JP2015112841A - Method for producing resin molding, and resin molding obtained thereby - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a resin molding, in which deformation of the resin molding having a transparent resin molding part and an opaque resin molding part and the internal stress or strain of the transparent resin molding part can be made smaller, and to provide the resin molding obtained by the method for producing the resin molding.SOLUTION: In the method for producing the resin molding, an injection molding method is adopted. Since the resin molding has a molding part comprising an opaque resin on the rear surface of another molding part comprising a transparent resin, a metal mold to be used for injection molding comprises a design-side metal mold and a non-design-side metal mold, a cavity for forming the transparent resin molding part is formed on the design-side metal mold and another cavity for forming the opaque resin molding part is formed on the non-design-side metal mold, the temperature of the non-design-side metal mold is made lower than that of the design-side metal mold, and a difference between the temperature of the non-design-side metal mold and that of the design-side metal mold is made lower than 20°C.

Description

  The present invention relates to an injection molding method and a resin molded body for integrally molding a transparent portion in a resin panel and a frame-shaped outer peripheral portion that supports the transparent portion.

2. Description of the Related Art Conventionally, a two-color injection molding method (double mold method) has been widely adopted as a method for integrally molding a transparent portion in a resin panel and an opaque portion that supports the transparent portion.
When an opaque part (support part) is provided on the outer peripheral part of the transparent part of the resin panel by this method, flare and ghosting can be prevented when used as an optical component. Further, by providing an opaque part around the transparent part such as an optical element, it is possible to provide a positioning function when the opaque part (supporting part) is incorporated in another component.

  As a general molding method of the two-color injection molding method, for example, first, a resin for primary molding is injected into a mold for primary molding to mold a transparent portion. Next, a resin for secondary molding is injected into a mold for secondary molding to mold the colored portion, and at the same time, the transparent portion and the colored portion are welded and integrated.

  However, in such a molding method, the resin pressure during the secondary molding and the contraction of the colored part during the cooling process cause the shape of the primary molding part (transparent part) to collapse, and the internal stress and strain of the primary molding part are reduced. There is a problem of increasing.

In order to solve this problem, for example, Patent Document 1 proposes a method in which a colored portion is formed by primary forming and then a transparent portion is subjected to secondary forming.
Patent Document 2 proposes that at least primary molding is injection compression molded in a method of molding a colored portion by secondary molding after molding a transparent portion by primary molding.

JP 2005-103907 A Japanese Examined Patent Publication No. 7-10031

  However, as in Patent Document 1, when the transparent part is subjected to secondary molding, the resin of the primary molded product is melted by the resin temperature of the secondary molding, and this resin enters the transparent resin of the secondary molding, and the desired optical characteristics. May not be obtained. In particular, such a phenomenon tends to appear remarkably when the transparent portion is very small.

  Further, in the case of Patent Document 2, as described above, even if the primary molding is injection compression molding, the secondary molding part is caused by the resin pressure during the secondary molding and the resin shrinkage of the secondary molding part during the cooling process. There is a risk that the shape of will collapse.

  Therefore, the present invention has been made to solve such a problem, and it is possible to reduce the deformation of the resin molded body including the transparent resin molded portion and the opaque resin molded portion and the internal stress and strain of the transparent resin molded portion. It aims at providing the manufacturing method of the resin molding, and its resin molding.

The present invention has been studied to achieve the above-mentioned goal, and the gist of the present invention resides in the following [1] to [10].
[1] A method for producing a resin molded body by injection molding, wherein the resin molded body includes a molded portion made of an opaque resin on the back surface of a molded portion made of a transparent resin, and is used for the injection molding. Is composed of a design side mold and a non-design side mold, the design side mold is formed with a cavity for forming the transparent resin molding part, and the non-design side mold is A cavity for forming an opaque resin molded part is formed, and the non-design side mold temperature is lower than the design-side mold temperature, and the difference between the non-design-side mold temperature and the design-side mold temperature Is produced by injection molding at a temperature of less than 20 ° C.

[2] The thickness of the transparent resin molded portion is thinner than the thickness of the opaque resin molded portion, and the difference between the thickness of the transparent resin molded portion and the thickness of the opaque resin molded portion is 18% or less. The manufacturing method of the resin molding as described in [1] characterized by the above-mentioned.

[3] A method for producing a resin molded body by injection molding, wherein the resin molded body includes a molded portion made of an opaque resin on the back surface of a molded portion made of a transparent resin, and is used for the injection molding. Is composed of a design side mold and a non-design side mold, the design side mold is formed with a cavity for forming the transparent resin molding part, and the non-design side mold is A cavity for forming an opaque resin molded part is formed, and the thickness of the transparent resin molded part is thinner than the thickness of the opaque resin molded part, and the thickness of the transparent resin molded part and the opaque resin molded part The manufacturing method of the resin molding characterized by the difference of thickness being 18% or less.

[4] The heat resistant temperature of the transparent resin molded part is lower than the heat resistant temperature of the opaque resin molded part, and the difference between the heat resistant temperature of the transparent resin molded part and the heat resistant temperature of the opaque resin molded part is 30 ° C. or less. The method for producing a resin molded article according to any one of [1] to [3].

[5] The transparent resin is a polycarbonate resin composition containing a polycarbonate resin containing 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. The method for producing a resin molded body according to any one of [1] to [4].

[6] The opaque resin is a polycarbonate resin composition including a polycarbonate 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. The manufacturing method of the resin molding as described in any one of [1]-[5] to do.

[7] The method for producing a resin molded article according to [5] or [6], wherein the dihydroxy compound is a compound represented by the following general formula (2).

[8] In the above [5] to [7], the polycarbonate resin further contains a structural unit derived from at least one compound selected from the group consisting of aliphatic dihydroxy compounds and alicyclic dihydroxy compounds. The manufacturing method of the resin molding as described in any one.
[9] The method for producing a resin molded body according to any one of [5] to [8], wherein the polycarbonate resin has a glass transition temperature of less than 145 ° C.

[10] The opaque resin is obtained by blending a colorant with the transparent resin, and the content of the colorant is 0.05 part by weight or more and 5 parts by weight or less with respect to 100 parts by weight of the polycarbonate resin. The method for producing a resin molded body according to any one of [1] to [9], wherein:
[11] A resin molded product produced by the method for producing a resin molded product according to any one of [1] to [10].

    According to the present invention, when the transparent portion and the opaque portion are integrally formed, there can be obtained a resin molded body that is not deformed and has less internal stress and distortion of the transparent portion.

Cross section of the primary resin mold Cross section of secondary resin mold Movable primary resin cavity layout (PL view) Fixed mold cavity layout for secondary resin (PL view) Transparent resin molding of the present invention (A) Two-color resin molded product of the present invention, (b) End view of bb cutting part of (a)

  DESCRIPTION OF EMBODIMENTS Embodiments of the present invention will be described in detail below. However, the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention. It is not limited to the contents.

  This invention is an invention relating to a method of producing a resin molded body by injection molding. This resin molded body has a molded part made of an opaque resin composition (hereinafter referred to as “opaque resin molded part”) on the back surface of a molded part made of a transparent resin composition (hereinafter referred to as “transparent resin molded part”). )).

[Transparent resin composition and opaque resin composition]
Each of the transparent resin composition and the opaque resin composition constituting the transparent resin molded part and the opaque resin molded part constituting the resin molded body contains a transparent resin. The transparent resin composition contains various additives if necessary for the transparent resin, and the opaque resin composition is made opaque by adding a colorant to the transparent resin. .

  Examples of the resin constituting the transparent resin include a polycarbonate resin composition, a styrene resin composition, a styrene / acrylonitrile resin composition, an acrylic resin composition, and the like.

[Styrenic resin composition, styrene / acrylonitrile resin composition, acrylic resin composition]
Examples of the styrenic resin composition include polystyrene resin. Examples of the styrene / acrylonitrile resin composition include transparent ABS resin (where ABS resin refers to acrylonitrile, butadiene, styrene copolymer synthetic resin) and the like. Furthermore, as the acrylic resin composition, MMA resin (where MMA resin is a generic name for a polymer of methyl methacrylate (methyl methacrylate = MMA) or a copolymer with an acrylic ester (acrylate)), etc. As an example.

[Polycarbonate resin composition]
The polycarbonate resin composition includes 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 (hereinafter referred to as “dihydroxy compound (1)”). It is a resin composition containing resin.

但し、前記一般式（１）で表される部位が−ＣＨ_２−Ｏ−Ｈの一部である場合を除く。

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

  Hereafter, the method for manufacturing the polycarbonate resin composition used for this invention is explained in full detail.

[Manufacture of polycarbonate resin]
<Raw material>
(Dihydroxy compound)
The polycarbonate resin used for this invention contains at least the structural unit derived from the dihydroxy compound (1) which has a site | part represented by the said General formula (1) in a part of structure.
That is, the dihydroxy compound (1) refers to a compound containing at least two hydroxyl groups and at least a site represented by the general formula (1).

  The ratio of the structural unit derived from the dihydroxy compound (1) to the structural unit derived from all the dihydroxy compounds constituting the polycarbonate resin used in the present invention is preferably 90 mol% or less, more preferably 85 mol% or less, particularly preferably. 80 mol% or less. On the other hand, it is preferably at least 20 mol%, more preferably at least 30 mol%, particularly preferably at least 40 mol%.

  When the proportion of the structural unit derived from the dihydroxy compound (1) is too large, when a molded product obtained by molding the polycarbonate resin composition used in the present invention is subjected to irradiation treatment using a sunshine carbon arc, cracking occurs. In addition, transparency may deteriorate and haze may increase. However, it is also possible to prevent this cracking by incorporating a light-resistant stabilizer described later, particularly a predetermined amount of a hindered amine-based light-resistant stabilizer into the polycarbonate resin composition. The details of the cause of the cracking are not clear, but if the proportion of the structural unit derived from the dihydroxy compound (1) is too large, the surface of the resulting molded product is deteriorated by ultraviolet irradiation and hydrolyzed, and the polycarbonate resin This is thought to be due to a decrease in molecular weight. However, as described above, it is possible to prevent cracking of the molded product by including the light-resistant stabilizer in the polycarbonate resin composition. Although the details of this cause are not clear, it is considered that the light-resistant stabilizer suppresses ultraviolet irradiation deterioration and hydrolysis on the surface of the molded product, and the molecular weight of the polycarbonate resin is difficult to decrease.

  On the other hand, if the proportion of the structural unit derived from the dihydroxy compound (1) in the polycarbonate resin is too small, the heat resistance of the obtained molded product may be lowered.

  The dihydroxy compound (1) is not particularly limited as long as it has a site represented by the general formula (1) in a part of its structure. Specific examples include oxyalkylene glycols such as diethylene glycol, triethylene glycol and tetraethylene glycol, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 9,9-bis (4- (2-hydroxy Ethoxy) -3-methylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-isopropylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-isobutyl Phenyl) 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-phenylphenol L) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3,5-dimethylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-tert-butyl-6 -Methylphenyl) fluorene, phenyl substituted fluorene such as 9,9-bis (4- (3-hydroxy-2,2-dimethylpropoxy) phenyl) fluorene, etc., having an aromatic group in the side chain and aromatic in the main chain A compound having an ether group bonded to an aromatic group, an anhydrosugar alcohol typified by a dihydroxy compound represented by the following general formula (2), and a cyclic ether structure such as spiroglycol represented by the following general formula (3) A compound (cyclic ether) etc. are mentioned.

Among these, diethylene glycol and triethylene glycol are preferable from the viewpoint of easy availability, handling, reactivity during polymerization, and hue of the obtained polycarbonate resin. From the viewpoint of heat resistance, the following general formula (2) The anhydrous sugar alcohol represented by the dihydroxy compound represented, and the compound which has a cyclic ether structure represented by following General formula (3) are preferable.
These may be used alone or in combination of two or more depending on the required performance of the polycarbonate resin to be obtained.

  Examples of the dihydroxy compound represented by the general formula (2) include isosorbide, isomannide, and isoidet, which have 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 polycarbonate resin, and among them, it is abundant as a plant-derived resource and is produced from various easily available starches. 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 polycarbonate resin used in the present invention may contain a structural unit derived from a dihydroxy compound other than the dihydroxy compound (1) (hereinafter sometimes referred to as “other dihydroxy compound”). Other dihydroxy compounds include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-heptane Diols, aliphatic dihydroxy compounds such as 1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, pentacyclopentadecanedi Methanol, 2,6-decalin dimethanol, 1,5-decalin dimethanol, 2,3-decalin dimethanol, 2,3-norbornane dimethanol, 2,5-norbornane dimethanol, 1,3-adamantane dimethanol, etc. Alicyclic dihydroxy compounds of 2,2- (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) cyclohexane, bis (4 Hydroxyphenyl) sulfone, 2,4′-dihydroxydiphenylsulfone, bis (4-hydroxyphenyl) sulfide, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dichlorodiphenyl ether, 9,9- Fragrances such as bis (4- (2-hydroxyethoxy-2-methyl) phenyl) fluorene, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-2-methylphenyl) fluorene Group bisphenols. These may be used individually by 1 type and may be used in combination of 2 or more type.

  Among these, from the viewpoint of the light resistance of the polycarbonate resin, a dihydroxy compound having no aromatic ring structure in the molecular structure, that is, an aliphatic dihydroxy compound and / or an alicyclic dihydroxy compound is preferable. As the aliphatic dihydroxy compound, In particular, 1,3-propanediol, 1,4-butanediol, and 1,6-hexanediol are preferable. As the alicyclic dihydroxy compound, 1,4-cyclohexanedimethanol and tricyclodecanedimethanol are particularly preferable.

  By using these other dihydroxy compounds, it is possible to obtain the effects of improving the flexibility and moldability of the polycarbonate resin, but the content ratio of structural units derived from other dihydroxy compounds is too large. And the lowering of the mechanical properties and the heat resistance, the ratio of the structural unit derived from the dihydroxy compound (1) to the structural unit derived from all dihydroxy compounds in the polycarbonate resin is the lower limit described above. It is preferable to use so that it may become more than a value.

  The dihydroxy compound (1) used for the synthesis of the polycarbonate resin contains stabilizers such as a reducing agent, an antioxidant, an oxygen scavenger, a light stabilizer, an antacid, a pH stabilizer, and a heat stabilizer. In particular, since the dihydroxy compound of the present invention is easily altered under acidic conditions, it is preferable to include a basic stabilizer.

  Basic stabilizers include hydroxides, carbonates, phosphates, phosphites, hypophosphites of group 1 or group 2 metals in the long-period periodic table (Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005). , Borate, fatty acid salt, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, triethyl Methylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydro Basic ammonium compounds such as xoxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide, butyltriphenylammonium hydroxide, 4-amino Pyridine, 2-aminopyridine, N, N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2-dimethylaminoimidazole, 2-methoxyimidazole, imidazole Amine compounds such as 2-mercaptoimidazole, 2-methylimidazole and aminoquinoline. Of these, sodium or potassium phosphates and phosphites are preferable, and disodium hydrogen phosphate and disodium hydrogen phosphite are particularly preferable because of their effects and ease of distillation removal described later.

  Although there is no restriction | limiting in particular in content in the dihydroxy compound (1) of these basic stabilizers, if too little, there exists a possibility that the effect which prevents the modification of dihydroxy compound (1) may not be acquired, and if too much, a dihydroxy compound Since the modification of (1) may be caused, 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 (1).

  When the dihydroxy compound (1) containing these basic stabilizers is used as a raw material for the production of polycarbonate resin, the basic stabilizer itself becomes a polymerization catalyst, which makes it difficult to control the polymerization rate and quality. It is preferable to remove the basic stabilizer by ion exchange resin, distillation or the like before using it as a raw material for producing polycarbonate resin in order to cause deterioration of hue and consequently deteriorate light resistance of the molded product.

  When the dihydroxy compound (1) has a cyclic ether structure such as isosorbide, it is likely to be gradually oxidized by oxygen. Therefore, during storage and production, in order to prevent decomposition by oxygen, water should not be mixed, It is important to use an oxygen 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 the production of polycarbonate resin, there is a possibility that coloring of the obtained polycarbonate resin and further polycarbonate resin composition may be caused, and physical properties may be significantly deteriorated. In some cases, the polymerization reaction is affected and a high molecular weight polymer cannot be obtained.

  In order to obtain the dihydroxy compound (1) which does not contain the oxidative decomposition product, and in order to remove the aforementioned 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 distillation purification, the content of decomposition products such as formic acid in the dihydroxy compound (1) is adjusted to 20 ppm by weight or less, preferably 10 ppm by weight or less, particularly preferably 5 ppm by weight or less. When the dihydroxy compound containing 1) is used as a polycarbonate resin production raw material, a polycarbonate resin excellent in hue and thermal stability can be produced without impairing polymerization reactivity. The content of decomposition products such as formic acid is measured by ion chromatography.

(Carbonated diester)
The polycarbonate resin used in the present invention can be obtained by polycondensation by a transesterification reaction using a dihydroxy compound containing the above-mentioned dihydroxy compound (1) and a carbonic acid diester as raw materials.

  Examples of the carbonic acid diester used for the reaction include those represented by the following general formula (4). These carbonic acid diesters may be used alone or in combination of two or more.

In the general formula (4), A1 and A2 are each a substituted or unsubstituted aliphatic group having 1 to 18 carbon atoms or a substituted or unsubstituted aromatic group, and A1 and A2 are the same. May be different.

  Examples of the carbonic acid diester represented by the general formula (4) (hereinafter sometimes referred to as “carbonic acid diester (4)”) include substituted diphenyl carbonates such as diphenyl carbonate and ditolyl carbonate, dimethyl carbonate, and diethyl carbonate. And di-t-butyl carbonate and the like are exemplified, but diphenyl carbonate and substituted diphenyl carbonate are preferred, and diphenyl carbonate is particularly preferred.

  In addition, the carbonic acid diester may contain impurities such as chloride ions, and these impurities may inhibit the polymerization reaction or worsen the hue of the resulting polycarbonate resin. It is preferable to use one purified by distillation or the like.

<Transesterification reaction catalyst>
The polycarbonate resin used in the present invention is produced by transesterification of the dihydroxy compound containing the dihydroxy compound (1) and the carbonic acid diester (4) as described above. More specifically, it can be obtained by transesterification and removing by-product monohydroxy compounds and the like out of the system. In this case, polycondensation is usually carried out by transesterification in the presence of a transesterification catalyst.

  The transesterification reaction catalyst (hereinafter simply referred to as “catalyst” or “polymerization catalyst”) that can be used in the production of the polycarbonate resin used in the present invention is a light transmittance at a wavelength of 350 nm of the obtained polycarbonate resin composition. In addition, the yellow index (YI) value may be affected.

  As the catalyst used, any of the light resistance, transparency, hue, heat resistance, thermal stability, moldability, and mechanical strength of the manufactured polycarbonate resin composition can satisfy the light resistance. Although not limited, metal compounds, basic boron compounds, basic phosphorus compounds, basic compounds of Group 1 or Group 2 (hereinafter simply referred to as “Group 1” or “Group 2”) in the long-period periodic table 1 type, or 2 or more types of basic compounds, such as an ammonium compound and an amine compound, are mentioned. Preferably, Group 1 metal compounds and / or Group 2 metal compounds are used.

  It is also 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 above-mentioned Group 1 metal compound and / or Group 2 metal compound. However, it is particularly preferable to use only Group 1 metal compounds and / or Group 2 metal compounds.

  The group 1 metal compound and / or group 2 metal compound is 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 ease of handling, hydroxides, carbonates and acetates are preferable, and acetates are preferable from the viewpoint of hue and polymerization activity.

  Examples of the Group 1 metal compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, cesium hydrogen carbonate, sodium carbonate, potassium carbonate, and carbonic acid. Lithium, cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride, hydrogenated Cesium boron, sodium phenide boron, potassium phenide boron, lithium phenide boron, cesium phenide boron, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, hydrogen phosphate 2 Thorium, 2 potassium hydrogen phosphate, 2 lithium hydrogen phosphate, 2 cesium hydrogen phosphate, 2 sodium phenyl phosphate, 2 potassium phenyl phosphate, 2 lithium phenyl phosphate, 2 cesium phenyl phosphate, sodium, potassium, lithium, Examples include cesium alcoholate, phenolate, disodium salt of bisphenol A, 2 potassium salt, 2 lithium salt, 2 cesium salt, etc. Among them, lithium compounds are preferable.

  Examples of the Group 2 metal compound include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, barium carbonate, carbonic acid. Magnesium, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate, etc. Among them, magnesium compound, calcium compound, barium compound are preferable, polymerization activity From the viewpoint of the hue of the polycarbonate resin composition obtained, a magnesium compound and / or a calcium compound is more preferable, and most preferably a calcium compound. It is.

  Examples of the basic boron compound include tetramethyl boron, tetraethyl boron, tetrapropyl boron, tetrabutyl boron, trimethylethyl boron, trimethylbenzyl boron, trimethylphenyl boron, triethylmethyl boron, triethylbenzyl boron, triethylphenyl boron, Sodium salt such as tributylbenzylboron, tributylphenylboron, tetraphenylboron, benzyltriphenylboron, methyltriphenylboron, butyltriphenylboron, sodium salt, potassium salt, lithium salt, calcium salt, barium salt, magnesium salt, strontium salt, etc. Is mentioned.

  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 Dorokishido, 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, and 4-methoxypyridine. , 2-dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, aminoquinoline and the like.

  The amount of the polymerization catalyst used is usually 0.1 μmol to 300 μmol, preferably 0.5 μmol to 100 μmol per 1 mol of all dihydroxy compounds used for polymerization, and at least one selected from the group consisting of lithium and group 2 among them. When using a compound containing any of these metals, particularly when using a magnesium compound and / or a calcium compound, the metal amount is usually 0.1 μmol or more, preferably 0.5 μmol or more, particularly preferably, per 1 mol of the total dihydroxy compound. Is 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 is slowed down. As a result, when trying to obtain a polycarbonate resin having a desired molecular weight, the polymerization temperature has to be increased, and the hue and light resistance of the obtained polycarbonate resin are deteriorated. Or the unreacted raw material volatilizes during the polymerization, and the molar ratio of the dihydroxy compound containing the dihydroxy compound (1) of the present invention to the carbonic acid diester (4) may collapse, and the desired molecular weight may not be reached. On the other hand, when there is too much usage-amount of a polymerization catalyst, the hue of the polycarbonate resin obtained will be deteriorated and the light resistance of a polycarbonate resin may deteriorate.

  Furthermore, when the polycarbonate resin used in the present invention is produced by using substituted diphenyl carbonate such as diphenyl carbonate and ditolyl carbonate as the carbonic acid diester (4), phenol and substituted phenol are by-produced in the polycarbonate resin. Residual and contained in the polycarbonate resin composition is unavoidable, but the remaining phenol and substituted phenol also has an aromatic ring, so it not only absorbs ultraviolet rays but may cause deterioration of light resistance. , It may cause odor during molding.

  The polycarbonate 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. Using a horizontal reactor with excellent performance and an extruder with a vacuum vent, these are devolatilized and removed, and the content of the aromatic monohydroxy compound in the polycarbonate resin is 700 ppm by weight or less, preferably 500 ppm by weight or less. In particular, the content is preferably 300 ppm by weight or less. However, it is difficult to industrially completely remove the aromatic monohydroxy compound in the polycarbonate resin, and the lower limit of the content of the aromatic monohydroxy compound in the polycarbonate resin 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, Group 1 metals, especially lithium, sodium, potassium, and cesium, especially sodium, potassium, and cesium, may adversely affect the hue when contained in a large amount in the polycarbonate resin, but the metal is a catalyst used. The total amount of these metals in the polycarbonate resin is usually not more than 1 ppm by weight, preferably not more than 0.8 ppm by weight, more preferably because it may be mixed not only from the raw materials but also from raw materials and reactors. Of 0.7 ppm by weight or less.

  The amount of metal in the polycarbonate resin can be measured using a method such as atomic emission, atomic absorption, Inductively Coupled Plasma (ICP) after recovering the metal in the polycarbonate resin by a method such as wet ashing. .

  The glass transition temperature of the polycarbonate resin is preferably less than 145 ° C, and preferably less than 130 ° C. If it is higher than 145 ° C., the material becomes brittle and may be destroyed during practical use. On the other hand, the lower limit of the glass transition temperature is preferably 80 ° C. or higher, and preferably 90 ° C. or higher. If it is lower than 80 ° C., it may be thermally deformed during practical use.

<Manufacturing method>
The polycarbonate resin used in the present invention is obtained by polycondensation of a dihydroxy compound containing the dihydroxy compound (1) and a carbonic acid diester (4) by an ester exchange reaction. The raw material dihydroxy compound and carbonic acid diester are transesterified. It is preferable to mix uniformly before the reaction.

  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 resulting in problems such as solidification. If the mixing temperature is too high, the dihydroxy compound may be thermally deteriorated, resulting in a deterioration of the hue of the polycarbonate resin thus obtained, which may adversely affect light resistance.

  The operation of mixing the dihydroxy compound containing the dihydroxy compound (1), which is a raw material of the polycarbonate resin used in the present invention, and the carbonic acid diester (4) is performed at an oxygen concentration of 10 vol% or less, more preferably 0.0001 vol% to 10 vol%, especially 0 From the viewpoint of preventing deterioration of hue, it is preferable to carry out in an atmosphere of 0.0001 vol% to 5 vol%, particularly 0.0001 vol% to 1 vol%.

  In order to obtain the polycarbonate resin used in the present invention, the carbonic acid diester (4) is preferably used in a molar ratio of 0.90 to 1.20 with respect to the dihydroxy compound including the dihydroxy compound (1) used in the reaction. More preferably, the molar ratio is 0.95 to 1.10.

  When this molar ratio is decreased, the terminal hydroxyl group of the produced polycarbonate resin is increased, the thermal stability of the obtained polycarbonate resin is deteriorated, coloring occurs during molding, the rate of transesterification reaction is decreased, May not be obtained. Moreover, when this molar ratio becomes large, the rate of transesterification may decrease, or it may be difficult to produce a polycarbonate resin having a desired molecular weight. The decrease in the transesterification reaction rate may increase the heat history during the polymerization reaction, and may deteriorate the hue and light resistance of the resulting polycarbonate resin.

  Furthermore, when the molar ratio of the carbonic acid diester (4) is increased with respect to the dihydroxy compound containing the dihydroxy compound (1), the amount of carbonic acid diester in the obtained polycarbonate resin increases, and as a result, the polycarbonate resin used in the present invention. The carbonate diester content in the composition is also increased. The residual carbonic acid diester in the polycarbonate resin composition may absorb ultraviolet rays and deteriorate the light resistance of the polycarbonate resin composition. The concentration of the carbonic acid diester in the polycarbonate resin composition used in the present invention is preferably 60 ppm by weight or less, more preferably 40 ppm by weight or less, and particularly preferably 30 ppm by weight or less. Actually, the polycarbonate resin composition may contain unreacted carbonic acid diester, and the lower limit of the concentration is usually 1 ppm by weight.

  The method of polycondensing the dihydroxy compound containing the dihydroxy compound (1) and the carbonic acid diester (4) is usually performed 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 is distilled, and the dihydroxy compound containing the dihydroxy compound (1) and the carbonic acid diester (4) It is possible that the molar ratio of these is deviated, leading to a decrease in the polymerization rate, or a polycarbonate resin having a predetermined molecular weight or terminal group cannot be obtained, and as a result, the object of the present invention cannot 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 cooler can be appropriately selected according to the monomer used. Usually, the temperature of the refrigerant introduced into the reflux cooler is 45 ° C. to 180 ° C. at the inlet of the reflux cooler. Preferably, it is 80 degreeC-150 degreeC, Most preferably, it is 100 degreeC-130 degreeC. If the temperature of the refrigerant introduced into the reflux condenser is too high, the reflux amount is reduced and the effect is reduced. If it is too low, the distillation efficiency of the monohydroxy compound to be originally distilled tends to be reduced. As the refrigerant, hot water, steam, heat medium oil or the like is used, and steam or heat medium oil is preferable.

  In order to maintain the polymerization rate appropriately and suppress the distillation of the monomer, while keeping the hue, thermal stability, light resistance, etc. of the final polycarbonate resin composition, The selection of the quantity is important.

  The polycarbonate resin used in the present invention is preferably produced by polymerizing in a plurality of stages using a plurality of reactors using a catalyst, but the reason for carrying out the polymerization in a plurality of reactors is the initial stage of the polymerization reaction. In order to shift the equilibrium to the polymerization side in the latter stage of the polymerization reaction, it is important to suppress the volatilization of the monomer while maintaining the necessary polymerization rate because there are many monomers contained in the reaction solution. This is because it is important to sufficiently distill off the by-produced monohydroxy compound. Thus, in order to set different polymerization reaction conditions, it is preferable from the viewpoint of production efficiency to use a plurality of polymerization reactors arranged in series.

As described above, the reactor used for the production of the polycarbonate resin used in the present invention may be at least two or more, but from the viewpoint of production efficiency, etc., three or more, preferably 3 to 5, particularly Preferably, 4 groups.
If there are two or more reactors, a plurality of reaction stages with different conditions may be further provided in the reactor, or the temperature and pressure may be continuously changed.

  The polymerization catalyst can be added to the raw material preparation tank, the raw material storage tank, or directly to the polymerization tank. From the viewpoint of supply stability and polymerization control, the raw material before being supplied to the polymerization tank is used. A catalyst supply line is installed in the middle of the line and is preferably supplied as an aqueous solution.

  If the temperature of the polymerization reaction is too low, the productivity decreases due to a decrease in reaction rate or reaction time, and if it is too high, not only will the vaporization of the monomer occur, but also the decomposition and coloring of the polycarbonate resin may be promoted. is there.

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

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

  In particular, in order to suppress the coloring and thermal deterioration of the polycarbonate resin and obtain a polycarbonate resin having a good hue and light resistance, the maximum internal temperature in all reaction stages is less than 250 ° C., particularly 225 ° C. to 245 ° C. preferable. 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 polycarbonate resin having a predetermined molecular weight, if the polymerization temperature is set high and the polymerization time is too long, the ultraviolet transmittance tends to decrease and the yellow index (YI) value of the resulting polycarbonate resin tends to increase.

  The monohydroxy compound produced as a by-product is preferably reused as a raw material for diphenyl carbonate, bisphenol A, etc. after purification as necessary from the viewpoint of effective utilization of resources.

  The polycarbonate resin obtained as described above is usually cooled and solidified after polycondensation and pelletized with a rotary cutter or the like.

  The method of pelletization is not limited, but it is extracted from the final polymerization reactor in a molten state, cooled and solidified in the form of a strand and pelletized, or uniaxial or biaxial extrusion in the molten state from the final polymerization reactor. 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 Or after supplying resin to a twin-screw extruder, melt-extruding, cooling and solidifying and pelletizing, etc. are mentioned.

  At that time, in the extruder, the residual monomer under reduced pressure devolatilization, and generally known heat stabilizer, neutralizer, light stabilizer, mold release agent, colorant, antistatic agent, lubricant, lubricant, 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 polycarbonate resin, but is usually 150 ° C to 300 ° C, preferably 200 ° C to 270 ° C, more preferably 230 ° C to 260 ° C. When the melt-kneading temperature is lower than 150 ° C., the melt viscosity of the polycarbonate resin is high, the load on the extruder is increased, and the productivity is lowered. When the temperature is higher than 300 ° C., the polycarbonate resin is severely deteriorated by heat, resulting in a decrease in mechanical strength due to a decrease in molecular weight, coloring, and gas generation.

  When producing the polycarbonate resin used in the present invention, it is desirable to install a filter in the extruder in order to prevent foreign substances from entering. The filter installation position is preferably on the downstream side of the extruder, and the foreign matter removal size (opening) of the filter is preferably 100 μm or less as the filtration accuracy for 99% removal. In particular, when a minute foreign matter is not desired to be mixed, it is preferably 40 μm or less, more preferably 10 μm or less.

  Extrusion of the polycarbonate resin used in the present invention is preferably carried out in a clean room having a higher degree of cleanliness than Class 6, more preferably Class 6 as defined in JIS B 9920 (2002), in order to prevent foreign matter from being mixed after extrusion. It is desirable to do.

  Moreover, when cooling the extruded polycarbonate resin into chips, it is preferable to use a cooling method such as air cooling or water cooling. As the air used for air cooling, it is desirable to use air from which foreign substances in the air have been removed in advance with a hepa filter or the like to prevent reattachment of foreign substances in the air. When water cooling is used, it is desirable to use water from which metal in water has been removed with an ion exchange resin or the like, and foreign matter in water has been removed with a filter. The opening of the filter to be used is preferably 10 μm to 0.45 μm as 99% removal filtration accuracy.

The molecular weight of the polycarbonate resin used in 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 reduced viscosity. Is usually 1.20 dL / g or less, more preferably 1.00 dL / g or less, and still more preferably 0.80 dL / g or less.
If the reduced viscosity of the polycarbonate resin is too low, the mechanical strength of the molded product may be small. 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 of the polycarbonate resin was measured using an Ubbelohde viscometer at a temperature of 20.0 ° C. ± 0.1 ° C., using methylene chloride as a solvent and preparing a polycarbonate solution concentration of 0.6 g / dL precisely. To do.

  Furthermore, the lower limit amount of the terminal group concentration (terminal phenyl group concentration) represented by the following general formula (5) in the polycarbonate resin used in the present invention is preferably 20 μeq / g, more preferably 40 μeq / g, particularly preferably. Is 50 μeq / g, and the upper limit is preferably 160 μeq / g, more preferably 140 μeq / g, and particularly preferably 100 μeq / g.

  If the concentration of the terminal group represented by the general formula (5) of the polycarbonate resin is too high, the hue after exposure to ultraviolet rays may be deteriorated even if the hue immediately after polymerization or molding is good. If it is too low, the thermal stability may be reduced.

  In order to control the concentration of the terminal group represented by the general formula (5), in addition to controlling the molar ratio of the dihydroxy compound containing the dihydroxy compound (1) and the carbonic acid diester (4) as a raw material, And a method for controlling the type and amount of the catalyst, the polymerization pressure and the polymerization temperature.

  Further, when the equivalent number of hydrogen atoms bonded to the aromatic ring in the polycarbonate resin used in the present invention is “A” and the equivalent number of hydrogen atoms bonded to other than the aromatic ring is “B”, hydrogen bonded to the aromatic ring The ratio of the number of equivalents of atoms to the number of equivalents of all hydrogen atoms is represented by A / (A + B). However, as described above, there is a possibility that an aromatic ring having an ultraviolet absorbing ability affects the light resistance. Therefore, A / (A + B) is preferably 0.05 or less, more preferably 0.04 or less, particularly preferably 0.02 or less, and preferably 0.01 or less. A / (A + B) can be quantified by 1H-NMR.

[Transparent resin composition]
The transparent resin composition used in the present invention is not particularly limited, but it is preferable to use the polycarbonate resin among the transparent resins and include at least the colorant and the hindered amine light stabilizer.

<Hindered amine light stabilizer>
The molecular weight of the hindered amine light stabilizer used in the present invention is preferably 1000 or less, and more preferably 900 or less. When the molecular weight exceeds 1000, there is a possibility that sufficient weather resistance cannot be obtained when a two-color resin molded product is obtained. The molecular weight is preferably 300 or more, more preferably 400 or more. If the molecular weight is less than 300, the heat resistance is poor, the mold is contaminated when molding a two-color resin molded product, and a molded product with an excellent surface appearance may not be obtained.

The hindered amine light stabilizer used in the present invention is preferably a compound having a piperidine structure. The piperidine structure defined here may be a saturated 6-membered amine structure, and includes a structure in which a part of the piperidine structure is substituted with a substituent. Examples of the substituent include an alkyl group having 4 or less carbon atoms, and a methyl group is particularly preferable.
In particular, a compound having a plurality of piperidine structures is preferable, and a compound in which the plurality of piperidine structures are linked by an ester structure is preferable.

  Examples of the hindered amine light stabilizer of the present invention include 4-piperidinol, 2,2,6,6-tetramethyl-4-benzoate, bis (2,2,6,6-tetramethyl-piperidyl) sebacate, bis (1 , 2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethylpiperidine-4-carboxylic acid) 1,2,3,4-butanetetrayl, 2, Condensate of 2,6,6-tetramethyl-pyridinol, tridecyl alcohol and 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidyl, and tridecyl Alcohol and tridecyl-1,2,3,4-butanetetracarboxylate, bis (1,2,3,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1, -Dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, bis (2,2,26,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester decanedioic acid, 1,1-dimethyl Reaction product of ethyl hydroperoxide and octane, 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5- Di-tert-butyl-4--4-hydroxyphenyl) propionyloxy] ethyl] -2,2,6,6-tetramethylpiperidine, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1 , 2,3,4-Butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2, , 6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], N, N′-bis (2,2,6, 6-tetramethyl-4-piperidyl) -1,6-hexanediamine polymer and 2,4,6-trichloro-1,3,5-triazine, 1,2,3,4-butanetetracarboxylic acid and 2,2 , 6,6-Tetramethyl-4-piperidinol and β, β, β, β-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5,5] undecane-diethanol , N, N′-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6 -Chloro-1,3,5-triazine condensate, dimethyl succinate Le-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate and the like.

  The hindered amine light stabilizer used in the present invention is 0.001 to 5 parts by weight, preferably 0.005 to 3 parts by weight, more preferably 100 parts by weight of the polycarbonate resin. 0.01 parts by weight or more and 1 part by weight or less. If the amount of the hindered amine light stabilizer added is more than 5 parts by weight, it tends to be colored, and even if a colorant is added, it is difficult to obtain a jet black with depth and clarity. When the addition amount is less than 0.001 part by weight, there is a possibility that sufficient weather resistance cannot be obtained when a two-color resin molded product is obtained.

<Antioxidant>
The resin composition used in the present invention may contain an antioxidant. As the antioxidant, general antioxidants used for resins can be used, but from the viewpoint of oxidation stability, thermal stability, jet blackness, etc., phosphite antioxidants, sulfur antioxidants, and Phenol antioxidants are preferred.

Here, the addition amount of the antioxidant is usually preferably 0.001 part by weight or more, more preferably 0.002 part by weight or more, and further preferably 0.005 part by weight or more with respect to 100 parts by weight of the polycarbonate resin. The amount is usually preferably 5 parts by weight or less, more preferably 3 parts by weight or less, still more preferably 2 parts by weight or less.
If the amount of the antioxidant added is more than 5 parts by weight, the mold may be contaminated during molding, and a molded product having an excellent surface appearance may not be obtained. When the amount is less than 0.001 part by weight, there is a tendency that a sufficient improvement effect for the weather resistance test cannot be obtained.

(Phosphite antioxidant)
Phosphite antioxidants include triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl Phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert- Butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol Diphosphite, bis (2,4-di -tert- butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, and the like.

  Among these, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6 -Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is preferably used. These compounds can be used alone or in combination of two or more.

(Sulfur-based antioxidant)
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. . Of the above, pentaerythritol tetrakis (3-laurylthiopropionate) is preferred.

(Phenolic antioxidant)
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-bull-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} -2,4,8,10-tetraoxaspiro (5,5) undecane, 2,6-di-tert-butyl-p-cresol, 2 Compounds such as 6-di -tert- butyl-4-ethyl phenol.

  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.

<Colorant>
Examples of the colorant used in the present invention include organic dyes such as inorganic pigments, organic pigments, and organic dyes.
Specific examples of the inorganic pigment include carbon black; titanium oxide, zinc white, petal, chromium oxide, iron black, titanium yellow, zinc-iron brown, copper-chromium black, copper-iron black, and the like. Examples thereof include oxide pigments.

  Specific examples of organic dyes such as organic pigments and organic dyes include phthalocyanine dyes and pigments; condensation of azo, thioindigo, perinone, perylene, quinacridone, dioxazine, isoindolinone, quinophthalone, etc. Examples of polycyclic dyes include anthraquinone, perinone, perylene, methine, quinoline, heterocyclic, and methyl dyes.

These colorants may be used alone or in combination of two or more.
Examples thereof include inorganic pigments and organic dyes and pigments (such as organic pigments and organic dyes). Of these, inorganic pigments are preferred. By using an inorganic pigment as a colorant, jetness and the like can be maintained for a long time even when used as a two-color resin molded product outdoors.

  The amount of the colorant used in the present invention is usually 0 part by weight or more and less than 0.05 part by weight with respect to 100 parts by weight of the polycarbonate resin. The lower limit is preferably as low as possible, and the upper limit is preferably 0.04 parts by weight or less, more preferably 0.03 parts by weight or less, and further preferably 0.02 parts by weight or less. When the amount of the colorant is 0.05 parts by weight or more, it is difficult to obtain a transparent resin composition having good transparency.

<Total light transmittance>
When the total light transmittance (thickness 3 mm) of the transparent resin composition of the present invention is less than 60%, it may be difficult to use it suitably in the electric / electronic field, the automobile field, the optical part field, and the like. . The total light transmittance (thickness 3 mm) of the polycarbonate resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and particularly preferably 90% or more.
The upper limit is preferably as high as possible, but from the viewpoint of difficulty of realization, the upper limit of the total light transmittance (thickness 3 mm) is 94%.
The total light transmittance (thickness 3 mm) of the transparent resin composition is specifically measured by the method described in the Examples section below.

<Other additives>
In addition, neutralizers, UV absorbers, mold release agents, antistatic agents, lubricants, lubricants, plasticizers, compatibilizers, flame retardants, etc. are added as long as the depth and clarity can be maintained. You can also
In addition, glass fiber, glass milled fiber, glass flakes, glass beads, silica, alumina, titanium oxide, calcium sulfate powder, gypsum, gypsum whisker, barium sulfate, talc as long as the depth and clarity can be maintained. , Calcium silicates such as mica and wollastonite; 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 Inorganic fillers such as whiskers, powdered organic fillers such as wood powder, bamboo powder, coconut starch, cork powder and pulp powder; baluns such as crosslinked polyester, polystyrene, styrene / acrylic copolymer, urea resin Spherical organic filler: Fibrous organic filler such as carbon fiber, synthetic fiber, natural fiber It can also be added.

  In the present embodiment, the mixing timing and mixing method of the colorant, hindered amine light stabilizer and the like to be blended with the polycarbonate resin are not particularly limited. As the mixing time, for example, when the polycarbonate resin is produced by the transesterification method, at the end of the polymerization reaction; and regardless of the polymerization method, the polycarbonate resin in the middle of kneading the polycarbonate resin and other compounding agents is melted Using an extruder or the like, and blending and kneading with a solid polycarbonate resin such as pellets or powder. As a mixing method, a method of directly mixing or kneading the colorant or the like with a polycarbonate resin; a method of manufacturing a high-concentration masterbatch comprising a colorant and a small amount of a polycarbonate resin, and adding the masterbatch to the polycarbonate resin, etc. Is mentioned.

[Opaque resin composition]
The opaque resin composition used in the present invention is not particularly limited, but the same resin composition as that described in the above [Transparent resin composition] is used, but the colorant content is different.
<Colorant>
In the present invention, an opaque resin can be obtained by adding a colorant to a composition equivalent to the transparent tree composition described above, and the opaque resin molded part can be constituted.
Examples of the colorant used in the present invention include organic dyes such as inorganic pigments, organic pigments, and organic dyes.
Specific examples of the inorganic pigment include carbon black; titanium oxide, zinc white, petal, chromium oxide, iron black, titanium yellow, zinc-iron brown, copper-chromium black, copper-iron black, and the like. Examples thereof include oxide pigments.

  Specific examples of organic dyes such as organic pigments and organic dyes include phthalocyanine dyes and pigments; condensation of azo, thioindigo, perinone, perylene, quinacridone, dioxazine, isoindolinone, quinophthalone, etc. Examples of polycyclic dyes include anthraquinone, perinone, perylene, methine, quinoline, heterocyclic, and methyl dyes.

These colorants may be used alone or in combination of two or more.
Examples thereof include inorganic pigments and organic dyes and pigments (such as organic pigments and organic dyes). Of these, inorganic pigments are preferred. By using an inorganic pigment as a colorant, jetness and the like can be maintained for a long time even when used as a two-color resin molded product outdoors.

The amount of the colorant used in the present invention is usually 0.05 parts by weight or more and 5 parts by weight or less with respect to 100 parts by weight of the polycarbonate resin. Preferably they are 0.06 weight part or more and 3 weight parts or less, More preferably, they are 0.07 weight part or more and 2 weight parts or less, More preferably, they are 0.08 weight part or more and 1 weight part or less. If the amount of the colorant is less than 0.05 parts by weight, it is difficult to obtain an opaque resin composition having a depth and clarity. When the amount is more than 5 parts by weight, the surface roughness of the two-color resin molded product increases, and it is difficult to obtain a jet black with depth and clarity.
However, the content of the colorant in the opaque resin composition refers to the final total amount when the colorant is included in the transparent resin composition.

<Total light transmittance>
The total light transmittance (thickness 3 mm) of the opaque resin composition of the present invention is lower than that of the transparent resin composition, and the lower limit is preferably as low as possible, preferably 0% or more.
Moreover, as an upper limit, 10% or less is preferable and 5% or less is more preferable.
The total light transmittance (thickness 3 mm) of the polycarbonate resin is specifically measured by the method described in the Examples section below.

  The opaque resin molded part of the resin molded body of the present invention is excellent in jet blackness and preferably has low brightness. That is, the L * value based on JIS Z 8729 of the molded part (thickness 3 mm) molded from the opaque resin composition is preferably 30 or less, more preferably 25 or less, and still more preferably 20 or less.

Jetness (L * value) can be measured as follows.
A 90 mm × 50 mm × 3 mmt sheet was molded from the resin composition by an injection molding machine (Toshiba Machine Co., Ltd .: EC-75SX). Using this sheet, the L * value can be measured with a spectrocolor difference COLOR-7x manufactured by Kurashiki Boseki Co., Ltd. according to JIS Z 8729. It can be said that blackness is so high that this value is small.

{Manufacture of polycarbonate resin composition}
The polycarbonate resin composition used in 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. it can.

The polycarbonate resin composition used in the present invention thus obtained is excellent in light resistance, transparency, hue, heat resistance, thermal stability, moldability, surface hardness and mechanical strength.
Below, the outline of the manufacturing method of the resin molding of this invention is demonstrated.

<Production method of resin molding>
This manufacturing method is a method of manufacturing a resin molded body by injection molding.
First, the resin molded body includes a molded part made of an opaque resin on the back surface of a molded part made of a transparent resin. And the metal mold | die used for this injection molding is comprised from the design side metal mold | die and the non-design side metal mold | die. A cavity for forming the transparent resin molded part is formed in the design side mold, and a cavity for forming the opaque resin molded part is formed in the non-design side mold.
The non-design side mold temperature is lower than the design-side mold temperature, and the resin is molded by injection molding at a difference between the non-design-side mold temperature and the design-side mold temperature of less than 20 ° C. A molded body can be produced.

Moreover, the following method is mention | raise | lifted as another manufacturing method of the resin molding of this invention.
This manufacturing method is a method of manufacturing a resin molded body by injection molding.
First, the resin molded body includes a molded part made of an opaque resin on the back surface of a molded part made of a transparent resin. And the metal mold | die used for this injection molding is comprised from the design side metal mold | die and the non-design side metal mold | die. A cavity for forming the transparent resin molded part is formed in the design side mold, and a cavity for forming the opaque resin molded part is formed in the non-design side mold.
The thickness of the transparent resin molded part is smaller than the thickness of the opaque resin molded part, and the difference between the thickness of the transparent resin molded part and the thickness of the opaque resin molded part is 18% or less. Thus, a resin molded body can be manufactured.
Next, the detail of the manufacturing method of the resin molding of this invention is demonstrated below.

[Molding die equipment]
As shown in FIGS. 1 and 2, a resin molding die apparatus 1 according to the present invention includes two molds constituting the mold apparatus 1, that is, a fixed side mold 2 and a movable side mold 3. The In addition, as shown in FIG. 3, the movable die 3 has two recesses constituting a cavity (also referred to as “primary cavity”) 7 having the same shape for filling the primary resin. As shown in FIG. 4, the fixed mold 2 is formed with a single recess that constitutes a cavity 12 (also referred to as “secondary cavity”) for filling the secondary resin. These recesses form a cavity by closing these two molds.
3 and 4 are views in which the mold apparatus 1 is opened and viewed from a parting line (PL) which is a contact surface between the fixed mold 2 and the movable mold 3.

  Of the two molds, a concave part of one (movable side) mold is formed with a design surface side cavity surface (also referred to as a “primary cavity surface”) having a design surface, and the other (fixed side). A non-design surface side cavity surface (also referred to as a “secondary side cavity surface”) that does not have a design surface is formed in the concave portion of the mold of FIG.

  1 to 4, a design surface side cavity surface having a design surface is formed in the movable mold 3, and the non-design surface side cavity surface having no design surface is formed in the fixed mold 2. However, the present invention is not limited to this and may be reversed.

  As shown in FIGS. 1 and 3, at least one side surface of the cavity 7 of the movable mold 3, at the boundary between the design surface side cavity surface and the non-design surface side cavity surface of the cavity. A primary side gate 8 for supplying the resin is provided. Resin is fed into the side gate 8 via the primary spray 4, the primary pin gate 6, and the primary runner 5 for introducing the resin from the outside of the resin molding die device 1. The resin is supplied from the side gate 8 to the primary side cavity (design surface side cavity) 7.

As shown in FIGS. 2 and 4, a secondary pin gate 11 for supplying the resin is provided at at least one end of the cavity 12 of the fixed mold 2. Further, the cavity 12 of the fixed mold 2 is formed in the insert mold 13 and the thickness of the resin molded body can be adjusted by replacing the insert (not shown).
The secondary side pin gate 11 is fed with resin through the secondary side spray 9 and the secondary side runner 10 for introducing the resin from the outside of the resin molding die device 1. Then, after adjusting the nesting to a predetermined position, the resin is supplied from the secondary side pin gate 11 to the secondary side cavity 12.

“Injection molding using resin mold equipment”
Examples of a method for producing an injection-molded body using the resin molding die apparatus 1 include the following methods.
First, the design side (transparent part) resin and the non-design side (opaque part) resin are once pelletized directly or by a melt extruder. At this time, when a plurality of resins are used or when an additive such as a colorant is used, they are mixed and kneaded into pellets by the melt extruder.

  Next, a design side (transparent portion) resin is placed in the primary cylinder (not shown) of the injection molding machine, and a non-design side (opaque portion) resin is melted in the secondary cylinder (not shown). Then, the movable mold 3 is brought into contact with the fixed mold 2 to close the mold, and the primary spray 4, the primary pin gate 6, the primary runner 5, and the primary side of the resin molding mold apparatus 1. The design side (transparent portion) resin is filled into the primary side cavity 7 through the gate 8 and the pressure is maintained. Thereafter, the resin in the primary cavity 7 is cooled, the mold is opened, the design side (transparent portion) resin is left in the cavity 7 of the movable mold 3, and the movable mold 3 is rotated by 180 °.

  Next, the movable mold 3 is brought into contact with the fixed mold 2, the mold is closed, and the non-design side (opaque part) resin is applied to the secondary spray 9, secondary of the resin mold apparatus 1. The non-design side (colored portion) resin is filled into the secondary cavity 12 via the side runner 10 and the secondary pin gate 11, and the pressure is maintained. Thereafter, the resin in the secondary cavity 12 is cooled, the mold is opened, and the two-color resin molded body is taken out.

  The mold apparatus 1 for resin molding includes a movable side cooling pipe 14 in a movable side mold 3 and a fixed side cooling pipe 15 in a fixed side mold 2. It is connected from a separate mold temperature controller so that the temperature can be adjusted, and water can be passed.

  The cavity 12 of the fixed mold 2 of the resin mold apparatus 1 can be adjusted to have a thickness of 2 mm, 1.8 mm, and 1.6 mm by exchanging the insert in advance.

  The injection molding conditions vary depending on the type of resin used, but when the polycarbonate resin composition is used, the cylinder temperature of the injection molding machine is set to 220 ° C. to 260 ° C., and the mold for the resin molding die device is used. The mold temperature is preferably 40 ° C to 90 ° C. In particular, the non-design side mold temperature is lower than the design-side mold temperature, and a difference between the non-design-side mold temperature and the design-side mold temperature is less than 20 ° C. Moreover, as an upper limit, it is preferable that it is 19 degrees C or less, It is more preferable that it is 18 degrees C or less, It is especially preferable that it is 17 degrees C or less. Moreover, as a lower limit, it is preferable that it is 1 degreeC or more, It is more preferable that it is 3 degreeC or more, It is more preferable that it is 6 degreeC or more, It is especially preferable that it is 8 degreeC or more. By setting it as this range, when integrally forming the transparent part and the opaque part of the obtained resin molding, there is no deformation, and internal stress and distortion of the transparent part can be reduced. On the other hand, when the difference in mold temperature is smaller than the above range, there is a case where warpage deformation becomes large. Furthermore, if the difference in mold temperature is larger than the above range, problems such as poor resin adhesion and damage to the mold may occur.

  As described above, the thickness of the opaque resin molded portion can be adjusted by exchanging the insert. At this time, the thickness of the transparent resin molded portion is thinner than the thickness of the opaque resin molded portion, and the difference between the thickness of the transparent resin molded portion and the thickness of the opaque resin molded portion is 18% or less. It is preferable. Moreover, as an upper limit, it is more preferable that it is 16% or less, It is more preferable that it is 14% or less, It is especially preferable that it is 12% or less. In addition, the lower limit is preferably 1% or more, more preferably 3% or more, further preferably 5% or more, and particularly preferably 8% or more. By setting it within this range, the feature that warpage deformation can be reduced can be exhibited. On the other hand, if the thickness difference is smaller than the above range, there may be a problem that warpage deformation becomes large. Furthermore, if the wall thickness difference is larger than the above range, warping deformation increases if the opaque resin wall thickness is large. If the opaque resin wall thickness is small, the primary resin is eluted due to the filling pressure. There is a case.

  As the resin used in the resin molded body according to the present invention, the above-described resin can be used, and the resin used has a predetermined relationship between the heat resistant temperature of the transparent resin molded portion and the heat resistant temperature of the opaque resin molded portion. It is preferable to be within the range. That is, the heat resistant temperature of the transparent resin molded part is lower than the heat resistant temperature of the opaque resin molded part, and the difference between the heat resistant temperature of the transparent resin molded part and the heat resistant temperature of the opaque resin molded part is preferably 30 ° C. or less. . Moreover, as an upper limit, it is more preferable that it is 25 degrees C or less, It is more preferable that it is 20 degrees C or less, It is especially preferable that it is 18 degrees C or less. Moreover, as a lower limit, it is preferable that it is 1 degreeC or more, It is more preferable that it is 3 degreeC or more, It is further more preferable that it is 5 degreeC or more, It is especially preferable that it is 8 degreeC or more. By setting it within this range, it is possible to exhibit the feature that the adhesiveness of the resin is improved. On the other hand, if the difference in heat resistant temperature is smaller than the above range or the heat resistance of the opaque resin is high, there may be a problem that the primary side resin is eluted. Furthermore, if the difference in heat resistant temperature is larger than the above range or the heat resistant temperature is low, there may be a problem that thermal deformation occurs during actual use.

[Resin molding]
The transparent resin molded part 16 obtained by the above method has a shape as shown in FIG. 5 and is a resin molded body 18 which is a laminate of the transparent resin molded part 16 and the opaque resin molded part 17 obtained by the above method. Has a shape as shown in FIGS.

[Various resin panels]
The resin molded body according to the present invention can be produced by injection molding (double molding) the polycarbonate resin composition by the above-described method using the above-described two-color resin molding die apparatus.

  The two-color resin molded article produced by the production method of the present invention is particularly suitable for various resin display panels, utilizing its weather resistance, colored sharpness due to transparency, and long-term durability of these characteristics. Used.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention more concretely, this invention is not limited to a following example at all.

[Method for producing isosorbide polycarbonate resin composition (hereinafter sometimes referred to as “ISP resin composition”)]
(1) Measurement of structural unit ratio (composition ratio) derived from each dihydroxy compound in polycarbonate copolymer or resin composition Structural unit ratio derived from each dihydroxy compound in polycarbonate copolymer or resin composition is polycarbonate. 30 mg of resin is weighed and dissolved in about 0.7 mL of deuterated chloroform to obtain a solution, which is put in an NMR tube having an inner diameter of 5 mm, and 1H NMR spectrum at room temperature using JNM-AL400 (resonance frequency 400 MHz) manufactured by JEOL Ltd. Was measured. 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 structural unit ratio may be simply referred to as a composition ratio.

(2) Measurement of glass transition temperature (Tg) The glass transition temperature (Tg) was measured using a differential scanning calorimeter (DSC6220, manufactured by SII Nanotechnology). About 10 mg of a resin sample was sealed in an aluminum pan manufactured by the same company, and the temperature was raised from room temperature to 250 ° C. at a temperature rising rate of 20 ° C./min under a nitrogen stream of 50 mL / min. After maintaining the temperature for 3 minutes, it was cooled to 30 ° C. at a rate of 20 ° C./min. The temperature was maintained at 30 ° C for 3 minutes, and the temperature was increased again to 200 ° C at a rate of 20 ° C / min. The value of the peak top of the DDSC in the measurement data obtained by the second temperature increase was defined as Tg.

(3) Measurement of reduced viscosity A polycarbonate copolymer or resin composition sample was dissolved using a mixed solvent of phenol and 1,1,2,2-tetrachloroethane methylene chloride in a mass ratio of 1: 1. A polycarbonate solution with a concentration of 00 g / dL was precisely prepared. Made by Moriyu Rika Kogyo Co., Ltd .: Measured at a temperature of 20.0 ° C. ± 0.1 ° C. using an Ubbelohde type viscosity tube. From the following equation, the relative viscosity is calculated from the solvent passage time t ₀ and the polycarbonate solution passage time t _Find η _rel ,
η _rel = t / t ₀
From the relative viscosity, the specific viscosity η _sp was determined from the following equation.
η _sp = (η−η ₀ ) / η ₀ = η _rel −1
Then, the reduced viscosity η _sp / c was determined by dividing the specific viscosity by the concentration c (g / dL). The higher this value, the higher the molecular weight.

(4) Preparation method of test piece The pellet of polycarbonate resin was dried at 80 degreeC for 6 hours using the hot air dryer. 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 the injection molded plate is subjected to a resin temperature of 240 ° C., a mold temperature of 60 ° C., and a molding cycle of 40 seconds. ISO test pieces for mechanical properties (width 60 mm × length 60 mm × thickness 3 mm) were molded.

(5) Total light transmittance and haze measurement In accordance with JIS K7105 (1981), the injection molded plate obtained in (2) above was used as a D65 light source using a haze meter (NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd.). The total light transmittance and haze of the test piece were measured.

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 (manufactured by Shin Nippon Rika Co., Ltd., trade name: SKY CHDM)
・ DPC: Diphenyl carbonate (Mitsubishi Chemical Corporation)
AS2112: Compound name, tris (2,4-di-t-butylphenyl) phosphite (manufactured by ADEKA)
IRGANOX 1010: Compound name, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (manufactured by BASF Japan Ltd.)
E-275: Compound name, ethylene glycol distearate (manufactured by NOF Corporation)

(Production Example 1)
In a polymerization reactor equipped with a stirring blade and a reflux condenser controlled at 100 ° C., ISB and CHDM, DPC and calcium acetate monohydrate having a chloride ion concentration of 10 ppb or less by purification by distillation, in a molar ratio. ISB / CHDM / DPC / calcium acetate monohydrate = 0.70 / 0.30 / 1.00 / 1.3 × 10 ⁻⁶ , fully substituted with nitrogen, oxygen concentration 0.0005 The volume was adjusted to 0.001% by volume. 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. After the contents thus oligomerized are once restored to atmospheric pressure, they are transferred to another polymerization reaction apparatus equipped with a stirring blade and a reflux condenser controlled in the same manner as described above. The internal temperature was set to 220 ° C. and the pressure was set to 200 Pa in 60 minutes.
Thereafter, the internal temperature was set to 230 ° C. over 20 minutes, the pressure was reduced to 133 Pa or less, the pressure was restored when the predetermined stirring power was reached, the contents were extracted in the form of strands, and the pellets of polycarbonate copolymer were formed with a rotary cutter. The obtained resin is referred to as “resin 1”.

(Production Example 2)
Manufacture except that in Preparation Example 1, the charge composition was changed to ISB / CHDM / DPC / calcium acetate monohydrate = 0.60 / 0.40 / 1.00 / 1.3 × 10 ⁻⁶ In the same manner as in Example 1, polycarbonate copolymer pellets were obtained. The obtained resin is referred to as “resin 2”.

(Production Example 3)
Manufacture except that in Preparation Example 1, the charge composition was changed to ISB / CHDM / DPC / calcium acetate monohydrate = 0.50 / 0.50 / 1.00 / 1.3 × 10 ⁻⁶ In the same manner as in Example 1, polycarbonate copolymer pellets were obtained. The obtained resin is referred to as “resin 3”.

(Production Example 4)
Manufacture except that in Preparation Example 1, the charging composition was changed to ISB / CHDM / DPC / calcium acetate monohydrate = 0.80 / 0.20 / 1.00 / 1.3 × 10 ⁻⁶ In the same manner as in Example 1, polycarbonate copolymer pellets were obtained. The obtained resin is referred to as “resin 4”.

  Resin 1 to Resin 4 are summarized in Table 1 below.

(Preparation of transparent resin composition)
The polycarbonate copolymer pellets (resin 1 to resin 4) produced in Production Example 1 to Production Example 4 were further mixed with 0.05% by weight of AS2112 as an antioxidant, 0.1% by weight of IRGANOX 1010, and a release agent. E-275 is blended by 0.3% by weight, extruded at a resin temperature of 250 ° C. using a twin screw extruder (TEX30HSS-32) manufactured by Nippon Steel Works, cooled and solidified with water, and then a rotary cutter. A transparent resin composition (hereinafter, referred to as “transparent resin 1” to “transparent resin 4”) was produced by pelletizing.

(Preparation of opaque resin composition)
Pigment White 6 as a colorant, 0.015 part by weight, Pigment Red 101 as 0.012 part by weight, and Pigment Brown 24 as 0.02 part by weight per 100 parts by weight of each of the transparent resin 1 to the transparent resin 4 obtained above. 005 parts by weight, Pigment Blue 29 0.02 part by weight, Pigment Black 7 0.12 part by weight, and hindered amine light stabilizer (C-1) 0.05 part by weight are blended by Nippon Steel Works Using an extruder (TEX30HSS-32), the resin was extruded at a resin temperature of 250 ° C., cooled and solidified with water, and then pelletized with a rotary cutter to form an opaque resin (hereinafter “opaque resin 1” to “opaque resin 4”. ").

[Example 1]
The injection mold shown in FIGS. 1 to 4 was used as the resin mold.
This mold has two recesses (width 40 mm, length 120 mm, thickness 2 mm) for filling the movable side mold 3 shown in FIG. 3 with the resin on the design side (transparent part), fixed as shown in FIG. One frame-shaped recess (width 40 mm, length 120 mm, wall thickness 2 mm, frame width 4 mm) for filling the non-design side (opaque part) resin in the side mold 2 is formed.
The mold temperature of the movable mold 3 was adjusted to 80 ° C. by passing hot water of 80 ° C. through a cooling pipe 14 shown in FIG.
The mold temperature of the fixed mold was adjusted to 65 ° C. by passing 65 ° C. hot water from a mold temperature controller (not shown) through the cooling pipe 15 shown in FIG.
The molding machine uses a DC120-9a2 color molding machine manufactured by Nissei Plastic Industry Co., Ltd., and the transparent resin 1 which is the design side (transparent part) resin in the A side cylinder is 250 ° C. and the non-design side is in the B side cylinder ( The opaque resin 1 which is the resin of the opaque part) is melted at 250 ° C., the movable mold 3 is brought into contact with the fixed mold 2, the mold is closed, and the two-color resin molding mold spray 4 is closed. The resin on the design side (transparent portion) is filled into the primary cavity 7 through the pin gate 6, the runner 5, and the side gate 8, and the pressure is maintained. Thereafter, the resin in the cavity was cooled, the mold was opened, the design side (transparent portion) resin was left in the cavity 7 of the movable side mold 3, and the movable side mold 3 was rotated 180 °.
Next, the movable mold 3 is brought into contact with the fixed mold 2, the mold is closed, and the resin on the non-design side (opaque part) is sprayed with the resin molding mold spray 9, runner 10, and pin gate 11. Thus, the resin on the non-design side (opaque part) is filled in the secondary cavity 12 and the pressure is maintained. Thereafter, the resin in the cavity was cooled, the mold was opened, and the resin molded body was taken out.

  When the obtained resin molded body is placed on a regular board with the resin side of the non-design side (opaque part) as the bottom, the central part of the resin on the design side (transparent part) is on the design side (transparent part) Although a convex deformation 0.2 mm higher than both ends of the resin was observed, the function as a resin panel was satisfactory, and the two-color resin molded article had a beautiful appearance over the entire surface.

[Example 2]
As shown in Table 2 below, injection molding was performed in the same manner as in Example 1 except that the mold temperature of the fixed mold was adjusted to 75 ° C.
When the obtained resin molding is placed on a regular board with the non-design side (opaque part) resin at the bottom, the central part of the design side (transparent part) resin is the resin on the design side (transparent part) A convex deformation 0.5 mm higher than both ends was observed, but the function as a resin panel was satisfactory, and the two-color resin molded article had a beautiful appearance over the entire surface.

[Example 3]
As shown in Table 2 below, the frame-shaped recess for filling the resin on the non-design side (opaque part) in the stationary mold shown in FIG. Injection molding was performed in the same manner as in Example 1 except that the movable mold temperature and the fixed mold temperature were adjusted to 80 ° C.
When the obtained resin molded product is placed on a regular board with the resin on the non-design side (opaque part) at the bottom, the central part of the design side (transparent part) resin is the resin on the design side (transparent part). Although a convex deformation 0.3 mm higher than both ends was observed, the function as a resin panel was satisfactory, and the two-color resin molded article had a beautiful appearance over the entire surface.

[Example 4]
As shown in Table 2 below, injection molding was performed in the same manner as in Example 1 except that the non-design side (opaque part) resin was changed to opaque resin 3 in the B side cylinder.
When the obtained resin molding is placed on a regular board with the non-design side (opaque part) resin at the bottom, the central part of the design side (transparent part) resin is the resin on the design side (transparent part) A convex deformation 0.5 mm higher than both ends was observed, but the function as a resin panel was satisfactory, and the two-color resin molded article had a beautiful appearance over the entire surface.

[Comparative Example 1]
As shown in Table 2 below, injection molding was performed in the same manner as in Example 1 except that the mold temperature of the movable mold was adjusted to 80 ° C.
When the obtained resin molding is placed on a regular board with the non-design side (opaque part) resin at the bottom, the central part of the design side (transparent part) resin is the resin on the design side (transparent part) A convex deformation 1.7 mm higher than both ends was observed, and the function as a resin panel was not satisfied.

[Comparative Example 2]
As shown in Table 2 below, injection molding was performed in the same manner as in Example 1 except that the mold temperature of the fixed mold was adjusted to 60 ° C.
When the obtained resin molding is placed on a regular board with the non-design side (opaque part) resin at the bottom, the central part of the design side (transparent part) resin is the resin on the design side (transparent part) Convex-shaped deformation that was 2.3 mm higher than both ends was observed, and the function as a resin panel was not satisfied.

[Comparative Example 3]
As shown in Table 2 below, injection molding was performed in the same manner as in Example 1 except that the mold temperature of the fixed mold was adjusted to 90 ° C.
When the obtained resin molded product is placed on the regular board with the resin on the non-design side (opaque part) at the bottom, the central part of the resin on the non-design side (opaque part) comes into contact with the regular board and the design side ( At both ends of the resin of the transparent part), convex deformation that was 0.8 mm higher than the center of the design side (transparent part) was observed, and the function as a resin panel was not satisfied.

DESCRIPTION OF SYMBOLS 1 Resin mold apparatus 2 Fixed side mold 3 Movable side mold 4 Primary side spray 5 Primary side runner 6 Primary side pin gate 7 Primary side cavity 8 Primary side gate 9 Secondary side spray 10 Secondary side runner 11 2 Secondary side pin gate 12 Secondary side cavity 13 Nesting mold 14 Movable side cooling pipe 15 Fixed side cooling pipe 16 Transparent (design side) resin molding part 17 Opaque (non-design side) resin molding part 18 Resin molding

Claims (11)

A method for producing a resin molded body by injection molding,
The resin molded body includes a molded portion made of an opaque resin on the back surface of a molded portion made of a transparent resin,
The mold used for the injection molding is composed of a design side mold and a non-design side mold,
A cavity for forming the transparent resin molding part is formed in the design side mold,
A cavity for forming the opaque resin molding part is formed in the non-design side mold,
The resin characterized in that the non-design side mold temperature is lower than the design side mold temperature, and the injection molding is performed at a difference between the non-design side mold temperature and the design side mold temperature of less than 20 ° C. Manufacturing method of a molded object.   The thickness of the transparent resin molded portion is smaller than the thickness of the opaque resin molded portion, and the difference between the thickness of the transparent resin molded portion and the thickness of the opaque resin molded portion is 18% or less. The manufacturing method of the resin molding of Claim 1. A method for producing a resin molded body by injection molding,
The resin molded body includes a molded portion made of an opaque resin on the back surface of a molded portion made of a transparent resin,
The mold used for the injection molding is composed of a design side mold and a non-design side mold,
A cavity for forming the transparent resin molding part is formed in the design side mold,
A cavity for forming the opaque resin molding part is formed in the non-design side mold,
The thickness of the transparent resin molded portion is smaller than the thickness of the opaque resin molded portion, and the difference between the thickness of the transparent resin molded portion and the thickness of the opaque resin molded portion is 18% or less. A method for producing a resin molded product.   The heat resistant temperature of the transparent resin molded part is lower than the heat resistant temperature of the opaque resin molded part, and the difference between the heat resistant temperature of the transparent resin molded part and the heat resistant temperature of the opaque resin molded part is 30 ° C. or less. The manufacturing method of the resin molding as described in any one of Claims 1-3 to do. The said transparent resin is a polycarbonate resin composition containing a polycarbonate resin containing at least a structural unit derived from a dihydroxy compound having a site represented by the following general formula (1) in a part of its structure. The manufacturing method of the resin molding as described in any one of 1-4.

The opaque resin is a polycarbonate resin composition containing a polycarbonate resin containing 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. The manufacturing method of the resin molding as described in any one of 1-5.

The said dihydroxy compound is a compound represented by following General formula (2), The manufacturing method of the resin molding of Claim 5 or 6 characterized by the above-mentioned.

  The said polycarbonate resin further contains the structural unit derived from the at least 1 sort (s) of compound chosen from the group which consists of an aliphatic dihydroxy compound and an alicyclic dihydroxy compound, The any one of Claims 5-7 characterized by the above-mentioned. The manufacturing method of the resin molding of description.   The glass transition temperature of the said polycarbonate resin is less than 145 degreeC, The manufacturing method of the resin molding as described in any one of Claims 5-8 characterized by the above-mentioned. The opaque resin is obtained by blending a colorant with the transparent resin,
Content of a coloring agent is 0.05 to 5 weight part with respect to 100 weight part of polycarbonate resin, The resin molded object as described in any one of Claims 1-9 characterized by the above-mentioned. Production method.   The resin molding manufactured by the manufacturing method of the resin molding as described in any one of Claims 1-10.

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