JP5652056B2 - Resin composition and resin molded body - Google Patents

Description

  The present invention relates to a resin composition and a resin molded article excellent in low optical distortion, light resistance, transparency, hue, heat resistance, thermal stability, and mechanical strength.

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

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

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

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

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

International Publication No. 04/111106 Pamphlet JP 2006-232897 A JP 2006-28441 A JP 2008-24919 A JP 2009-91404 A JP 2009-91417 A JP 2009-102537 A JP 2009-242752 A

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

  An object of the present invention is to provide a resin composition and a resin molded article that solve the above-mentioned conventional problems and are excellent in low optical distortion, light resistance, hue, transparency, thermal stability, and mechanical strength. It is in.

As a result of intensive studies to solve the above problems, the present inventor has found that the number average molecular weight (Mn1) of the resin and the maximum phase difference (Re) of the molded body (thickness 3 mm) molded from the resin composition containing the resin. _MAX ) is a resin composition characterized by having the relationship of the following formula (I): not only has excellent low optical distortion, but also excellent light resistance, hue, transparency, thermal stability, And the present invention has been found.

Re ≦ −0.006Mn1 + 350 (I)
That is, the gist of the present invention resides in the following [1] to [18].
[1] The relationship of the following formula (I) between the number average molecular weight (Mn1) of a resin and the maximum phase difference (Re _MAX ) of a molded product (thickness 3 mm) molded from the resin composition containing the resin: A resin composition comprising:

Re _MAX ≦ −0.006Mn1 + 350 (I)
[2] The resin composition according to [1], comprising a resin including at least a structural unit derived from a dihydroxy compound having a site represented by the following general formula (1) in a part of the structure. .

(However, the site represented by the above general formula (1) unless it is part of _-CH 2 -O-H.)
[3] The resin composition further includes a structural unit derived from at least one compound selected from the group consisting of an aliphatic dihydroxy compound and an alicyclic hydrocarbon dihydroxy compound [1] or The resin composition as described in [2].
[4] The structural unit derived from a dihydroxy compound having a site represented by the following general formula (1) in a part of the structure with respect to all dihydroxy compounds is 30 to 80 mol% [2] or [ 3].

(However, the site represented by the above general formula (1) unless it is part of _-CH 2 -O-H.)
[5] The dihydroxy compound having a part represented by the following general formula (1) in a part of the structure is a compound represented by the following general formula (2) [2] to [4] The resin composition in any one of.

(However, the site represented by the above general formula (1) unless it is part of _-CH 2 -O-H.)

[6] It contains at least one metal compound selected from the group consisting of lithium and a metal of Group 2 of the long-period periodic table, and the content of the metal compound is 20 ppm or less as a metal amount The resin composition according to any one of [1] to [5].
[7] The at least one metal compound selected from the group consisting of metals of Group 2 of the long-period periodic table is at least one metal compound selected from the group consisting of magnesium compounds and calcium compounds. The resin composition according to [6].
[8] The resin composition according to any one of [1] to [7], which contains 60 ppm by weight or less of carbonic acid diester represented by the following general formula (3).

(In General Formula (3), A ¹ and A ² are each independently a substituted or unsubstituted aliphatic group having 1 to 18 carbon atoms or a substituted or unsubstituted aromatic group, and A ¹ and A ² may be the same or different.)
[9] The resin composition according to any one of [1] to [8], which contains 700 ppm by weight or less of an aromatic monohydroxy compound.
[10] The resin according to any one of [1] to [9], wherein the concentration of the terminal group represented by the following general formula (4) is in the range of 20 μeq / g to 160 μeq / g. Composition.

[11] A / (A + B) ≦ 0.05, where (A) is the number of moles of H bonded to an aromatic ring and (B) is the number of moles of H bonded to an aromatic ring. The resin composition according to any one of [1] to [10].
[12] The rate of change between the number average molecular weight (Mn1) of the resin and the number average molecular weight (Mn2) of a molded article molded from the resin composition containing the resin is within 10% [1] Thru | or the resin composition in any one of [11].
[13] The resin molded product (thickness 3 mm) molded from the resin composition has a light transmittance of 60% or more at a wavelength of 350 nm, according to any one of [1] to [12] Resin composition.
[14] The resin molded body (thickness 3 mm) molded from the resin composition has a light transmittance of 30% or more at a wavelength of 320 nm, according to any one of [1] to [13] Resin composition.
[15] An initial yellow index value of a resin molded body (thickness 3 mm) molded from the resin composition and a wavelength of 300 nm to 400 nm using a metal halide lamp in an environment of 63 ° C. and a relative humidity of 50%. The absolute value of the difference from the yellow index (YI) value according to ASTM D 1925-70 measured with transmitted light after irradiation treatment at an irradiance of 1.5 kW / m ² for 100 hours is 6 or less. The resin composition according to any one of [1] to [14].
[16] A resin molded article obtained by injection molding the resin composition according to any one of [1] to [15].
[17] The resin molded article according to [16], wherein the injection molding is injection press molding.
[18] The resin molded article according to any one of [16] and [17], wherein the maximum projected area is 500 to 50,000 cm ² .

According to the present invention, a resin molded product having not only excellent low optical distortion but also excellent light resistance, hue, transparency, thermal stability, and mechanical strength can be obtained. Applicable to a wide range of fields such as injection molding for automobile parts, lens applications such as camera lenses, viewfinder lenses, CCD and CMOS lenses, optical disks, optical materials, optical components, binders for immobilizing dyes, charge transfer agents, etc. It becomes possible to provide a possible resin composition and resin molding.

Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the invention.
(1) Resin composition Hereinafter, the resin composition for obtaining the resin molding of this invention is explained in full detail.
[resin]
<Raw material>
(Dihydroxy compound)
The resin used in the present invention (hereinafter sometimes referred to as “the resin of the present invention”) is a dihydroxy compound (hereinafter referred to as “the present invention”) having a portion represented by the following general formula (1) in a part of its structure. At least a structural unit derived from “dihydroxy compound”. That is, the dihydroxy compound of the present invention refers to a compound containing at least two hydroxyl groups and at least a structural unit of the following general formula (1).

(However, the site represented by the above general formula (1) unless it is part of _-CH 2 -O-H.)
The dihydroxy compound of the present invention is not particularly limited as long as it has a site represented by the above general formula (1) in a part of its structure. Specifically, diethylene glycol, triethylene glycol, Oxyalkylene glycols such as tetraethylene glycol, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-isopropylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-isobutylphenyl) fluorene, 9,9-bis ( 4- (2-hydroxyethoxy) -3-tert-butylphenyl) fluorene, 9,9-bis (4- (2 Hydroxyethoxy) -3-cyclohexylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3, 5-Dimethylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-tert-butyl-6-methylphenyl) fluorene 9,9-bis (4- (3-hydroxy-2,2 -Dimethylpropoxy) phenyl) fluorene and the like, a compound having an aromatic group in the side chain and an ether group bonded to the aromatic group in the main chain, represented by the dihydroxy compound represented by the following general formula (2) Examples include anhydrous sugar alcohols and compounds having a cyclic ether structure such as spiroglycol represented by the following general formula (5). Ease, handling, reactivity during polymerization, from the viewpoint of the hue of the resulting resin, diethylene glycol, triethylene glycol are preferable, from the viewpoint of heat resistance, sugar alcohol anhydride, a compound having a cyclic ether structure preferred.

  These may be used alone or in combination of two or more depending on the required performance of the resin to be obtained.

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

  The resin of the present invention may contain a structural unit derived from a dihydroxy compound other than the above-mentioned dihydroxy compound of the present invention (hereinafter sometimes referred to as “other dihydroxy compound”). As other dihydroxy compounds, Ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-heptanediol, 1,6-hexane Aliphatic dihydroxy compounds such as diol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, pentacyclopentadecane dimethanol, 2,6-deca Lindimethanol, 1,5-decalindimethanol, 2 3- decalin methanol, 2,3-norbornane methanol, 2,5-norbornane methanol, 1,3-adamantane dimethanol, dihydroxy compound alicyclic hydrocarbon and the like and the like.

Also, 2,2-bis (4-hydroxyphenyl) propane [= bisphenol A], 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3) , 5-diethylphenyl) propane, 2,2-bis (4-hydroxy- (3,5-diphenyl) phenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2, 2-bis (4-hydroxyphenyl) pentane, 2,4′-dihydroxy-diphenylmethane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-5-nitrophenyl) methane, 1,1-bis (4- Hydroxyphenyl) ethane, 3,3-bis (4-hydroxyphenyl) pentane, 1,1-bis (4-hydroxyphenyl) cyclohexa Bis (4-hydroxyphenyl) sulfone, 2,4′-dihydroxydiphenylsulfone, bis (4-hydroxyphenyl) sulfide, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dichloro Diphenyl ether, 9,9-bis (4- (2-hydroxyethoxy-2-methyl) phenyl) fluorene, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-2-methyl) Aromatic bisphenols such as phenyl) fluorene can also be used.

  Among these, from the viewpoint of the light resistance of the resin, at least one compound selected from the group consisting of dihydroxy compounds having no aromatic ring structure in the molecular structure, that is, aliphatic dihydroxy compounds and alicyclic hydrocarbon dihydroxy compounds, is used. 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol are particularly preferable as the aliphatic hydrocarbon dihydroxy compound, and as the alicyclic dihydroxy compound, particularly 1, 4-cyclohexanedimethanol and tricyclodecane dimethanol are preferred.

By using these other dihydroxy compounds, it is possible to obtain effects such as improvement in flexibility of the resin, improvement in heat resistance, improvement in moldability, etc., but inclusion of structural units derived from other dihydroxy compounds If the proportion is too large, mechanical properties and heat resistance may be lowered. Therefore, the proportion of structural units derived from the dihydroxy compound of the present invention with respect to the total dihydroxy compound is preferably 30 mol% or more, and more Preferably it is 40 mol% or more, particularly preferably 45 mol% or more, most preferably 65 mol5% or more, on the other hand, preferably 80 mol% or less, more preferably 78 mol% or less, particularly preferably 75 mol% or less. .
Between the resin composition of the present invention, that is, the number average molecular weight (Mn1) of the resin and the maximum phase difference (Re _MAX ) of a molded body (thickness 3 mm) molded from the resin composition containing the resin (re _MAX ) I)
One means for achieving a resin composition characterized by having the formula relationship is to set the ratio of the dihydroxy compound of the present invention to the specific range relative to the total dihydroxy compound.

Re _MAX ≦ −0.006Mn1 + 350 (I)
The dihydroxy compound of the present invention may contain a stabilizer such as a reducing agent, antioxidant, oxygen scavenger, light stabilizer, antacid, pH stabilizer, heat stabilizer, etc. Since the dihydroxy compound is easily altered, it is preferable to include a basic stabilizer. Basic stabilizers include the long-period periodic table (Nomenclature of Inorganic Chemistry IUPAC Recommendations
Group 1 or Group 2 metal hydroxides, carbonates, phosphates, phosphites, hypophosphites, borates, fatty acid salts, tetramethylammonium hydroxide, tetraethylammonium hydroxide , Tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributyl Benzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriflate Basic ammonium compounds such as nyl ammonium hydroxide, methyl triphenyl ammonium hydroxide, butyl triphenyl ammonium hydroxide, 4-aminopyridine, 2-aminopyridine, N, N-dimethyl-4-aminopyridine, 4-diethylaminopyridine Amine compounds such as 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2-dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, and aminoquinoline. Of these, sodium or potassium phosphates and phosphites are preferred, and disodium hydrogen phosphate and disodium hydrogen phosphite are particularly preferred because of their effects and ease of distillation removal described below.

The content of these basic stabilizers in the dihydroxy compound of the present invention is not particularly limited, but if it is too small, there is a possibility that the effect of preventing alteration of the dihydroxy compound of the present invention may not be obtained, and if it is too large, the present invention. Therefore, it is usually 0.0001% by weight to 1% by weight, preferably 0.001% by weight to 0.1% by weight, based on the dihydroxy compound of the present invention.

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

  When the dihydroxy compound of the present invention has a cyclic ether structure such as isosorbide, it is likely to be gradually oxidized by oxygen. It is important to use an oxygen agent or the like or handle it under a nitrogen atmosphere. When isosorbide is oxidized, decomposition products such as formic acid may be generated. For example, when isosorbide containing these decomposition products is used as a raw material for producing the resin of the present invention, the resulting resin of the present invention may be colored, and the physical properties may be significantly deteriorated. The polymerization reaction is affected, and a high molecular weight polymer may not be obtained.

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

  By such purification by distillation, the dihydroxy compound of the present invention is contained by adjusting the formic acid content in the dihydroxy compound of the present invention to 20 ppm by weight or less, preferably 10 ppm by weight or less, particularly preferably 5 ppm by weight or less. When a dihydroxy compound is used as a raw material for producing the resin of the present invention, a resin excellent in hue and thermal stability can be produced without impairing polymerization reactivity. The formic acid content is measured by ion chromatography.

(Carbonated diester)
The resin of the present invention can be obtained by polycondensation by a transesterification reaction using the above-mentioned dihydroxy compound containing the dihydroxy compound of the present invention and a carbonic acid diester as raw materials.
As a carbonic acid diester used, what is normally represented by following General formula (3) is mentioned. These carbonic acid diesters may be used alone or in combination of two or more.

(In General Formula (3), A ¹ and A ² are each independently a substituted or unsubstituted aliphatic group having 1 to 18 carbon atoms or a substituted or unsubstituted aromatic group, and A ¹ and A ² may be the same or different.)
Examples of the carbonic acid diester represented by the general formula (3) include substituted diphenyl carbonate such as diphenyl carbonate and ditolyl carbonate, dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate. Diphenyl carbonate and substituted difel carbonate are preferable, and diphenyl carbonate is particularly preferable. Carbonic acid diesters may contain impurities such as chloride ions, which may hinder the polymerization reaction or worsen the hue of the resulting resin. It is preferable to use one.
The resin of the present invention is preferably a polycarbonate resin, and a preferred resin composition is a polycarbonate resin composition.

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

The transesterification reaction catalyst (hereinafter sometimes simply referred to as “catalyst” or “polymerization catalyst”) that can be used in the production of the resin of the present invention has an influence on the light transmittance at a wavelength of 350 nm and the yellow index value. Can give.
The catalyst used is not limited as long as the light resistance can be satisfied, that is, the light transmittance at a wavelength of 350 nm or the yellow index can be set to a predetermined value, but the first group in the long-period periodic table is not limited. Or a basic compound such as a metal compound, a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound of Group 2 (hereinafter, simply referred to as “Group 1” or “Group 2”). Can be mentioned. Preferably, Group 1 metal compounds and / or Group 2 metal compounds are used.

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

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

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

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

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

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

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

If the amount of the catalyst is too small, the polymerization rate will slow down. As a result, when trying to obtain a resin with the desired molecular weight, the polymerization temperature will have to be increased, and the hue and light resistance of the resulting resin will deteriorate. The unreacted raw material volatilizes during the polymerization, and the molar ratio of the dihydroxy compound containing the dihydroxy compound of the present invention to the carbonic acid diester represented by the general formula (3) may collapse, and the desired molecular weight may not be reached. . On the other hand, when the amount of the polymerization catalyst used is too large, the hue of the resulting resin is deteriorated, and the light resistance of the resin may be deteriorated.

Further, Group 1 metals, especially sodium, potassium and cesium, especially lithium, sodium, potassium and cesium, may have a bad influence on the hue when contained in the resin in a large amount. However, the total amount of these compounds in the resin is usually 1 ppm by weight or less, preferably 0.8 ppm by weight or less, and more preferably 0.8 ppm or less as the amount of metal because they may be mixed from raw materials or reaction equipment. 7 ppm by weight or less.
The amount of metal in the resin can be measured using a method such as atomic emission, atomic absorption, or inductively coupled plasma (ICP) after recovering the metal in the resin by a method such as wet ashing.

<Manufacturing method>
The resin of the present invention can be obtained by polycondensation of a dihydroxy compound containing the dihydroxy compound of the present invention and a carbonic acid diester by an ester exchange reaction. The raw material dihydroxy compound and the carbonic acid diester are uniformly mixed before the ester exchange reaction. It is preferable to mix.

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

The operation of mixing the dihydroxy compound containing the dihydroxy compound of the present invention, which is the raw material of the resin of the present invention, and the carbonic acid diester is an oxygen concentration of 10 vol% or less, more preferably 0.0001 vol% to 10 vol%, especially 0.0001 vol% to 5 vol%. In particular, it is preferable to perform in an atmosphere of 0.0001 vol% to 1 vol% from the viewpoint of preventing hue deterioration.
In order to obtain the resin of the present invention, the carbonic acid diester represented by the general formula (3) is used in a molar ratio of 0.90 to 1.20 with respect to all the dihydroxy compounds including the dihydroxy compound of the present invention used in the reaction. The ratio is preferably used, and more preferably a molar ratio of 0.95 to 1.10.

Moreover, when this molar ratio becomes large, the rate of the transesterification reaction may decrease, or it may be difficult to produce a desired molecular weight. The decrease in the transesterification reaction rate may increase the thermal history during the polymerization reaction, and may deteriorate the hue and light resistance of the resulting resin.
Furthermore, when the molar ratio of the carbonic diester represented by the general formula (3) is increased with respect to all the dihydroxy compounds including the dihydroxy compound of the present invention, the amount of residual carbonic diester in the resulting resin increases. May absorb ultraviolet rays and deteriorate the light resistance of the resin, which is not preferable. The concentration of the carbonic acid diester represented by the general formula (3) remaining in the resin of the present invention is preferably 60 ppm by weight or less, more preferably 50 ppm by weight or less, and particularly preferably 40 ppm by weight or less. In reality, the resin may contain unreacted carbonic acid diester, and the lower limit of the concentration is usually 1 ppm by weight.

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

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

In order to maintain the polymerization rate appropriately and suppress the distillation of the monomer, but not to impair the final resin hue, thermal stability, light resistance, etc., select the type and amount of the catalyst described above. is important.
The resin of the present invention is preferably produced by polymerizing in multiple stages using a plurality of reactors using a catalyst, but the reason for carrying out the polymerization in a plurality of reactors is the reaction at the initial stage of the polymerization reaction. Since many monomers are contained in the liquid, it is important to suppress the volatilization of the monomers while maintaining the necessary polymerization rate. In the late stage of the polymerization reaction, by-products are generated in order to shift the equilibrium to the polymerization side. This is because it is important to sufficiently distill off the monohydroxy compound. Thus, in order to set different polymerization reaction conditions, it is preferable from the viewpoint of production efficiency to use a plurality of polymerization reactors arranged in series.

As described above, the number of reactors used in the method of the present invention may be at least two or more. However, from the viewpoint of production efficiency and the like, three or more, preferably 3 to 5, particularly preferably 4 are used. One.
In the present invention, if there are two or more reactors, a plurality of reaction stages having different conditions may be provided in the reactor, or the temperature and pressure may be continuously changed.

In the present invention, the polymerization catalyst can be added to the raw material preparation tank, the raw material storage tank, or can be added directly to the polymerization tank. From the viewpoint of supply stability and polymerization control, the polymerization catalyst is supplied to the polymerization tank. A catalyst supply line is installed in the middle of the raw material line before being fed, and preferably supplied as an aqueous solution.
If the temperature of the polymerization reaction is too low, the productivity is lowered and the thermal history of the product is increased. If it is too high, not only the monomer is volatilized, but also decomposition and coloring of the resin may be promoted.

  Specifically, the first stage reaction is carried out at 140 to 270 ° C., preferably 180 to 240 ° C., more preferably 200 to 230 ° C. as the maximum internal temperature of the polymerization reactor, preferably 110 to 1 kPa, Is carried out at a pressure of 70 to 5 kPa, more preferably 30 to 10 kPa (absolute pressure) for 0.1 to 10 hours, preferably 0.5 to 3 hours, while distilling off the generated monohydroxy compound out of the reaction system. Is done.

In the second and subsequent stages, the pressure in the reaction system is gradually reduced from the pressure in the first stage, and the monohydroxy compound that is subsequently generated is removed from the reaction system. 2
The maximum internal temperature is 210 to 270 ° C., preferably 220 to 250 ° C., usually 0.1 to 10 hours, preferably 1 to 6 hours, particularly preferably 0.5 to 3 hours.

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

In order to obtain a resin having a predetermined molecular weight, if the polymerization temperature is increased and the polymerization time is too long, the ultraviolet transmittance tends to decrease and the YI value tends to increase.
The monohydroxy compound produced as a by-product is preferably reused as a raw material for diphenyl carbonate, bisphenol A, etc. after purification as necessary from the viewpoint of effective utilization of resources.
As described above, the resin of the present invention is usually cooled and solidified after polycondensation and pelletized with a rotary cutter or the like.

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

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

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

Extrusion of the resin of the present invention is preferably carried out in a clean room having a higher degree of cleanliness than class 7 as defined in JIS B 9920 (2002), more preferably higher than class 6, in order to prevent foreign matter from being mixed after extrusion. Is desirable.
Further, when cooling the extruded resin into chips, it is preferable to use a cooling method such as air cooling or water cooling. As the air used for air cooling, it is desirable to use air from which foreign substances in the air have been removed in advance with a hepa filter or the like to prevent reattachment of foreign substances in the air. When water cooling is used, it is desirable to use water from which metal in water has been removed with an ion exchange resin or the like, and foreign matter in water has been removed with a filter. The opening of the filter to be used is preferably 10 to 0.45 μm as 99% removal filtration accuracy.

The molecular weight of the resin of the present invention thus obtained can be represented by a reduced viscosity, and the reduced viscosity is usually 0.30 dL / g or more, preferably 0.35 dL / g or more, and the upper limit of the reduced viscosity. Is more preferably 1.20 dL / g or less and 1.00 dL / g or less, and still more preferably 0.80 dL / g or less.
If the reduced viscosity of the resin is too low, the mechanical strength of the molded product may be small, and if it is too large, the fluidity at the time of molding tends to decrease, and the productivity and moldability tend to decrease.

The reduced viscosity is measured using a Ubbelohde viscometer at a temperature of 20.0 ° C. ± 0.1 ° C., using methylene chloride as a solvent and precisely preparing a resin concentration of 0.6 g / dL.
Further, the lower limit of the concentration of the terminal group represented by the following general formula (4) in the resin of the present invention (referred to as “terminal phenyl group concentration”) is preferably 20 μeq / g, more preferably 40 μeq / g, particularly preferably. Is 50 μeq / g, while the upper limit is preferably 160 μeq / g, more preferably 140 μeq / g, particularly preferably 100 μeq / g.

If the concentration of the end group represented by the following general formula (4) is too high, even if the hue at the time of polymerization or molding is good, the hue after exposure to ultraviolet light may be deteriorated. Thermal stability may be reduced.
In order to control the concentration of the terminal group represented by the following general formula (4), the molar ratio of the dihydroxy compound containing the dihydroxy compound of the present invention as a raw material and the carbonic acid diester represented by the general formula (3) is controlled. In addition, the method and the like of controlling the type and amount of the catalyst during the transesterification reaction, the polymerization pressure and the polymerization temperature can be mentioned.

  When using the substituted diphenyl carbonate such as diphenyl carbonate and ditolyl carbonate as the carbonic acid diester represented by the general formula (4) to produce the resin of the present invention, phenol and substituted phenol are by-produced and remain in the resin. However, since phenol and substituted phenol also have an aromatic ring, they may absorb ultraviolet rays and cause deterioration of light resistance, and may cause odor during molding. The resin contains an aromatic monohydroxy compound having an aromatic ring such as by-product phenol of 1000 ppm by weight or more after a normal batch reaction, but from the viewpoint of light resistance and odor reduction, it is devolatilized. It is preferably 700 ppm by weight or less, more preferably 500 ppm by weight or less, and particularly preferably 300 ppm by weight or less using a horizontal reactor having excellent performance or an extruder with a vacuum vent. However, it is difficult to remove completely industrially, and the lower limit of the content of the aromatic monohydroxy compound is usually 1 ppm by weight.

These aromatic monohydroxy compounds may naturally have a substituent depending on the raw material used, and may have, for example, an alkyl group having 5 or less carbon atoms.
Further, when the number of moles of H bonded to the aromatic ring of the resin of the present invention is (A) and the number of moles of H bonded to other than the aromatic ring is (B), the total number of moles of H bonded to the aromatic ring The ratio of H to the number of moles is represented by A / (A + B). However, since the aromatic ring having the ability to absorb ultraviolet rays may affect the light resistance as described above, A / (A + B ) Is preferably 0.05 or less, more preferably 0.03 or less, particularly preferably 0.02 or less, and preferably 0.01 or less. A / (A + B) can be quantified by ¹ H-NMR.

[Other additives]
The resin composition of the present invention usually further contains other additives in the resin of the present invention. For example, antioxidants, acidic compounds, ultraviolet absorbers, light stabilizers, inorganic fillers and the like can be mentioned.
The antioxidant is preferably at least one selected from the group consisting of phenolic antioxidants, phosphate antioxidants and sulfur antioxidants, and phenolic antioxidants and / or phosphate oxidations. An inhibitor is more preferred.

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

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

  Examples of the phosphate antioxidant include triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, tri Octadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert -Butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaeri Li diphosphite, bis (2,4-di -tert- butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, and the like.

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

Examples of the sulfur-based antioxidant include dilauryl-3,3′-thiodipropionate, ditridecyl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, diester Stearyl-3,3′-thiodipropionate, laurylstearyl-3,3′-thiodipropionate, pentaerythritol tetrakis (3-laurylthiopropionate), bis [2-methyl-4- (3 -Laurylthiopropionyloxy) -5-tert-butylphenyl] sulfide, octadecyl disulfide, mercaptobenzimidazole, 2-mercapto-6-methylbenzimidazole, 1,1′-thiobis (2-naphthol) and the like. Among the above, pentaerythritol tetrakis (3-lauryl thiopropionate) is preferable.
The content of the antioxidant is preferably 0.001 part by weight or more, more preferably 0.01 part by weight or more, particularly preferably 0.05 part by weight or more, with respect to 100 parts by weight of the resin of the present invention. The amount is preferably 1 part by weight or less, more preferably 0.7 part by weight or less, and particularly preferably 0.5 part by weight or less. If the content of the antioxidant is excessively small, the coloring suppression effect during molding may be insufficient. Also, if the content of the antioxidant is excessively large, the amount of deposits on the mold during injection molding increases or the number of deposits on the roll increases when forming a film by extrusion. The surface appearance of the product may be damaged.

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

These acidic compounds can be added in the production process of the resin composition as compounds that neutralize the basic transesterification catalyst used in the above-described resin polycondensation reaction.
The compounding amount of the acidic compound is 0.00001 part by weight or more and 0.1 part by weight or less, preferably 0.0001 part by weight or more and 0.01 part by weight or less, based on 100 parts by weight of the resin. Preferably they are 0.0002 weight part or more and 0.001 weight part or less. If the blending amount of the acidic compound is excessively small, it may not be possible to sufficiently suppress coloring when the residence time of the resin composition in the injection molding machine becomes long during injection molding. Moreover, when there are too many compounding quantities of an acidic compound, the hydrolysis resistance of a resin composition may fall remarkably.

The resin composition of the present invention can contain an ultraviolet absorber and a light stabilizer as long as the object of the present invention is not impaired. The content of the stabilizer is preferably 0.01 part by weight to 2 parts by weight with respect to 100 parts by weight of the resin.
Examples of the inorganic filler include glass fiber, glass milled fiber, glass flake, glass bead, carbon fiber, silica, alumina, titanium oxide, calcium sulfate powder, gypsum, gypsum whisker, barium sulfate, talc, mica, and wallast. Calcium silicate such as knight; carbon black, graphite, iron powder, copper powder, molybdenum disulfide, silicon carbide, silicon carbide fiber, silicon nitride, silicon nitride fiber, brass fiber, stainless steel fiber, potassium titanate fiber, whisker, etc. It is done. Among these, glass fiber filler, glass powder filler, glass flake filler; carbon fiber filler, carbon powder filler, carbon flake filler; various whiskers, mica Talc is preferred. More preferably, glass fiber, glass flake, glass milled fiber, carbon fiber, wollastonite, mica and talc are mentioned.

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

  The resin composition of the present invention can be produced by mixing the above components simultaneously or in any order with a mixer such as a tumbler, V-type blender, nauter mixer, Banbury mixer, kneading roll, or extruder. Furthermore, a nucleating agent, a flame retardant, an inorganic filler, an impact modifier, a foaming agent, a dye / pigment and the like that are usually used in the resin composition may be contained within a range not impairing the object of the present invention.

The resin composition of the present invention contains at least one metal compound selected from the group consisting of a lithium compound and a metal of Group 2 of the long-period periodic table, and the content of the metal compound is preferably as a metal amount. Is 0.1 ppm by weight or more, more preferably 0.5 ppm by weight or more, and particularly preferably 0.7 ppm by weight or more. The the upper limit, preferably 20 ppm by weight or less, more preferably 10 weight ppm or less, particularly preferably 3 ppm by weight, most preferably from 1.5 ppm by weight or less, with preference 1.0 wt ppm or less.

The resin molded body in the present invention, the maximum projected area of the molded resin from the viewpoint of use in optical applications, preferably 500～50,000Cm ^2, more preferably 1000～20,000Cm ^2, particularly preferably 1500 ~10,000cm ² there.
The lower limit amount of the terminal group concentration (referred to as “terminal phenyl group concentration”) represented by the following general formula (4) in the resin composition of the present invention is preferably 20 μeq / g, more preferably 40 μeq / g, particularly The upper limit is preferably 160 μeq / g, more preferably 140 μeq / g, particularly preferably 100 μeq / g.
If the concentration of the end group represented by the following general formula (4) is too high, even if the hue at the time of polymerization or molding is good, the hue after UV exposure may be deteriorated. Thermal stability may be reduced.

The resin composition of the present invention preferably contains an aromatic monohydroxy compound in an amount of 700 ppm by weight or less, more preferably 500 ppm by weight or less, and particularly preferably 300 ppm by weight or less. However, it is difficult to remove completely industrially, and the lower limit of the content of the aromatic monohydroxy compound is usually 1 ppm by weight.
The concentration of the carbonic acid diester represented by the general formula (3) remaining in the resin composition of the present invention is preferably 60 ppm by weight or less, more preferably 50 ppm by weight or less, and particularly preferably 40 ppm by weight or less. is there. In reality, the resin may contain unreacted carbonic acid diester, and the lower limit of the concentration is usually 1 ppm by weight.

In the resin molded body of the present invention, the light transmittance of the resin molded body (thickness 3 mm) at a wavelength of 350 nm is preferably 60% or more, more preferably 65% or more, and particularly preferably 70% or more. When the light transmittance at the wavelength is less than 60%, the absorption increases and the light resistance may deteriorate.
The resin molded body of the present invention preferably has a light transmittance at a wavelength of 320 nm of the resin molded body (3 mm thick flat plate) of 30% or more, more preferably 40% or more, and particularly preferably 50% or more. preferable. When the light transmittance at the wavelength is less than 30%, the light resistance tends to deteriorate.

  The resin molded body of the present invention is a 1.5 kW irradiance having a wavelength of 300 nm to 400 nm using a metal halide lamp in an environment of 63 ° C. and a relative humidity of 50%. After the irradiation treatment at m2, the yellow index (YI) value based on ASTM D1925-70 measured with transmitted light is 12 or less, preferably 10 or less, particularly preferably 8 or less.

In addition, although the irradiation process using the metal halide lamp in the present invention will be described later, a specific device is used and a specific filter or the like is used to mainly emit light having a wavelength of 300 nm to 400 nm (light having a wavelength outside this wavelength range can be as much as possible). Removed), which means irradiating the sample for 100 hours with an irradiance of 1.5 kW / m ² .
When the yellow index (YI) value according to ASTM D1925-70 measured after 100 hours of irradiation treatment with a irradiance of 1.5 kW / m ² at a wavelength of 300 nm to 400 nm using the metal halide lamp exceeds 12, immediately after molding Found that even if it is not colored, it may be colored when exposed to light containing ultraviolet light, and surprisingly, it includes the heat history received in the transesterification reaction (polycondensation reaction) and the catalyst used. This is based on the knowledge that it can be solved by controlling the metal component, the content of a substance having a specific molecular structure, and the like.

In addition, the resin composition of the present invention is molded into a 3 mm-thick flat plate from the resin composition, and the yellow index value (initial value) measured with transmitted light without performing irradiation treatment with the metal halide lamp as described above. Of the yellow index value, which is referred to as the initial YI value) is preferably 10 or less, more preferably 7 or less, particularly preferably 5 or less, and the absolute value of the difference between the yellow index values before and after the metal halide lamp irradiation. Is preferably 6 or less, more preferably 4 or less, and particularly preferably 3 or less.
In addition, the preferable resin molding in this invention is the polycarbonate resin molding which was injection-molded from the polycarbonate resin composition.

<Manufacturing method>
The resin molded product is manufactured by various methods. Among them, extrusion molding is generally used, but the shape of the resin molded product is limited, and it is difficult to manufacture a resin molded product having a complicated shape.
The resin molded body of the present invention is manufactured by injection molding. In particular, it is preferably performed by injection press molding from the viewpoint of low optical distortion of the resin molded body. In the case of injection molding, a resin molded body having a complicated shape can be produced by using a mold corresponding to the shape of the resin molded product.

Injection molding is performed by an injection molding machine, and suitable molding conditions are appropriately set according to the resin composition to be used and the product shape. The molding conditions include cylinder temperature, mold temperature, injection pressure, holding pressure, screw rotation speed, cushion amount, injection speed, injection time, pressure holding time, cooling time, and the like.
In particular, in the production of the resin molded body of the present invention, the cylinder temperature is preferably 200 to 300 ° C, more preferably 210 to 280 ° C, particularly preferably 220 to 270 ° C, and most preferably 230 to 260 ° C. If the cylinder temperature is too low, the maximum phase difference (Re _MAX )
On the other hand, if it is too high, the resin composition is thermally decomposed and the resin molded product tends to be colored.

The mold temperature is preferably 40 to 120 ° C, more preferably 50 to 100 ° C, and particularly preferably 60 to 80 ° C. If the mold temperature is too high, the productivity of the resin molded product tends to decrease, while if too low, the maximum phase difference (Re _MAX ) tends to increase.
Between the resin composition of the present invention, that is, the number average molecular weight (Mn1) of the resin and the maximum phase difference (Re _MAX ) of a molded body (thickness 3 mm) molded from the resin composition containing the resin (re _MAX ) I)
One of means for achieving the resin composition characterized by having the formula relationship is that, as described above, the ratio of the dihydroxy compound of the present invention to the total dihydroxy compound is within a specific range, the cylinder temperature and The mold temperature is set to the above specific range.

Re _MAX ≦ −0.006Mn1 + 350 (I)
When the number average molecular weight (Mn1) of the resin is large, the fluidity of the resin composition is lowered, the maximum phase difference (Re _MAX ) is increased, and the maximum phase difference (Re _MAX ) satisfies the relationship of the above formula (I). On the other hand, when the number average molecular weight (Mn1) of the resin is small, the maximum phase difference (Re _MAX
) Satisfies the relationship of the formula (I), but the mechanical properties tend to decrease.

  According to the present invention, it is possible to provide a resin composition and a resin molded article excellent in low optical distortion, light resistance, transparency, hue, heat resistance, thermal stability, and mechanical strength.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by a following example, unless the summary is exceeded.
In the following, physical properties or characteristics of the resin composition and the resin molded body were evaluated by the following methods.
(1) Measurement of oxygen concentration
The oxygen concentration in the polymerization reaction apparatus was measured using an oxygen meter (manufactured by AMI: 1000RS).

(2) Measurement of reduced viscosity
A sample of the polycarbonate resin composition was dissolved using methylene chloride as a solvent to prepare a polycarbonate solution having a concentration of 0.6 g / dL. Using Moritomo Rika Co. Ubbelohde viscometer tube was measured at a temperature of 20.0 ° C. ± 0.1 ° C., determine the relative viscosity ηrel using the following equation from the transit time t of the solvent passage time t ₀ and a solution,
ηrel = t / t ₀
From the relative viscosity, the specific viscosity ηsp was determined from the following formula.

ηsp = (η−η ₀ ) / η ₀ = ηrel ⁻¹
The reduced viscosity ηsp / c was determined by dividing the specific viscosity by the concentration c (g / dL). The higher this value, the higher the molecular weight.
(3) Measurement of metal concentration in polycarbonate resin composition About 0.5 g of polycarbonate resin composition pellets were precisely weighed in a microwave decomposition vessel manufactured by PerkinElmer, and 2 mL of 97% sulfuric acid was added to make a sealed state at 230 ° C. Microwave heated for 10 minutes. After cooling to room temperature, 1.5 mL of 68% nitric acid is added, sealed and microwave heated at 150 ° C. for 10 minutes, cooled again to room temperature, added with 2.5 mL of 68% nitric acid, and sealed again. And microwaved at 230 ° C. for 10 minutes to completely decompose the contents. After cooling to room temperature, the liquid obtained above was diluted with pure water and quantified with ICP-MS manufactured by ThermoQuest.

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

The terminal phenyl group concentration was determined from the signal intensity ratio based on the internal standard and the terminal phenyl group by measuring ¹ H-NMR in the same manner as described above using 1,1,2,2-tetrabromoethane as the internal standard.
(5) Measurement of content of aromatic monohydroxy compound in polycarbonate resin composition, content of carbonic acid diester represented by general formula (3) 1.25 g of polycarbonate resin composition sample was dissolved in 7 ml of methylene chloride and After that, acetone was added so that the total amount was 25 ml, and reprecipitation was performed. Next, the treatment liquid was filtered through a 0.2 μm disk filter and quantified by liquid chromatography.

(6) Ratio of moles of H bonded to the aromatic ring (A) to moles of total H (A + B) (where (B) is the number of moles of H not bonded to the aromatic ring)
A spectrum of only deuterated chloroform to which tetramethylsilane (TMS) is added and mixed in advance as an internal standard substance is measured, and a signal ratio of residual H contained in TMS and deuterated chloroform is determined. Next, 30 mg of polycarbonate resin was weighed and dissolved in about 0.7 mL of the deuterated chloroform. This was put into an NMR tube having an inner diameter of 5 mm, and a ¹ H NMR spectrum was measured at room temperature using JNM-AL400 (resonance frequency 400 MHz) manufactured by JEOL. From the integrated value of the signal appearing at 6.5 ppm to 8.0 ppm in the obtained NMR chart, the integrated value of the residual H signal contained in deuterated chloroform (the integrated value of the TMS signal and the previously calculated TMS and The value obtained by subtracting (determined from the ratio to the residual H contained in chloroform) is a. On the other hand, when the integral value of the signal appearing at 0.5 ppm to 6.5 ppm is b, a / (a + b) = A / (A + B) is obtained.

(7) Measurement of phase difference of molded product A 500 mm × 500 mm × 3 mm molded plate was divided, and a phase difference with respect to a wavelength of 590 nm was measured by a phase difference measuring device “KOBRA WWR / XY” manufactured by Oji Scientific Instruments.
(8) Measurement of number average molecular weight ¹ H NMR spectrum was measured at room temperature by the method of (6) above, and the number of terminal groups was determined from the integrated value of the signal appearing at 6.5 ppm to 8.0 ppm of the obtained NMR chart. And the number of all monomer units was determined and calculated from these ratios.

(9) Evaluation Method of Initial Hue of Polycarbonate Resin Composition The pellets of the polycarbonate resin composition were dried at 110 ° C. for 10 hours in a nitrogen atmosphere. Next, the pellets of the dried polycarbonate resin composition are supplied to an injection molding machine (J75EII type manufactured by Nippon Steel Co., Ltd.), and injection molded pieces (width 60 mm × length) under the conditions of a resin temperature of 220 ° C. and a molding cycle of 23 seconds. 60 mm × thickness 3 mm) is repeated, and the yellow index (initial YI) value in the transmitted light in the thickness direction of the injection molded pieces obtained in the 10th to 20th shots is determined by a color tester (Konica Minolta, Inc.). An average value was calculated using CM-3700d). The smaller the YI value, the better the quality without yellowness.

(10) Metal halide lamp irradiation test Using a metal ring weather meter M6T manufactured by Suga Test Instruments Co., Ltd., a horizontal metal ring lamp as a light source, quartz as an inner filter, and quartz Attach a # 500 filter as an outer filter around, set the irradiance at a wavelength of 300 nm to 400 nm to 1.5 kw / m ² , and obtain the 20th shot flat plate obtained in (8) above (width 60 mm × length A square surface having a thickness of 60 mm × thickness of 3 mm was subjected to irradiation treatment for 100 hours. The YI value after irradiation was measured in the same manner as (8) above.

The abbreviations of the compounds used in the description of the following examples are as follows.
ISB: Isosorbide (Rocket Fleure, trade name POLYSORB)
CHDM: 1,4-cyclohexanedimethanol (New Nippon Rika Co., Ltd., SKY CHDM)
DPC: Diphenyl carbonate (Mitsubishi Chemical Corporation)
NOVAREX 7022R: aromatic polycarbonate resin having a structure derived only from 2,2-bis- (4-hydroxyphenyl) propane, viscosity average molecular weight 22,000 (manufactured by Mitsubishi Engineering Plastics)
(Antioxidant)
Irganox 1010: Pentaerythrityl-tetrakis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (Ciba Specialty Chemicals)
Irgaphos 168: Tris (2,4-di-tertbutylphenyl) phosphite (Ciba Specialty Chemicals)
(Release agent)
NAA-180: Stearic acid (manufactured by NOF Corporation)
[Example 1]
In a polymerization reactor equipped with a stirring blade and a reflux condenser controlled at 100 ° C., ISB and CHDM, DPC and calcium acetate monohydrate having a chloride ion concentration of 10 ppb or less by purification by distillation, in a molar ratio. ISB / CHDM / DPC / calcium acetate monohydrate = 0.69 / 0.31 / 1.00 / 1.3 × 10 ⁻⁶ , and sufficiently purged with nitrogen (oxygen concentration 0.0005 vol% -0.001 vol%). Subsequently, heating was performed with a heating medium, and stirring was started when the internal temperature reached 100 ° C., and the contents were melted and made uniform while controlling the internal temperature to be 100 ° C. After that, temperature increase was started, the internal temperature was adjusted to 210 ° C. in 40 minutes, and when the internal temperature reached 210 ° C., control was performed so as to maintain this temperature, and at the same time, pressure reduction was started and the temperature reached 210 ° C. After 90 minutes, the pressure was changed to 13.3 kPa (absolute pressure, the same applies hereinafter), and the pressure was maintained for another 60 minutes. The phenol vapor produced as a by-product with the polymerization reaction is led to a reflux condenser using a steam controlled at 100 ° C. as the inlet temperature to the reflux condenser, and a monomer component contained in the phenol vapor in a slight amount is introduced into the polymerization reactor. Then, the phenol vapor that did not condense was recovered by guiding it to a condenser using 45 ° C. warm water as a refrigerant.

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

  Further, the polycarbonate resin in the molten state is continuously supplied to a twin-screw extruder provided with 3 vents and water injection equipment, and “Irganox 1010” and “Irgaphos 168” are used as antioxidants so as to have the compositions shown in Table 1. "NAA-180" is continuously added as a release agent at a predetermined ratio, and a low molecular weight product such as phenol is devolatilized under reduced pressure at each vent section provided in the twin screw extruder, and then a pelletizer. Was pelletized to obtain a pellet of a polycarbonate resin composition.

Using the obtained polycarbonate resin composition pellets, a mold capable of obtaining a plate with a projected area of 250,000 mm ² (500 mm × 500 mm) and a thickness of 3 mm is attached to an injection press molding machine with a clamping force of 700 tons made by Engel Machine. Cylinder temperature 240 ° C., hot runner temperature 230 ° C., mold temperature 80 ° C., injection speed 50 mm / sec, holding pressure 20 MPa, holding pressure 1 second, cooling time 30 seconds, mold opening distance 2 mm, clamping pressure 700 tons The molded plate was molded with a re-clamping time of 15 seconds. Various physical properties and the like were evaluated by the evaluation methods described above. The obtained results are shown in Table 1.

[Example 2]
The same operation as in Example 1 was performed except that the cylinder temperature at the time of injection press molding in Example 1 was set to 260 ° C.
[ Reference Example 3]
The calcium acetate monohydrate of Example 1 was changed to cesium carbonate, and the molar ratio was ISB / CHDM / DPC / cesium carbonate = 0.69 / 0.31 / 1.00 / 1.0 × 10 ⁻⁶ . The procedure was the same as in Example 1 except for the change.

[Comparative Example 1]
ISB / CHDM, DPC and calcium acetate monohydrate in a molar ratio of ISB / CHDM / DPC / calcium acetate monohydrate = 0.70 / 0.30 / 1.00 / 2.5 × 10 ⁻⁶ The same procedure as in Example 1 was performed, except that charging was performed.
[Comparative Example 2]
The polycarbonate resin of Example 1 is changed to “NOVAREX 7022R”, the cylinder temperature is 300 ° C., the hot runner temperature is 300 ° C., the mold temperature is 80 ° C., the injection speed is 50 mm / sec, the pressure is 20 MPa, the pressure is 1 second, and the cooling is performed. The molding plate was molded at a time of 30 seconds, a mold opening distance of 2 mm, a mold clamping pressure of 700 tons, and a re-clamping time of 15 seconds.

Claims (13)

A resin comprising at least a structural unit derived from a compound represented by the following general formula (2) in a part of the structure;
The structural unit derived from the dihydroxy compound having a site represented by the following general formula (2) in a part of the structure with respect to all dihydroxy compounds is 30 to 80 mol%,
The resin further includes a structural unit derived from at least one compound selected from the group consisting of an aliphatic dihydroxy compound and an alicyclic hydrocarbon dihydroxy compound,
Containing at least one metal compound selected from the group consisting of metals of Group 2 of the Long Periodic Periodic Table;
The content of the metal compound is 20 ppm by weight or less as the amount of metal,
The total amount of sodium, potassium and cesium compounds in the resin is 1 ppm by weight or less as the amount of metal,
Maximum phase difference (Re) of a molded body (thickness 3 mm) injection- molded at a cylinder temperature of 200 to 300 ° C. and a mold temperature of 40 to 120 ° C. from the resin number-average molecular weight (Mn1) and the resin composition containing the resin _(MAX )) and a resin composition having the relationship of the following formula (I):
Re _MAX ≦ −0.006 Mn1 + 350 (I)

The at least one metal compound selected from the group consisting of metals of Group 2 of the long-period periodic table is at least one metal compound selected from the group consisting of magnesium compounds and calcium compounds. 2. The resin composition according to 1 . Following general formula (3) The resin composition according to claim 1 or 2, characterized in that it comprises a carbonic acid diester 60 ppm by weight or less, represented by.

(In General Formula (3), A ¹ and A ² are each independently a substituted or unsubstituted aliphatic group having 1 to 18 carbon atoms or a substituted or unsubstituted aromatic group, and A ¹ and A ² may be the same or different.) The resin composition according to any one of claims 1 to 3 , comprising 700 ppm by weight or less of an aromatic monohydroxy compound. Concentration of the terminal group represented by the following general formula (4) is a resin composition according to any one of claims 1 to 4, characterized in that a range of 20μeq / g or more 160μeq / g.

A / (A + B) ≦ 0.05, where (A) is the number of moles of H bonded to the aromatic ring and (B) is the number of moles of H bonded to other than the aromatic ring. Item 6. The resin composition according to any one of Items 1 to 5 . The number average molecular weight of the resin (Mn1) and of claims 1 to 6 the number average molecular weight of the molded article molded from a resin composition comprising the resin (Mn2) of the rate of change is equal to or within 10% The resin composition according to any one of the above. The resin composition according to any one of claims 1 to 7 , wherein the resin molded product (thickness 3 mm) molded from the resin composition has a light transmittance at a wavelength of 350 nm of 60% or more. . The resin composition according to any one of claims 1 to 8, wherein a light transmittance at a wavelength of 320 nm of a resin molded body (thickness: 3 mm) molded from the resin composition is 30% or more. . Irradiance 1 with a wavelength of 300 nm to 400 nm using a metal halide lamp in an environment with an initial yellow index value and a relative humidity of 50% of a resin molded body (thickness 3 mm) molded from the resin composition. The absolute value of the difference from the yellow index (YI) value according to ASTM D 1925-70 measured with transmitted light after irradiation treatment at 0.5 kW / m ² for 100 hours is 6 or less. The resin composition according to any one of 1 to 9 . A resin molded article obtained by injection-molding the resin composition according to any one of claims 1 to 10 . The resin molding according to claim 11 , wherein the injection molding is injection press molding. 13. The resin molded body according to claim 11, wherein the maximum projected area is 500 to 50,000 cm ² .