° C, and particularly preferably 110 to 130 ° C.
When the glass transition temperature (Tg) of the polycarbonate resin is 70 ° C. or higher, the heat resistance is sufficient when used as an optical molded body, which is preferable. Moreover, it is preferable that the glass transition temperature (Tg) of the polycarbonate resin is 150 ° C. or less because the moldability during injection molding is good.
The glass transition temperature (Tg) is measured at 29 ° C./min using a 2910 type DSC manufactured by TA Instruments Japan.

(Photoelastic coefficient)
The photoelastic coefficient of the polycarbonate resin used in the present invention is preferably 30 × 10 ⁻¹² Pa ⁻¹ or less, more preferably 28 × 10 ⁻¹² Pa ⁻¹ or less, and particularly preferably 20 × 10 ⁻¹² Pa ^−1. It is as follows. Since it is hard to generate | occur | produce the optical distortion by stress as it is 30 * 10 <^-12> Pa < ^{-1 >} or less, it is preferable as a display front board.

(Pencil hardness)
The polycarbonate resin used in the present invention preferably has a pencil hardness of HB or higher. In terms of excellent scratch resistance, F or higher is more preferable, and H or higher is more preferable. The pencil hardness can be increased by increasing the composition of the repeating units (B-1) to (B-3) based on all repeating units. In the present invention, the pencil hardness is a hardness that does not leave a scratch mark even when the resin of the present invention is rubbed with a pencil having a specific pencil hardness, and measured according to JIS K-5600. The pencil hardness used for the surface hardness test of the paint film that can be used is used as an index. Pencil hardness becomes soft in the order of 9H, 8H, 7H, 6H, 5H, 4H, 3H, 2H, H, F, HB, B, 2B, 3B, 4B, 5B, 6B, the hardest is 9H, The soft one is 6B.

(Saturated water absorption)
The saturated water absorption of the polycarbonate resin of the present invention is 2.5% or less, preferably 2.2% or less, and more preferably 2.0% or less. When the saturated water absorption rate is higher than 2.5%, various physical properties such as dimensional change and warpage due to water absorption are remarkable in the molded product, which is not preferable.
In the polycarbonate resin of the present invention, the relationship between the glass transition temperature (Tg ° C.) and the water absorption (Wa%) preferably satisfies the following formula (I), and satisfies the following formula (Ia). Is more preferable. When the following formula (I) is satisfied, the polycarbonate resin is excellent in heat resistance and has a low water absorption rate, which is preferable because it can suppress changes in physical properties and deformation in a humid heat environment. The upper limit of the TW value is not particularly limited, but 10 or less is sufficient.
2.5 ≦ TW value = Tg × 0.04-Wa (I)
2.6 ≦ TW value = Tg × 0.04−Wa (I−a)

(Low temperature impact)
In the polycarbonate resin of the present invention, the fracture mode of the low-temperature surface impact is ductile fracture, and the low-temperature impact property is excellent. The low temperature surface impact property was measured using a 2 mm thick square plate at a test temperature of −20 ° C., a test speed of 7 m / sec, a striker diameter of 1/2 inch and a receiving diameter of 1 inch using a high-speed impact tester. It is preferable that the probability of occasional brittle fracture is 50% or less. More preferably, it is 40% or less, more preferably 30% or less, particularly preferably 20% or less, and most preferably 15% or less. The 50% fracture energy is preferably 20 J or more. More preferably, it is 25J or more, More preferably, it is 30J or more, Most preferably, it is 35J or more. When the probability that the fracture mode of the low-temperature surface impact is brittle fracture exceeds 50%, or when the 50% fracture energy is less than 20J, it may be difficult to use in a cold region.

(Dynamic viscoelasticity)
The polycarbonate resin of the present invention preferably has a temperature at which tan δ of dynamic viscoelasticity measurement has a maximum value of −78 ° C. or lower. -79 degrees C or less is more preferable, and -80 degrees C or less is still more preferable.

(Additives, etc.)
The polycarbonate resin used in the present invention is a heat stabilizer, a plasticizer, a light stabilizer, a polymerized metal deactivator, a flame retardant, a lubricant, an antistatic agent, a surfactant, an antibacterial agent, if necessary and necessary. Additives such as ultraviolet absorbers and mold release agents can be blended.
Further, the polycarbonate resin used in the present invention may be used in combination with other resins as long as the effects of the present invention are not impaired.

(Flame retardants)
In the present invention, a flame retardant can be blended in the resin composition constituting the substrate. 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.

（式中、Ｒ^１は炭素原子数６〜１５のアリール基、炭素原子数７〜２０のアラルキル基、Ｘ^１及びＸ^２は同一又は異なり、炭化水素基、アルコキシ基、アリールオキシ基、またはアラルキルオキシ基を示す。Ｘ^１及びＸ^２は互いに結合して隣接するリン原子とともに環を形成してもよい。）
で表される有機リン化合物である事が好ましい。より具体的には下記式（ａ−１）

で表される有機リン化合物である事が好ましい。上記式（ａ−１）中、Ｒ^１は炭素原子数６〜１５のアリール基、炭素原子数７〜２０のアラルキル基であることが好ましく、炭素原子数７〜２０のアラルキル基であることがより好ましい。上記式（ａ−１）中、Ｒ^２，Ｒ^３はそれぞれ独立して水素原子、ハロゲン原子、炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基、炭素原子数６〜１５のアリール基、炭素原子数６〜１５のアリールオキシ基、炭素原子数７〜２０のアラルキル基、または炭素原子数７〜２０のアラルキルオキシ基であることが好ましく、水素原子、炭素原子数１〜１０のアルキル基、炭素原子数６〜１５のアリール基、炭素原子数７〜２０のアラルキル基がより好ましく、水素原子、炭素原子数１〜１０のアルキル基が特に好ましい。 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.
Preferably the following formula (a)

(Wherein R ¹ is an aryl group having 6 to 15 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, X ¹ and X ² are the same or different, and a hydrocarbon group, an alkoxy group, an aryloxy group, or an aralkyl group. Represents an oxy group, and X ¹ and X ² may be bonded to each other to form a ring with an adjacent phosphorus atom.
It is preferable that it is an organic phosphorus compound represented by these. More specifically, the following formula (a-1)

It is preferable that it is an organic phosphorus compound represented by these. In the above formula (a-1), R ¹ is preferably an aryl group having 6 to 15 carbon atoms and an aralkyl group having 7 to 20 carbon atoms, and preferably an aralkyl group having 7 to 20 carbon atoms. More preferred. In the formula (a-1), R ² and R ³ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or 6 to 6 carbon atoms. It is preferably a 15 aryl group, an aryloxy group having 6 to 15 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an aralkyloxy group having 7 to 20 carbon atoms. 10 to 10 alkyl groups, aryl groups having 6 to 15 carbon atoms, and aralkyl groups having 7 to 20 carbon atoms are more preferable, and hydrogen atoms and alkyl groups having 1 to 10 carbon atoms are particularly preferable.

（式中、Ｘ^１、Ｘ^２は同一もしくは異なり、下記式（２）で表される芳香族置換アルキル基である。） Another preferred organophosphorus compound is represented by the following formula (1).

(In formula, X < ¹ >, X < ² > is the same or different, and is an aromatic substituted alkyl group represented by following formula (2).)

（式中、ＡＬは炭素数１〜５の分岐状または直鎖状の脂肪族炭化水素基であり、Ａｒは置換基を有しても良いフェニル基、ナフチル基、またはアントリル基である。ｎは１〜３の整数を示し、ＡｒはＡＬ中の任意の炭素原子に結合することができる。）

(In the formula, AL is a branched or linear aliphatic hydrocarbon group having 1 to 5 carbon atoms, and Ar is a phenyl group, a naphthyl group, or an anthryl group which may have a substituent. Represents an integer of 1 to 3, and Ar can be bonded to any carbon atom in AL.)

（式中、Ｒ^２、Ｒ^５は同一または異なっていてもよく、置換基を有しても良いフェニル基、ナフチル基、またはアントリル基である。Ｒ^１、Ｒ^３、Ｒ^４、Ｒ^６は同一または異なっていてもよく、水素原子、炭素数１〜４の分岐状または直鎖状のアルキル基、置換基を有しても良いフェニル基、ナフチル基、またはアントリル基から選択される置換基である。） Preferably they are 1 type, or 2 or more types of mixtures selected from the organic phosphorus compound group represented by following formula (3) and (4).

(In the formula, R ² and R ⁵ may be the same or different, and may be a phenyl group, a naphthyl group, or an anthryl group that may have a substituent. R ¹ , R ³ , R ⁴ , R ⁶ are Substituents which may be the same or different and are selected from a hydrogen atom, a branched or straight chain alkyl group having 1 to 4 carbon atoms, an optionally substituted phenyl group, naphthyl group, or anthryl group .)

（式中、Ａｒ^１およびＡｒ^２は、同一又は異なっていても良く、フェニル基、ナフチル基またはアントリル基であり、その芳香環に置換基を有していてもよい。Ｒ^１１、Ｒ^１２、Ｒ^１３およびＲ^１４は、同一又は異なっていても良く、水素原子、炭素数１〜３の脂肪族炭化水素基またはフェニル基、ナフチル基もしくはアントリル基であり、その芳香環に置換基を有していてもよい。ＡＬ^１およびＡＬ^２は、同一又は異なっていても良く、炭素数１〜４の分岐状または直鎖状の脂肪族炭化水素基である。Ａｒ^３およびＡｒ^４は、同一又は異なっていても良く、フェニル基、ナフチル基またはアントリル基であり、その芳香環に置換基を有していてもよい。ｐおよびｑは０〜３の整数を示し、Ａｒ^３およびＡｒ^４はそれぞれＡＬ^１およびＡＬ^２の任意の炭素原子に結合することができる。）

(In formula, Ar < ¹ > and Ar < ² > may be the same or different, and are a phenyl group, a naphthyl group, or an anthryl group, and may have a substituent in the aromatic ring. R < ¹¹ >, R < ¹² >, R ¹³ and R ¹⁴ may be the same or different, and are a hydrogen atom, an aliphatic hydrocarbon group having 1 to 3 carbon atoms, a phenyl group, a naphthyl group or an anthryl group, and have a substituent in the aromatic ring. AL ¹ and AL ² may be the same or different and are branched or straight-chain aliphatic hydrocarbon groups having 1 to 4 carbon atoms, Ar ³ and Ar ⁴ may be the same or It may be different, and may be a phenyl group, a naphthyl group or an anthryl group, and may have a substituent on the aromatic ring, p and q each represent an integer of 0 to ^3, and Ar ³ and Ar ⁴ each represent AL ¹ Contact It can be attached to any carbon atom of the fine AL ^2.)

Furthermore, it is preferably a phosphorus compound represented by the following formulas (5), (6), (7), (8).

In the formula, R ²¹ and R ²² are the same or different and are a phenyl group, a naphthyl group or an anthryl group which may have a substituent on the aromatic ring, and among them, a phenyl group is preferable. The phenyl group, naphthyl group or anthryl group of R ²¹ and R ²² may be substituted with a hydrogen atom of the aromatic ring, and as a substituent, methyl, ethyl, propyl, butyl or a bonding group of the aromatic ring is Examples thereof include an aryl group having 6 to 14 carbon atoms via an oxygen atom, a sulfur atom, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.

In the above formula (6), R ³¹ and R ³⁴ may be the same or different and are a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. Preferred are a hydrogen atom, a methyl group, and an ethyl group, and particularly preferred is a hydrogen atom. R ³³ and R ³⁶ may be the same or different and are each an aliphatic hydrocarbon group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group. R ³² and R ³⁵ may be the same or different, and are a phenyl group, a naphthyl group or an anthryl group, and may have a substituent on the aromatic ring. Preferably, it represents a phenyl group, and may have a substituent in any part other than the part bonded to phosphorus via a carbon atom on the aromatic ring, and includes methyl, ethyl, propyl (including isomers) , Butyl (including isomers) or a group bonded to the aromatic ring thereof is an aryl group having 6 to 14 carbon atoms via oxygen, sulfur or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
In the above formula (6), preferred specific examples of R ³² and R ³⁵ include phenyl group, cresyl group, xylyl group, trimethylphenyl group, 4-phenoxyphenyl group, cumyl group, naphthyl group, 4-benzylphenyl group and the like. In particular, a phenyl group is preferable.

In the above formula (7), Ar ¹ and Ar ² may be the same or different, and are a phenyl group, a naphthyl group, or an anthryl group, and may have a substituent on the aromatic ring. R ¹¹ , R ¹² , R ¹³ and R ¹⁴ may be the same or different and are a hydrogen atom, an aliphatic hydrocarbon group having 1 to 3 carbon atoms, a phenyl group, a naphthyl group or an anthryl group, and its aromatic ring May have a substituent. Preferably, it represents a phenyl group, and may have a substituent in any part other than the part bonded to phosphorus via a carbon atom on the aromatic ring, and includes methyl, ethyl, propyl (including isomers) , Butyl (including isomers) or a group bonded to the aromatic ring thereof is an aryl group having 6 to 14 carbon atoms via oxygen, sulfur or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.

In the above formula (7), preferred specific examples of Ar ¹ and Ar ² include phenyl group, cresyl group, xylyl group, trimethylphenyl group, 4-phenoxyphenyl group, cumyl group, naphthyl group, 4-benzylphenyl group and the like. In particular, a phenyl group is preferable.
In the above formula (7), AL ¹ and AL ² may be the same or different and are branched or straight-chain aliphatic hydrocarbon groups having 1 to 4 carbon atoms. A branched or straight chain aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferable, and a branched or straight chain aliphatic hydrocarbon group having 1 to 2 carbon atoms is particularly preferable.
In the above formula (7), preferred specific examples of AL ¹ and AL ² include a methylene group, an ethylene group, an ethylidene group, a trimethylene group, a propylidene group, an isopropylidene group, and the like. In particular, a methylene group, an ethylene group, and Ethylidene groups are preferred.

In the above formula (7), Ar ³ and Ar ⁴ may be the same or different, and are a phenyl group, a naphthyl group or an anthryl group, and may have a substituent on the aromatic ring. Preferably, it represents a phenyl group, and may have a substituent in any part other than the part bonded to phosphorus via a carbon atom on the aromatic ring, and includes methyl, ethyl, propyl (including isomers) , Butyl (including isomers) or a group bonded to the aromatic ring thereof is an aryl group having 6 to 14 carbon atoms via oxygen, sulfur or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
In the above formula (7), p and q is an integer of 0 to 3, Ar ³ and Ar ⁴ may be bonded to any carbon atoms of AL ¹ and AL ^2, respectively. p and q are preferably 0 or 1, particularly preferably 0.

In the above formula (8), R ⁴¹ and R ⁴⁴ may be the same or different and are a hydrogen atom, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, a phenyl group, a naphthyl group or an anthryl group, The ring may have a substituent. Preferably they are a hydrogen atom, a C1-C3 aliphatic hydrocarbon group, or a phenyl group which may have a substituent. When R ⁴¹ and R ⁴⁴ are phenyl groups, they may have a substituent in any part other than the part bonded to phosphorus via a carbon atom on the aromatic ring, and methyl, ethyl, propyl (isomer The linking group to the aromatic ring is oxygen, sulfur or an aryl group having 6 to 14 carbon atoms via an aliphatic hydrocarbon group having 1 to 4 carbon atoms. .
In the above formula (8), preferred examples of R ⁴¹ and R ⁴⁴ include hydrogen atom, methyl group, ethyl group, propyl group (including isomers), phenyl group, cresyl group, xylyl group, trimethylphenyl group, A 4-phenoxyphenyl group, a cumyl group, a naphthyl group, a 4-benzylphenyl group, and the like can be given. A hydrogen atom, a methyl group, or a phenyl group is particularly preferable.

R ⁴² , R ⁴³ , R ⁴⁵ and R ⁴⁶ may be the same or different and are a phenyl group, a naphthyl group or an anthryl group, and may have a substituent on the aromatic ring. Preferably, it represents a phenyl group and may have a substituent in any part other than the part bonded to phosphorus via a carbon atom on the aromatic ring, and includes methyl, ethyl, propyl (including isomers) ), Butyl (including isomers) or a group bonded to the aromatic ring thereof is an aryl group having 6 to 14 carbon atoms via oxygen, sulfur or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
In the above formula (8), preferred specific examples of R ⁴² , R ⁴³ , R ⁴⁵ and R ⁴⁶ include phenyl group, cresyl group, xylyl group, trimethylphenyl group, 4-phenoxyphenyl group, cumyl group, naphthyl group, 4-benzylphenyl group etc. are mentioned, A phenyl group is especially preferable.

The organophosphorus compound represented by the formula (1) exhibits an extremely excellent flame retardant effect on the resin. As far as the present inventors know, in the conventional flame-retarding of the resin by halogen-free, it is difficult to flame-retardant with a small amount of flame retardant, and there are many problems in practical use.
However, according to the present invention, surprisingly, the organophosphorus compound can easily achieve flame retardancy of the resin by itself in a small amount, and does not impair the original properties of the resin.
A preferred organophosphorus compound as a flame retardant is represented by the above formula (1), and the most preferred representative compounds are the following formulas (1-a), (1-b), (1-c), (1- It is a compound shown by d).

  The flame retardant content is preferably in the range of 0.05 to 50 parts by weight per 100 parts by weight of the polycarbonate resin. Preferably it is 1-40 weight part, More preferably, it is 2-30 weight part, More preferably, it is 3-20 weight part, Especially preferably, it is 3-15 weight part. If it is 0.05 parts by weight or more, sufficient flame retardancy is exhibited, and if it is 50 parts by weight or less, the strength and heat resistance of the molded product are not impaired.

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

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

In injection press molding, the need to fill the resin at high pressure is reduced, so that distortion in the molded product is reduced. Such distortion reduction is important in the uniformity of transmitted light. Furthermore, the reduction of the distortion enables the application of a hard coat agent with higher adhesion.
From the viewpoint of reducing distortion on the surface of the molded product, it is also preferable to combine heat insulating mold forming and rapid heating / cooling mold forming (halogen lamp irradiation, induction heating, high-speed switching of heat medium, ultrasonic mold, etc.) It is.

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

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

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

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

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

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

  The amount of movement of the mold from the intermediate clamping state to the final clamping state of injection press molding (hereinafter sometimes referred to as a compression stroke) is preferably in the range of 1 to 10 mm, more preferably in the range of 1 to 6 mm. A range of 2 to 5 mm is more preferable. A retreat amount in such a range achieves both a low clamping force, which is an advantage of the injection press molding method, and good molding efficiency and appearance of the molded product. Further, the thickness of the molded product is preferably in the range of 0.5 to 5 mm, more preferably in the range of 1 to 4 mm.

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

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

  In the molded product of the present invention, the thickness of the plate-like portion is 0.5 mm to 5 mm, preferably 1 mm to 4 mm. Further, the proportion of the area where the retardation of the plate-like portion is 80 nm or less is 50% or more, preferably 55% or more, and more preferably 60% or more. Furthermore, the ratio of the area where the retardation value in the thickness direction of the plate-like portion of the molded product is 450 nm or less is 50% or more, preferably 55% or more, more preferably 60% or more. When the proportion of the area where the retardation of the plate-like portion is 80 nm or less is less than 50%, blackout occurs when viewed through uneven color or polarized sunglasses, which is not preferable, and the retardation value in the thickness direction of the plate-like portion of the molded product is 450 nm. When the ratio of the following area is less than 50%, color unevenness when viewed from an oblique direction or blackout occurs when viewed through polarized sunglasses, which is not preferable.

(Retardation film)
Next, the retardation film will be described. In the present invention, a retardation film can be laminated on the molded product of the present invention. Examples of the retardation film used in the present invention include polycarbonate, acrylic, polyester, TAC, COP, COC, polyarylate, and liquid crystal. Such a phase difference is not particularly limited, and the phase difference with respect to the wavelength of 590 nm may be 30 nm or more. Especially preferably, it is 50-200 nm, More preferably, it is 70-170 nm, More preferably, it is 90-160 nm. Moreover, 2000 nm or more may be sufficient. More preferably, it is 3000 nm-30000 nm, Most preferably, it is 4000 nm-20000 nm. By using the retardation film, it is possible to prevent darkening when using polarized sunglasses.

(Hard coat)
Next, the hard coat layer will be described. In the present invention, various hard coat agents can be used as a hard coat treatment for the molded article of the present invention. 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. Is exemplified. The hardness of the hard coat layer is not particularly limited as long as it is higher than the hardness of polycarbonate.

  The silicone resin hard coat agent forms a cured resin layer having a siloxane bond. For example, partial hydrolysis of a compound mainly composed of a compound corresponding to a trifunctional siloxane unit (trialkoxysilane compound, etc.). Condensates, preferably partially hydrolyzed condensates further containing compounds corresponding to tetrafunctional siloxane units (tetraalkoxysilane compounds etc.), and further partially hydrolyzed condensates filled with metal oxide fine particles such as colloidal silica Is mentioned. The silicone resin hard coat agent may further contain a bifunctional siloxane unit and a monofunctional siloxane unit. These include 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, an ultraviolet curable hard coat agent is particularly preferable. Furthermore, it is more preferable that the hard coat agent contains a structural unit obtained by copolymerizing an ultraviolet absorbing monomer and / or a photostable monomer. A more suitable organic resin hard coat agent is one in which a hard coat layer is formed by copolymerizing such a monomer and an alkyl (meth) acrylate monomer. Such an ultraviolet curable hard coat agent is preferable in that its processing is simple, and in addition, it is easy to include a structural unit obtained by copolymerizing an ultraviolet absorbing monomer and / or a light stable monomer. This is preferable in that the light resistance of the product can be greatly improved. As a commercial item of an acrylic hard coat agent, for example, Origin Electric series manufactured by Origin Electric Co., Ltd. and Nippon Shokubai Co., Ltd. Udouble series are exemplified. These can be used by mixing with a crosslinking agent component.

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

  Examples of the resin that forms such a primer layer (first layer) include urethane resins, acrylic resins, polyester resins, epoxy resins, melamine resins, amino resins, and polyester acrylates, urethane acrylates, and epoxy resins, which are composed of various blocked isocyanate components and polyol components. 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 primer layer of the silicone resin hard coat agent includes known light stabilizers and ultraviolet absorbers, silicone resin hard coat agent catalysts, thermal / photopolymerization initiators, polymerization inhibitors, silicone It can contain foaming agents, leveling agents, thickeners, suspending agents, anti-sagging agents, flame retardants, various organic / inorganic pigment / dye additives, and auxiliary additives.

（式中Ｒ^１１はメチル基またはエチル基である。）
で表される繰り返し単位、５〜３０モル％の下記式（Ｘ−２）

（式中Ｒ^１２は炭素数２〜５のアルキレン基である。式（Ｘ−２）で表される繰り返し単位において少なくとも一部のＲ^ａは単結合であり、残りが水素原子である。Ｒ^ａが単結合の場合はウレタン結合を介して、他の式（Ｘ−２）で表される繰り返し単位と結合している。）
で表される繰り返し単位、および０〜３０モル％の下記式（Ｘ−３）

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

（式中、Ｑ^１、Ｑ^２は、それぞれ炭素数１〜４のアルキル基、ビニル基、またはメタクリロキシ基、アミノ基、グリシドキシ基および３，４−エポキシシクロヘキシル基からなる群より選ばれる少なくとも一種の基で置換された炭素数１〜３のアルキル基である。）
で表される繰り返し単位からなり、該繰り返し単位の全量を１００モル％としたとき、式（ｐ−４）：８０〜１００モル％、式（ｐ−５）：０〜２０モル％、および式（ｐ−６）：０〜２０モル％である架橋したオルガノシロキサン重合体である、ハードコート層である。 The hard coat layer preferably contains an ultraviolet absorber because it has good durability (particularly durability against adhesion). Furthermore, the more suitable aspect of the hard-coat layer of this invention is as follows. That is, a hard coat layer having a configuration in which the first layer is formed on the surface of the molded article of the present invention and the second layer is formed on the surface of the first layer,
The first layer is composed of a crosslinked acrylic copolymer (acrylic copolymer-I) and an ultraviolet absorber, and the second layer is composed of a crosslinked organosiloxane polymer, and the crosslinked acrylic copolymer (acrylic copolymer). Polymer-I) is 50 mol% or more of the following formula (X-1)

(Wherein R ¹¹ is a methyl group or an ethyl group.)
A repeating unit represented by the formula: 5 to 30 mol% of the following formula (X-2)

(In the formula, R ¹² is an alkylene group having 2 to 5 carbon atoms. In the repeating unit represented by the formula (X-2), at least a part of R ^a is a single bond, and the remainder is a hydrogen atom. ^{When a} is a single bond, it is bonded to a repeating unit represented by the other formula (X-2) via a urethane bond.)
And a repeating unit represented by formula (X-3) of 0 to 30 mol%

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

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

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

(Total light transmittance)
The total light transmittance of the molded article of the present invention is preferably 80% or more, more preferably 88% or more, still more preferably 90% or more, and particularly preferably 91% or more. When it is 80% or more, the visibility is excellent and preferable.

(Display front plate)
The molded article of the present invention can be suitably used as a display front plate of a display device such as a liquid crystal display or organic EL display such as a TV, a computer, a mobile phone, a tablet PC monitor, and various touch panels. In such applications, it is often used as a planar member. In this case, the plate-like portion in the present invention is the entire surface of the molded product. 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.

  Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto. In the examples, “parts” means “parts by weight”. The resins used and the evaluation methods used in the examples are as follows.

1. Polymer composition ratio (NMR)
Each repeating unit was measured by proton NMR of JNM-AL400 manufactured by JEOL Ltd., and the polymer composition ratio (molar ratio) was calculated.

2. Specific Viscosity Measurement The viscosity was determined using an Ostwald viscometer from a solution of 0.7 g of polycarbonate resin in 100 ml of methylene chloride at 20 ° C.
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]

3. Glass transition temperature (Tg)
Temperature rise rate under a nitrogen atmosphere (nitrogen flow rate: 40 ml / min) in accordance with JIS K7121 using a thermal analysis system DSC-2910 manufactured by TA Instruments Co., Ltd. using 8 mg of polycarbonate resin : Measured under the condition of 20 ° C./min.

4). Photoelastic coefficient A film having a width of 1 cm and a length of 6 cm was prepared, and the phase difference of the film under no load state was determined by measuring the phase difference of light having a wavelength of 550 nm when loaded with 1N, 2N, 3N, and a spectroscopic ellipsometer manufactured by JASCO Corporation. It was determined by measuring with “M220” and calculating (phase difference) × (film width) / (load).

5. Birefringence The prepared molded product was measured for phase difference and orientation angle with respect to a wavelength of 590 nm using a micro-area phase difference measuring device KOBRA-CCD / XY30P Oji Scientific Instruments. Further, Rth was measured using Spectroellipometer M-220 manufactured by JASCO Corporation. The measurement was divided into 20 mm × 10 mm sections, and the ratio was calculated by measuring in each section.

6). Pencil hardness A pellet was molded into a 2 mm thick square plate at a cylinder temperature of 250 ° C., a mold temperature of 80 ° C., and a 1 minute cycle using an injection molding machine J85-ELIII manufactured by Tsunasho made in Japan. It was measured by the base plate test method of JIS K5600.

7). Surface impact test Using a high-speed impact tester, Shimadzu HYDROSHOTHITS-P10 (Shimadzu Corporation), a 2 mm thick square plate was used to evaluate cracking at a test speed of 7 m / sec, a striker diameter of 1/2 inch, and a receiving diameter of 1 inch. did.

8). Polarized Sunglass Evaluation The screen of the created display was visually evaluated using polarized sunglasses. The case where the screen looked dark was marked as x, and the case where the screen looked dark was marked as ◯.

[Example 1]
<Manufacture of polycarbonate resin>
375 parts of isosorbide (hereinafter abbreviated as ISS), 101 parts of 1,6-hexanediol (hereinafter abbreviated as HD), 750 parts of diphenyl carbonate (hereinafter abbreviated as DPC), and tetramethylammonium hydroxide 0.8 × 10 ⁻ as a catalyst ² parts and 0.6 × 10 ⁻⁴ parts of sodium hydroxide were heated to 180 ° C. in a nitrogen atmosphere and melted. Thereafter, the degree of vacuum was adjusted to 13.4 kPa over 30 minutes. Thereafter, the temperature was raised to 240 ° C. at a rate of 60 ° C./hr and maintained at that temperature for 10 minutes, and then the degree of vacuum was set to 133 Pa or less over 1 hour. The reaction was carried out with stirring for a total of 6 hours, discharged from the bottom of the reaction tank under nitrogen pressure, and cut with a pelletizer while cooling in a water tank to obtain a pellet. The specific viscosity of the pellet was measured.

<Manufacture of molded products>
Next, the obtained pellets were dried with a hot air circulation dryer at 90 ° C. for 12 hours. After drying, using an injection molding machine LGP450S manufactured by Meiki Seisakusho, cylinder temperature 230 ° C., mold temperature 70 ° C., injection speed 60 mm / second, filling time 2.1 seconds, press stroke 0.3 mm, press force 85 ton, cooling This was carried out for 25 seconds to obtain a molded product having a size of 200 mm × 100 mm and a thickness of 2.5 mm. The phase difference and appearance of the obtained molded product were confirmed.

[Example 2]
<Manufacture of polycarbonate resin>
Except that ISS 426 parts, 2,4-diethyl-1,5-pentanediol (hereinafter abbreviated as DEP) 83 parts, and DPC 750 parts were used as raw materials, the same operation as in Example 1 was performed and the same evaluation was performed. It was. The results are shown in Table 1.

<Manufacture of molded products>
Next, the obtained pellets were dried with a hot air circulation dryer at 90 ° C. for 12 hours. After drying, using an injection molding machine LGP450S manufactured by Meiki Seisakusho, cylinder temperature 240 ° C., mold temperature 100 ° C., injection speed 60 mm / second, filling time 2.1 seconds, press stroke 0.3 mm, press force 85 ton, cooling This was carried out for 25 seconds to obtain a molded product having a size of 200 mm × 100 mm and a thickness of 2.5 mm. The phase difference and appearance of the obtained molded product were confirmed.

[Example 3]
Except that ISS 426 parts, 1,9-nonanediol (hereinafter abbreviated as ND) 83 parts, and DPC 750 parts were used as raw materials, the same operation as in Example 1 was performed and the same evaluation was performed. The results are shown in Table 1.

<Manufacture of molded products>
Next, the obtained pellets were molded in the same manner as in Example 2, and the same evaluation was performed.

[Example 4]
The same evaluation as in Example 1 was performed except that 250 parts of ISS, 247 parts of 1,4-cyclohexanedimethanol (hereinafter abbreviated as CHDM), and 750 parts of DPC were used as raw materials. The results are shown in Table 1.

<Manufacture of molded products>
Next, the obtained pellets were molded in the same manner as in Example 1, and the same evaluation was performed.

[Example 5]
<Manufacture of polycarbonate resin>
375 parts of isosorbide (hereinafter abbreviated as ISS), 101 parts of 1,6-hexanediol (hereinafter abbreviated as HD), 750 parts of diphenyl carbonate (hereinafter abbreviated as DPC), and tetramethylammonium hydroxide 0.8 × 10 ⁻ as a catalyst ² parts and 0.6 × 10 ⁻⁴ parts of sodium hydroxide were heated to 180 ° C. in a nitrogen atmosphere and melted. Thereafter, the degree of vacuum was adjusted to 13.4 kPa over 30 minutes. Thereafter, the temperature was raised to 240 ° C. at a rate of 60 ° C./hr and maintained at that temperature for 10 minutes, and then the degree of vacuum was set to 133 Pa or less over 1 hour. The reaction was carried out with stirring for a total of 6 hours, discharged from the bottom of the reaction tank under nitrogen pressure, and cut with a pelletizer while cooling in a water tank to obtain a pellet. The specific viscosity of the pellet was measured.

<Manufacture of molded products>
Next, the obtained pellets were dried with a hot air circulation dryer at 90 ° C. for 12 hours. After drying, using an injection molding machine LGP450S manufactured by Meiki Seisakusho, cylinder temperature 230 ° C., mold temperature 70 ° C., injection speed 60 mm / second, filling time 2.1 seconds, press stroke 0.3 mm, press force 300 ton, cooling This was carried out for 25 seconds to obtain a molded product having a size of 200 mm × 100 mm and a thickness of 2.5 mm. The phase difference and appearance of the obtained molded product were confirmed.

[Example 6]
A retardation film (manufactured by Teijin Chemicals Ltd., trade name: Pure Ace S-142; retardation 142 nm) was bonded to the molded product obtained in Example 1 via an adhesive. The obtained laminated body was laminated | stacked on the outermost surface of liquid crystal television (BRAVIA KDL-22EX300 2010 made by SONY). Visual evaluation was performed through polarized sunglasses.

[Example 7]
A retardation film (manufactured by Teijin Chemicals Ltd., trade name: Pure Ace T-138; retardation 138 nm) was bonded to the molded product obtained in Example 2 via an adhesive. The obtained laminated body was laminated | stacked on the outermost surface of liquid crystal television (BRAVIA KDL-22EX300 2010 made by SONY). Visual evaluation was performed through polarized sunglasses.

[Comparative Example 1]
Except for using an acrylic resin (Acrypet VH-001 manufactured by Mitsubishi Rayon Co., Ltd.), the same operation as in Example 1 was performed and the same evaluation was performed. The results are shown in Table 1.

[Comparative Example 2]
Polycarbonate resin pellets (Teijin Kasei Co., Ltd. Panlite L-1250) were dried at 120 ° C for 4 hours with a hot air circulation dryer, the cylinder temperature was set to 300 ° C, and the mold temperature was set to 100 ° C. The same operation as in Example 1 was performed, and the same evaluation was performed. The results are shown in Table 1.

[Comparative Example 3]
ISS 375 parts, HD 101 parts and DPC 750 parts are used as raw materials, and tetramethylammonium hydroxide 0.8 × 10 ⁻² parts and sodium hydroxide 0.6 × 10 ⁻⁴ parts are heated to 180 ° C. in a nitrogen atmosphere and melted. I let you. Thereafter, the degree of vacuum was adjusted to 13.4 kPa over 30 minutes. Thereafter, the temperature was raised to 250 ° C. at a rate of 60 ° C./hr and held at that temperature for 10 minutes, and then the degree of vacuum was reduced to 133 Pa or less over 10 minutes. Except that the reaction was carried out under stirring for a total of 5 hours, the same operation as in Example 1 was performed and the same evaluation was performed. The results are shown in Table 1.

[Comparative Example 4]
ISS 375 parts, HD 101 parts and DPC 750 parts are used as raw materials, and tetramethylammonium hydroxide 0.8 × 10 ⁻² parts and sodium hydroxide 0.6 × 10 ⁻⁴ parts are heated to 180 ° C. in a nitrogen atmosphere and melted. I let you. Thereafter, the degree of vacuum was adjusted to 13.4 kPa over 30 minutes. Thereafter, the temperature was raised to 250 ° C. at a rate of 60 ° C./hr and held at that temperature for 10 minutes, and then the degree of vacuum was reduced to 133 Pa or less over 10 minutes. Except that the reaction was carried out with stirring for a total of 7 hours, the same operation as in Example 1 was performed, and the same evaluation was performed. The results are shown in Table 1.

[Comparative Example 5]
A retardation film (manufactured by Teijin Chemicals Ltd., trade name: Pure Ace T-138) was bonded to the molded product obtained in Comparative Example 2 via an adhesive. The obtained laminated body was laminated | stacked on the outermost surface of liquid crystal television (BRAVIA KDL-22EX300 2010 made by SONY). Visual evaluation was performed through polarized sunglasses.

  The molded article of the present invention is useful as a display front plate.

Claims (8)

A plate-shaped part comprising a carbonate unit (A) represented by the following formula (A) and formed from a polycarbonate resin having a specific viscosity of 0.3 to 0.5 measured with a 20 ° C. methylene chloride solution. Retardation in the thickness direction of the plate-shaped part of the molded product, wherein the thickness of the plate-shaped part is 0.5 mm to 5 mm, and the proportion of the area where the phase difference of the plate-shaped part is 80 nm or less is 50% or more A molded product characterized in that the ratio of the area having a value of 450 nm or less is 50% or more.

The molded article according to claim 1, wherein the absolute value of the photoelastic coefficient of the polycarbonate resin is 30 × 10 ⁻¹² Pa ⁻¹ or less.   The molded article according to claim 1, wherein the glass transition temperature of the polycarbonate resin is 70C to 150C.   The molded product according to claim 1, wherein the molded product is obtained by injection press molding.   2. The molded product according to claim 1, wherein a retardation film is laminated on at least one surface of the molded product.   2. The molded product according to claim 1, wherein at least one surface of the molded product is hard-coated.   The molded product according to claim 1, wherein at least one side of the molded product is decorated in a mold.   A display front plate formed from the molded product according to claim 1.