Resin composition and molded article

Abstract

To provide a resin composition excellent in scratch resistance, transparency and impact resistance and having high pencil hardness SOLUTION: A resin composition comprising one or more resins, wherein the one or more resins comprise a polycarbonate resin (A) comprising a structural unit (a1) derived from a predetermined dihydroxy compound, the resin composition further comprising a glass frit (B), and the content of the glass frit (B) is from 0.1 to 4.0 parts by mass based on 100 parts by mass of the total amount of the parts by mass of the one or more resins.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin composition and a molded article using the resin composition, and more particularly to a polycarbonate resin composition and a molded article using the polycarbonate resin composition. [Background technology]

[0002] Polycarbonate resins are generally made from bisphenols as monomer components, and taking advantage of their superior transparency, heat resistance, impact resistance, etc., they are widely used as so-called engineering plastics in fields such as electrical and electronic components, automotive parts, medical parts, building materials, films, sheets, bottles, optical recording media, and lenses. However, in recent years, there has been a demand for polycarbonate resins that are excellent in weather resistance and scratch resistance.

[0003] To solve these problems, polycarbonate resins using ether group-containing diols, such as isosorbide, have been developed (Patent Documents 1 and 2). Polycarbonate resins using isosorbide are known to have excellent transparency, weather resistance, scratch resistance, and impact resistance, and are known to be used in automotive interior and exterior materials, display panels, etc.

[0004] Even polycarbonate resins containing an isosorbide structure have the problem that molded articles are prone to scratches (scratches) when repeatedly wiped with a rag or tissue, etc. To solve this problem, a resin composition containing a silicone compound has been proposed (Patent Document 3). Furthermore, in order to provide a composition with good pencil hardness, a part formed from a composition in which an infinite filler is added to a polycarbonate resin has been proposed (Patent Document 4). In order to achieve both hardness and transparency, a resin composition has been proposed that contains an aliphatic polycarbonate resin as the main component and 2 to 40 mass % of a small glass filler whose refractive index for light with a wavelength of 589.3 nm is close to that of the polycarbonate resin (Patent Document 5). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. WO2004 / 111106 [Patent Document 2] International Publication No. WO2007 / 063823 [Patent Document 3] Japanese Patent Application Laid-Open No. 2015-199954 [Patent Document 4] Patent No. 5437580 [Patent Document 5] Patent No. 6131264 Summary of the Invention [Problem to be solved by the invention]

[0006] However, although the composition of Patent Document 3 improves scratch resistance, it does not improve pencil hardness, and there is room for improvement. In addition, because Patent Document 4 uses talc, there is a problem of reduced transparency, and there is still room for improvement in terms of suppressing the phenomenon in which the edges of the molded article turn white or the like and improving the aesthetics. Furthermore, the composition of Patent Document 5 has a significant decrease in impact resistance, and there is still room for improvement.

[0007] In view of the above problems, an object of the present invention is to provide a resin composition that is excellent in scratch resistance, transparency, and impact resistance and has high pencil hardness, and a molded article made from the resin composition. [Means for solving the problem]

[0008] As a result of extensive research to solve the above problems, the present inventors have found that a resin composition having excellent scratch resistance, transparency, and impact resistance can be obtained by using a resin composition containing a specific polycarbonate resin (A) and glass frit (B), and have arrived at the present invention as described below. That is, the present invention includes at least the following embodiments and embodiments that combine features of the following embodiments.

[0009] [1] A resin composition comprising one or more resins, The one or more resins include a polycarbonate resin (A) containing a structural unit (a1) derived from a dihydroxy compound represented by the following general formula (1): The resin composition further contains a glass frit (B), The resin composition has a content of the glass frit (B) of 0.1 to 4.0 parts by mass relative to 100 parts by mass of the total amount of the one or more resins.

[0010] [ka]

[0011] [2] The resin composition according to [1], wherein the polycarbonate resin (A) is a copolymer polycarbonate resin further containing structural units (a2) derived from one or more dihydroxy compounds selected from the group consisting of ether group-containing dihydroxy compounds, aliphatic dihydroxy compounds, and alicyclic dihydroxy compounds, which are different from the dihydroxy compound represented by formula (1).

[0012] [3] The resin composition according to [1] or [2], wherein the polycarbonate resin (A) contains 30 mol % or more and 95 mol % or less of the structural unit (a1) derived from the dihydroxy compound represented by the formula (1) above, relative to 100 mol % of all structural units derived from the dihydroxy compound.

[0013] [4] The resin composition according to any one of [1] to [3], wherein the absolute value of the difference in refractive index between the one or more resins and the glass frit (B) for light having a wavelength of 589.3 nm is 0.05 or less.

[0014] [5] The resin composition according to any one of [1] to [4], wherein the refractive index of the glass frit (B) for light having a wavelength of 589.3 nm is 1.480 to 1.520.

[0015] [6] The resin composition further contains an impact modifier (E), The resin composition according to any one of [1] to [5], wherein the content of the impact resistance modifier (E) is 0.1 to 50 parts by mass, with the total amount of the parts by mass of the one or more resins being 100 parts by mass.

[0016] [7] The resin composition according to [6], wherein the impact resistance modifier (E) is an elastomer having a core-shell structure.

[0017] [8] A molded article obtained by molding the resin composition according to any one of [1] to [7].

[0018] [9] A method for producing a composition, comprising: The method includes mixing 100 parts by mass of a resin with 0.1 parts by mass or more and 4.0 parts by mass or less of a glass frit (B), The method for producing a composition, wherein the resin comprises a polycarbonate resin (A) containing a structural unit (a1) derived from a dihydroxy compound represented by the following general formula (1):

[0019] [ka] [Effects of the Invention]

[0020] According to the present invention, it is possible to provide a resin composition having excellent scratch resistance, transparency, and impact resistance and high pencil hardness, and a molded article using the resin composition. DETAILED DESCRIPTION OF THE INVENTION

[0021] The following describes in detail the embodiments of the present invention. However, the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention, and the present invention is not limited to the following content as long as it does not exceed the gist of the present invention. [Resin composition] In one embodiment, the resin composition of the present invention comprises: A resin composition comprising one or more resins, The one or more resins include a polycarbonate resin (A) containing a structural unit (a1) derived from a dihydroxy compound represented by the following general formula (1): The resin composition further contains a glass frit (B), The resin composition has a content of the glass frit (B) of 0.1 to 4.0 parts by mass relative to 100 parts by mass of the total amount of the one or more resins.

[0022] [ka]

[0023] The resin composition of the present invention will be described in detail below.

[0024] <Polycarbonate resin (A)> The one or more resins contained in the resin composition of the present invention include a polycarbonate (A), and the polycarbonate resin (A) includes a structural unit (a1) derived from a dihydroxy compound represented by the following general formula (1) (hereinafter, sometimes referred to as "dihydroxy compound (1)").

[0025] [ka]

[0026] Examples of the dihydroxy compound (1) include isosorbide, isomannide, and isoidet, which are stereoisomers of the substance represented by the formula (1). These dihydroxy compounds (1) may be used singly or in combination of two or more. Among them, isosorbide, which is obtained by dehydration condensation of sorbitol, which is abundant and easily available as a plant-derived resource and is produced from various starches, is most preferred in terms of availability and ease of production, moldability, and properties of the resulting molded products (for example, heat resistance, impact resistance, surface hardness, and carbon neutrality).

[0027] The dihydroxy compound represented by formula (1) is easily oxidized gradually by oxygen, and when isosorbide is oxidized, decomposition products such as formic acid may be generated. Therefore, in order to prevent decomposition by oxygen during storage or handling during production, it is preferable to avoid moisture contamination, use an oxygen scavenger, or store under a nitrogen atmosphere. The use of such isosorbide as a raw material for producing the polycarbonate resin (A) tends to suppress coloration of the polycarbonate resin (A) and the resin composition of the present invention, and also tends to suppress deterioration of physical properties, promote favorable progress of the polymerization reaction, and facilitate the production of a high-molecular-weight polymer.

[0028] When the total amount of structural units derived from dihydroxy compounds contained in the polycarbonate resin (A) is taken as 100 mol %, the content of the structural unit (a1) is preferably 20 mol % or more and 95 mol % or less, more preferably 30 mol % or more and 85 mol % or less, and even more preferably 40 mol % or more and 85 mol % or less.

[0029] The polycarbonate resin (A) of the present invention may be a copolymer polycarbonate resin containing, in addition to the structural units derived from the dihydroxy compound (1), structural units derived from a dihydroxy compound other than the dihydroxy compound (1). Such polycarbonate resin (A) is produced, for example, using one or more dihydroxy compounds other than the dihydroxy compound (1) according to the production method of polycarbonate resin (A) described below.

[0030] The structural units derived from dihydroxy compounds other than dihydroxy compound (1) contained in the polycarbonate resin (A) of the present invention are not particularly limited, but are preferably structural units derived from one or more dihydroxy compounds selected from the group consisting of ether group-containing dihydroxy compounds other than the dihydroxy compound represented by formula (1), aliphatic dihydroxy compounds, and alicyclic dihydroxy compounds (hereinafter sometimes referred to as structural units (a2)). These dihydroxy compounds have flexible molecular structures, and therefore flexible structural units can be introduced into the polymer chain, thereby improving the toughness and impact resistance of the resin.

[0031] (aliphatic dihydroxy compounds) Examples of aliphatic dihydroxy compounds (aliphatic hydrocarbon dihydroxy compounds) include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, and 1, Examples include straight-chain aliphatic dihydroxy compounds such as 6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol, and branched-chain aliphatic dihydroxy compounds such as neopentyl glycol, 2-ethyl-1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, hydrogenated dilinoleyl glycol, and hydrogenated dioleyl glycol. Among these, linear aliphatic dihydroxy compounds such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol are preferred from the viewpoints of ease of availability and ease of handling. The above-mentioned exemplified compounds are only examples of aliphatic dihydroxy compounds that can be used in the present invention, and the present invention is not limited to these. These aliphatic dihydroxy compounds may be used alone or in combination of two or more.

[0032] (alicyclic dihydroxy compounds) Alicyclic dihydroxy compounds are not particularly limited, but include compounds having a 5-membered ring structure or a 6-membered ring structure. The 6-membered ring structure may be fixed in a chair or boat shape by a covalent bond. The number of carbon atoms contained in the alicyclic dihydroxy compound is usually 70 or less, preferably 50 or less, and more preferably 30 or less. By setting the number of carbon atoms to the above upper limit or less, synthesis and purification can be facilitated while ensuring heat resistance. By setting the number of carbon atoms to the above lower limit or more, purification and availability tend to be easy, while the ring structure is stabilized and synthesis is facilitated.

[0033] Examples of the alicyclic dihydroxy compound include cyclohexanediols such as 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, and 2-methyl-1,4-cyclohexanediol; cyclohexenediols such as 4-cyclohexene-1,2-diol; cyclohexanedimethanols such as 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, and 1,4-cyclohexanedimethanol; norbornanedimethanols such as 2,3-norbornanedimethanol and 2,5-norbornanedimethanol; tricyclodecane dimethanol, pentacyclopentadecanedimethanol, 1,3-adamantanediol, and 2,2-adamantanediol.

[0034] Among the specific examples of the above-mentioned alicyclic dihydroxy compounds, cyclohexane dimethanols such as 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, and 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, pentacyclopentadecanedimethanol, 1,3-adamantanediol, and 2,2-adamantanediol are preferred. In terms of availability and ease of handling, 1,4-cyclohexanedimethanol and 1,3-cyclohexanedimethanol are also preferred. Among these, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, and pentacyclopentadecanedimethanol are particularly preferred, and 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,4-cyclohexanedimethanol, and tricyclodecane dimethanol are most preferred. The above-mentioned exemplary compounds are merely examples of alicyclic dihydroxy compounds that can be used in the present invention, and the present invention is not limited to these. These alicyclic dihydroxy compounds may be used alone or in combination of two or more.

[0035] (Ether group-containing dihydroxy compounds other than the dihydroxy compound represented by formula (1)) Examples of ether group-containing dihydroxy compounds other than the dihydroxy compound represented by formula (1) include oxyalkylene glycols and dihydroxy compounds containing an acetal ring. Examples of oxyalkylene glycols that can be used include diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, and polypropylene glycol.

[0036] As the dihydroxy compound containing an acetal ring, for example, spiro glycol represented by the following formula (2) or dioxane glycol represented by the following formula (3) can be used.

[0037] [ka]

[0038] [ka]

[0039] From the viewpoint of further improving the heat resistance of the polycarbonate resin (A), the dihydroxy compound into which the structural unit (a) is introduced is preferably an aliphatic dihydroxy compound or an alicyclic dihydroxy compound, and more preferably an alicyclic dihydroxy compound. From the viewpoint of further improving the heat resistance and impact resistance, among the alicyclic dihydroxy compounds, it is particularly preferable to use one or more compounds selected from the group consisting of cyclobutanediol, cyclohexanedimethanol, and tricyclodecanedimethanol.

[0040] The range of copolymerization ratios of each of the multiple polycarbonate copolymers having different copolymerization ratios and the mixing ratio of the multiple polycarbonate copolymers are appropriately selected under the condition that the copolymerization ratio of the polycarbonate resin mixture obtained after mixing satisfies a predetermined range. When only one type of polycarbonate is used as the polycarbonate resin (A) and when multiple polycarbonate copolymers are mixed, the preferred range of copolymerization ratio of the polycarbonate resin mixture obtained after mixing is the same, and will be explained below.

[0041] When all structural units derived from dihydroxy compounds in the polycarbonate resin (A) used in the present invention are taken as 100 mol %, the content of the structural unit (a2) is usually 10 mol % or more and 80 mol % or less. The content of (a2) is preferably 15 mol% or more, more preferably 20 mol% or more, particularly preferably 25 mol% or more, and most preferably 30 mol% or more. The content of (a2) is preferably 75 mol% or less, more preferably 66 mol% or less, even more preferably 60 mol% or less, even more preferably 55 mol% or less, particularly preferably 50 mol% or less, and most preferably 45 mol% or less. When the content of (a2) in the polycarbonate resin (A) is at least the lower limit, a resin composition with good impact resistance tends to be obtained, and when it is at most the upper limit, a resin composition with good heat resistance tends to be obtained.

[0042] From the viewpoint of optical properties, it is preferable that the copolymerized polycarbonate resin used in the present invention does not contain an aromatic component as a structural unit. That is, it is preferable to use only compounds composed of non-aromatic structures as copolymerization monomers. If an aromatic component is contained in the main chain of the polymer, there is a concern that the weather resistance and transparency of the resin composition may be deteriorated. By employing the other structural unit that does not contain an aromatic component, it is possible to prevent the aromatic component from being incorporated into the main chain due to the structural unit.

[0043] On the other hand, in order to ensure optical properties while balancing heat resistance, mechanical properties, etc., it may be effective to incorporate an aromatic component into the main chain or side chain of the polymer. From the viewpoint of balancing various properties, the content of structural units containing aromatic groups in the resin is preferably 20 mol % or less, more preferably 10 mol % or less, even more preferably 5 mol % or less, and particularly preferably 1 mol % or less.

[0044] (Additives in raw materials for polycarbonate resin (A)) Stabilizers, etc. The dihydroxy compound used as a raw material for the polycarbonate resin (A) may contain a stabilizer such as a reducing agent, antioxidant, oxygen scavenger, light stabilizer, antacid, pH stabilizer, or heat stabilizer. Dihydroxy compound (1) is particularly susceptible to deterioration under acidic conditions. Therefore, the use of a basic stabilizer in the synthesis of the polycarbonate resin (A) can inhibit the deterioration of dihydroxy compound (1). This can further improve the quality of the resulting polycarbonate resin composition.

[0045] Examples of the basic stabilizer that can be used include the following compounds: hydroxides, carbonates, phosphates, phosphites, hypophosphites, borates, and fatty acid salts of metals of Group 1 or 2 of the long-form periodic table (Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005); 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, and methyltriphenylammonium hydroxide. basic ammonium compounds such as diethylamine, dibutylamine, triethylamine, morpholine, N-methylmorpholine, pyrrolidine, piperidine, 3-amino-1-propanol, ethylenediamine, N-methyldiethanolamine, diethylethanolamine, diethanolamine, triethanolamine, 4-aminopyridine, 2-aminopyridine, N,N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2-dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, and aminoquinoline; and hindered amine compounds such as di-(tert-butyl)amine and 2,2,6,6-tetramethylpiperidine.

[0046] The content of the basic stabilizer in the dihydroxy compound is not particularly limited. However, since the dihydroxy compound (1) is unstable under acidic conditions, it is preferable to set the content of the basic stabilizer so that the pH of an aqueous solution of the dihydroxy compound containing the basic stabilizer is around 7.

[0047] The content of the basic stabilizer in the dihydroxy compound (1) (specifically, the content of the basic stabilizer relative to 100% by mass of the total of the dihydroxy compound (1) and the basic stabilizer) is preferably 0.0001 to 1% by mass. In this case, the effect of preventing the deterioration of the dihydroxy compound (1) is sufficiently obtained. From the viewpoint of further enhancing this effect, the content of the basic stabilizer is more preferably 0.001 to 0.1% by mass.

[0048] (carbonate diester) The polycarbonate resin (A) is obtained by polycondensing a dihydroxy compound and a carbonic acid diester as raw materials, for example, by a transesterification reaction. As the carbonic acid diester, a compound represented by the following formula (4) is usually used. These carbonic acid diesters may be used alone or in combination of two or more.

[0049] [ka]

[0050] In the above formula (4), A 1 and A 2 are each independently a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 18 carbon atoms or a substituted or unsubstituted aromatic hydrocarbon group, and A 1 and A 2 A may be the same or different. 1 and A 2 is preferably a substituted or unsubstituted aromatic hydrocarbon group, more preferably an unsubstituted aromatic hydrocarbon group.

[0051] Examples of the carbonate diester represented by formula (4) include diphenyl carbonate (i.e., DPC) and substituted diphenyl carbonates such as ditolyl carbonate. Further, examples of the carbonate diester represented by formula (4) include dimethyl carbonate, diethyl carbonate, di-tert-butyl carbonate, and the like. Among these carbonate diesters, it is preferable to use diphenyl carbonate or a substituted diphenyl carbonate, and it is more preferable to use diphenyl carbonate. Carbonate diesters may contain impurities such as chloride ions, which may inhibit the polycondensation reaction or deteriorate the color tone of the resulting polycarbonate resin (A). Therefore, it is preferable to use a diester purified by distillation or the like, as necessary.

[0052] The concentration of the carbonic acid diester remaining in the polycarbonate resin (A) of the present invention is preferably 200 ppm by mass or less, more preferably 100 ppm by mass or less, particularly preferably 60 ppm by mass or less, and most preferably 30 ppm by mass or less. However, in reality, the polycarbonate resin (A) may contain unreacted carbonic acid diester, and the lower limit of the concentration of unreacted carbonic acid diester in the polycarbonate resin (A) is usually 1 ppm by mass. When the concentration of the unreacted carbonate diester in the polycarbonate resin (A) is equal to or less than the upper limit, deterioration of the polycarbonate resin (A) due to ultraviolet absorption can be suppressed.

[0053] <Method for producing polycarbonate resin (A)> The polycarbonate resin (A) can be synthesized by polycondensing the dihydroxy compound and the carbonic acid diester through a transesterification reaction. More specifically, the polycarbonate resin (A) can be obtained by removing the monohydroxy compound and other by-products produced in the transesterification reaction from the system during the polycondensation.

[0054] (polymerization catalyst) The transesterification reaction proceeds in the presence of a transesterification catalyst (hereinafter, the transesterification catalyst will be referred to as a "polymerization catalyst.") By selecting the type of polymerization catalyst, the reaction rate of the transesterification reaction and the quality of the resulting polycarbonate resin (A) can be appropriately adjusted.

[0055] Examples of transesterification catalysts (hereinafter sometimes referred to as "catalysts") that can be used in producing the polycarbonate resin (A) of the present invention include basic compounds such as metal compounds of Group 1 or 2 (hereinafter simply referred to as "Group 1" and "Group 2") in the long-form periodic table (Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005), basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds. Among these, Group 1 metal compounds and / or Group 2 metal compounds are preferably used.

[0056] Although it is possible to use a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound in combination with the Group 1 metal compound and / or the Group 2 metal compound as an auxiliary, it is particularly preferable to use only the Group 1 metal compound and / or the Group 2 metal compound. 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, carboxylate, or phenolate. From the viewpoints of availability and ease of handling, the hydroxide, carbonate, or acetate is preferred, and from the viewpoints of color and polymerization activity, the acetate is preferred.

[0057] Examples of Group 1 metal compounds 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, lithium carbonate, cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride, cesium borohydride, sodium phenylborohydride, potassium phenylborohydride, lithium phenylborohydride, and cesium phenylborohydride. , sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, dicesium hydrogen phosphate, disodium phenylphosphate, dipotassium phenylphosphate, dilithium phenylphosphate, dicesium phenylphosphate, alcoholates and phenolates of sodium, potassium, lithium and cesium, and disodium salts, dipotassium salts, dilithium salts and dicesium salts of bisphenol A. Among these, from the viewpoints of polymerization activity and the color tone of the resulting polycarbonate resin (A), cesium compounds or lithium compounds are preferred, and lithium compounds are more preferred.

[0058] Examples of Group 2 metal compounds 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, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, and strontium stearate. As the Group 2 metal compound, magnesium compounds, calcium compounds and barium compounds are preferred, and from the viewpoints of polymerization activity and the color tone of the resulting polycarbonate resin (A), magnesium compounds and / or calcium compounds are more preferred, and calcium compounds are most preferred.

[0059] Examples of basic boron compounds include sodium salts, potassium salts, lithium salts, calcium salts, barium salts, magnesium salts, and strontium salts of tetramethyl boron, tetraethyl boron, tetrapropyl boron, tetrabutyl boron, trimethylethyl boron, trimethylbenzyl boron, trimethylphenyl boron, triethylmethyl boron, triethylbenzyl boron, triethylphenyl boron, tributylbenzyl boron, tributylphenyl boron, tetraphenyl boron, benzyltriphenyl boron, methyltriphenyl boron, and butyltriphenyl boron.

[0060] Examples of basic phosphorus compounds include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, and quaternary phosphonium salts. Examples of basic ammonium compounds include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide, and butyltriphenylammonium hydroxide.

[0061] Examples of amine compounds include 4-aminopyridine, 2-aminopyridine, N,N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2-dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, and aminoquinoline.

[0062] From the viewpoint of providing the resulting polycarbonate resin (A) with excellent physical properties such as transparency, hue, and light resistance, it is preferable to use at least one metal compound selected from the group consisting of lithium compounds and Group 2 metal compounds, and it is more preferable to use at least one metal compound selected from the group consisting of magnesium compounds and calcium compounds.

[0063] The amount of the polymerization catalyst used is preferably 0.1 to 300 μmol, more preferably 0.5 to 100 μmol, and particularly preferably 1 to 50 μmol per mol of the total dihydroxy compounds used in the reaction.

[0064] In the case of a Group 1 metal compound and / or a Group 2 metal compound, the amount of the catalyst used is usually 0.1 μmol or more, preferably 0.5 μmol or more, more preferably 0.7 μmol or more, in terms of metal, relative to 1 mole of all dihydroxy compounds to be subjected to the reaction, and is usually 300 μmol or less, preferably 100 μmol or less, more preferably 50 μmol or less, even more preferably 25 μmol or less, still more preferably 20 μmol or less, particularly preferably 10 μmol or less, especially more preferably 3.0 μmol or less, and extremely preferably 2.0 μmol or less.

[0065] By adjusting the amount of polymerization catalyst used within the above range, the polymerization rate can be increased, making it possible to obtain a polycarbonate resin (A) with the desired molecular weight without necessarily increasing the polymerization temperature. This can suppress deterioration in the color tone of the polycarbonate resin (A). Furthermore, it can prevent unreacted raw materials from volatilizing during polymerization, which would disrupt the molar ratio of the dihydroxy compound to the carbonate diester, thereby more reliably obtaining a polycarbonate resin (A) with the desired molecular weight. Furthermore, it can suppress the occurrence of side reactions, which can further prevent deterioration in the color tone of the polycarbonate resin (A) or discoloration during molding.

[0066] Considering the adverse effects of sodium, potassium, or cesium, among the Group 1 metals, on the color tone of the polycarbonate resin (A), and the adverse effects of iron on the color tone of the polycarbonate resin (A), the total content of sodium, potassium, cesium, and iron in the polycarbonate resin (A) is preferably 1 ppm by mass or less, and more preferably 0.5 pp by mass or less. In this case, deterioration of the color tone of the polycarbonate resin (A) can be further prevented, and the color tone of the polycarbonate resin (A) can be further improved. Note that these metals may be mixed not only from the catalyst used, but also from raw materials or reaction equipment. Regardless of their origin, the total amount of compounds of these metals in the polycarbonate resin (A) is preferably within the above-mentioned range as the total content of sodium, potassium, cesium, and iron.

[0067] (Synthesis of polycarbonate resin (A)) The polycarbonate resin (A) of the present invention can be obtained by melt-polymerizing a dihydroxy compound including the dihydroxy compound (1) with a carbonate diester through transesterification.

[0068] The dihydroxy compound and the carbonate diester are preferably mixed uniformly before the transesterification reaction. The mixing temperature is usually 80°C or higher, preferably 90°C or higher, and more preferably 100°C or higher, and usually 250°C or lower, preferably 200°C or lower, more preferably 150°C or lower, and even more preferably 120°C or lower. In this case, the dissolution rate can be increased or the solubility can be sufficiently improved, and problems such as solidification can be sufficiently avoided. Furthermore, in this case, the thermal degradation of the dihydroxy compound can be sufficiently suppressed, and as a result, the color tone of the polycarbonate resin (A) can be made even better and the weather resistance also tends to be improved.

[0069] The operation of mixing the dihydroxy compound and the carbonate diester is carried out in an atmosphere with an oxygen concentration of 10% by volume or less, preferably 5% by volume or less, and more preferably 1% by volume or less. The lower the oxygen concentration, the better, but it is usually 0.0001% by volume or more. In this case, it is possible to obtain a better color tone and also to increase the reactivity.

[0070] The carbonic acid diester is preferably used in a molar ratio of 0.90 to 1.20, more preferably 0.95 to 1.10, even more preferably 0.96 to 1.10, and particularly preferably 0.98 to 1.04, relative to the total amount of dihydroxy compounds used in the melt polymerization. By setting this molar ratio to be equal to or greater than the above lower limit, an unexpected increase in the number of terminal hydroxyl groups in the produced polycarbonate resin (A) is suppressed, the thermal stability of the polymer is improved, discoloration during molding of the thermoplastic resin composition is prevented, a decrease in the rate of the transesterification reaction is prevented, and the desired high molecular weight product is more easily obtained.

[0071] Furthermore, by keeping this molar ratio at or below the above upper limit, a decrease in the rate of transesterification reaction is prevented under the same conditions, facilitating the production of a polycarbonate resin (A) with a desired molecular weight, and by preventing an increase in the amount of residual carbonate diester in the produced polycarbonate resin (A), this residual carbonate diester is prevented from causing odor during molding or in the molded product. Furthermore, an increase in the thermal history during the polymerization reaction is prevented, which tends to result in good color and weather resistance of the resulting polycarbonate resin (A).

[0072] The polycarbonate resin (A) of the present invention is preferably produced by melt polymerization in multiple stages using a catalyst in multiple reactors. The reason for carrying out melt polymerization in multiple reactors is that, in the early stages of the melt polymerization reaction, the reaction solution contains a large amount of monomer, so it is important to maintain the required polymerization rate while suppressing monomer evaporation. In the later stages of the melt polymerization reaction, it is important to sufficiently distill off the by-product monohydroxy compound in order to shift the equilibrium toward polymerization. Thus, in order to set different polymerization reaction conditions, it is preferable from the perspective of production efficiency to use multiple reactors arranged in series. As mentioned above, the number of reactors should be at least two, but from the perspective of production efficiency, it is three or more, preferably three to five, and particularly preferably four.

[0073] The method of polycondensing a dihydroxy compound and a carbonic acid diester is carried out in multiple stages using a plurality of reactors in the presence of the above-mentioned catalyst. The reaction may be carried out in a batchwise manner, a continuous manner, or a combination of a batchwise and continuous manner. From the viewpoint of obtaining polycarbonate resin (A) with less thermal history and excellent productivity, it is preferable to employ a continuous manner.

[0074] Furthermore, the polymerization rate in the polycondensation reaction is controlled by the balance between the hydroxyl group terminals and the carbonate group terminals. Therefore, by suppressing the distillation of unreacted monomers, the balance of the terminal groups is stabilized, making it easier to control the polymerization rate at a constant level and reducing fluctuations in the molecular weight of the resulting resin. Because the molecular weight of the resin correlates with the melt viscosity, when the resulting resin is melt-processed, the melt viscosity is stabilized, making it easier to maintain consistent quality in molded products. This effect is particularly pronounced when the polycondensation reaction is carried out in a continuous system.

[0075] The use of a reflux condenser in a polymerization reactor is effective in suppressing the amount of unreacted monomer distilled off, and is particularly effective in reactors in the early stages of polymerization where a large amount of unreacted monomer components is present. The temperature of the refrigerant introduced into the reflux condenser can be appropriately selected depending on the monomer used. Typically, the temperature of the refrigerant introduced into the reflux condenser at the inlet of the reflux condenser is 45 to 180°C, preferably 80 to 150°C, and particularly preferably 100 to 130°C. By adjusting the refrigerant temperature within these ranges, the reflux amount can be sufficiently increased, its effects can be fully achieved, and the efficiency of distillation of the monohydroxy compound to be distilled off can be sufficiently improved. As a result, a decrease in the reaction rate can be prevented, and discoloration of the resulting resin can be further prevented. Examples of refrigerants that can be used include hot water, steam, and heat transfer oil, with steam and heat transfer oil being preferred.

[0076] In order to maintain an appropriate polymerization rate and suppress distillation of monomers while not impairing the hue, thermal stability, light resistance, etc. of the polycarbonate resin (A) finally obtained, it is important to select the type and amount of the catalyst described above. In producing the polycarbonate resin (A) of the present invention, if there are two or more reactors, the reactors may have a plurality of reaction stages with different conditions, or the temperature and pressure may be changed continuously.

[0077] In the production of the polycarbonate resin (A) of the present invention, the catalyst can be added to the raw material preparation or raw material storage tank, or can be added directly to the reactor. From the viewpoint of supply stability and control of the polycondensation reaction, it is preferable to install a catalyst supply line in the raw material line before supplying the raw material to the reactor, and it is preferable to supply the catalyst in the form of an aqueous solution.

[0078] From the viewpoint of controlling the polymerization rate and improving the hue and light resistance of the resulting polycarbonate resin (A), it is preferable to appropriately select the jacket temperature, internal temperature, and pressure in the reaction system depending on the reaction stage. Specifically, it is preferable to obtain a prepolymer at a relatively low temperature and low vacuum in the early stage of the polycondensation reaction, and to increase the molecular weight to a predetermined value at a relatively high temperature and high vacuum in the later stage of the polymerization. In this case, the distillation of unreacted monomers is suppressed, and the molar ratio of the dihydroxy compound to the carbonic acid diester can be easily adjusted to the desired ratio. As a result, a decrease in the polymerization rate can be suppressed. Furthermore, it becomes possible to more reliably obtain a polymer having the desired molecular weight and terminal groups.

[0079] In the production of the polycarbonate resin (A) of the present invention, by adjusting the temperature of the polycondensation reaction, it is possible to improve productivity and avoid an increase in the thermal history of the product. Furthermore, it is possible to further prevent the volatilization of the monomer and the decomposition and coloration of the polycarbonate resin (A). Specifically, the following conditions can be adopted as reaction conditions for the first stage reaction. That is, the maximum internal temperature of the polymerization reactor is set in the range of usually 150 to 250°C, preferably 160 to 240°C, and more preferably 170 to 230°C. The pressure in the polymerization reactor (hereinafter, "pressure" refers to absolute pressure) is set in the range of usually 1 to 110 kPa, preferably 5 to 70 kPa, and more preferably 7 to 30 kPa. The reaction time is usually set within the range of 0.1 to 10 hours, preferably 0.5 to 3 hours. The first-stage reaction is preferably carried out while distilling off the generated monohydroxy compound outside the reaction system.

[0080] By setting the transesterification reaction temperature to the above upper limit or less, the color of the molded article can be improved and brittle fracture can be made less likely. By setting the transesterification reaction temperature to the above lower limit or more, the target molecular weight can be achieved, and the molecular weight distribution can be narrowed, resulting in good impact strength. Furthermore, by setting the residence time of the transesterification reaction to the above upper limit or less, brittle fracture can be made less likely. By setting the residence time to the above lower limit or more, the target molecular weight can be achieved and good impact strength can be made.

[0081] From the viewpoint of effective utilization of resources, it is preferable that the by-produced monohydroxy compound is purified as necessary and then reused as a raw material for carbonic acid diesters and various bisphenol compounds. In particular, from the viewpoint of suppressing the occurrence of discoloration, thermal degradation or "burn" of the polycarbonate resin (A) and obtaining a good polycarbonate resin (A) with high impact resistance, the maximum temperature inside the reactor in all reaction stages is preferably less than 255°C, more preferably 250°C or less, and even more preferably 180°C to 245°C. In order to prevent a decrease in the polymerization rate in the latter half of the polymerization reaction and to minimize thermal degradation of the polycarbonate resin (A) due to thermal history, it is preferable to use a horizontal reactor, which has excellent plug flow properties and interface renewal properties, in the final stage of the reaction.

[0082] In this specification, the term "burn" refers to a phenomenon in which burnt material is generated in a resin, a resin composition, a molded product, or the like, resulting in brown, tan, black, or other colored areas. This phenomenon generally occurs when an excessively heated area occurs within a resin production or processing system, causing the resin or resin composition that comes into contact with that area to partially combust. For example, this includes cases where, during resin molding, air bubbles are trapped when a resin or resin composition is injected into a cavity, and the bubbles compress and spontaneously ignite.

[0083] In addition, in order to obtain a polycarbonate resin (A) with high impact strength and a high molecular weight, the polymerization temperature may be increased as much as possible and the polymerization time may be prolonged. However, in this case, foreign matter or burns may be generated in the polycarbonate resin (A), making it more susceptible to brittle fracture. Therefore, in order to satisfy both the requirements of high impact strength and resistance to brittle fracture, it is preferable to keep the polymerization temperature low, use a highly active catalyst to shorten the polymerization time, and adjust the pressure of the reaction system appropriately. Furthermore, in order to prevent brittle fracture, it is also preferable to remove foreign matter or burns generated in the reaction system using a filter or the like during the reaction or at the final stage of the reaction.

[0084] When polycarbonate resin (A) is produced using a substituted diphenyl carbonate such as diphenyl carbonate or ditolyl carbonate as the carbonate diester represented by formula (4), phenol and substituted phenols are inevitably produced as by-products and remain in the polycarbonate resin (A). However, since phenol and substituted phenols also have aromatic rings, they absorb ultraviolet light, which may not only deteriorate lightfastness but also cause odor during molding. After a typical batch reaction, polycarbonate resin (A) contains 1,000 ppm by mass or more of aromatic monohydroxy compounds having aromatic rings, such as phenol, as by-products. From the viewpoint of lightfastness and odor reduction, it is preferable to use a horizontal reactor or an extruder equipped with a vacuum vent that has excellent devolatilization capabilities, and reduce the content of aromatic monohydroxy compounds in polycarbonate resin (A) to preferably 700 ppm by mass or less, more preferably 500 ppm by mass or less, and particularly 300 ppm by mass or less. However, it is difficult to completely remove aromatic monohydroxy compounds industrially, and the lower limit of the content of aromatic monohydroxy compounds in the polycarbonate resin (A) is usually 1 ppm by mass. Depending on the raw material used, these aromatic monohydroxy compounds may naturally have a substituent, such as an alkyl group having 5 or less carbon atoms.

[0085] Furthermore, Group 1 metals, particularly lithium, sodium, potassium, and cesium, and particularly sodium, potassium, and cesium, may be mixed in not only from the catalyst used but also from raw materials or reaction equipment. If these metals are contained in large amounts in the polycarbonate resin (A), this may adversely affect the hue. Therefore, the total content of these compounds in the polycarbonate resin (A) of the present invention is preferably as low as possible, and the amount of metal in the polycarbonate resin (A) is usually 1 ppm by mass or less, preferably 0.8 ppm by mass or less, and more preferably 0.7 ppm by mass or less.

[0086] The amount of metal in the polycarbonate resin (A) can be measured by various conventionally known methods. After recovering the metal in the polycarbonate resin (A) by a method such as wet ashing, the amount of metal can be measured by a method such as atomic emission, atomic absorption, or inductively coupled plasma (ICP). After the polycarbonate resin (A) of the present invention is melt-polymerized as described above, it is usually cooled and solidified, and then pelletized using a rotary cutter or the like.

[0087] The pelletizing method is not limited, and examples include a method in which the polycarbonate resin (A) is withdrawn in a molten state from the final polymerization reactor, cooled and solidified in the form of strands, and pelletized; a method in which the resin is supplied in a molten state from the final polymerization reactor to a single-screw or twin-screw extruder, melt-extruded, and then cooled and solidified to pelletize; and a method in which the resin is withdrawn in a molten state from the final polymerization reactor, cooled and solidified in the form of strands, and once pelletized, is again supplied to a single-screw or twin-screw extruder, melt-extruded, and then cooled and solidified to pelletize.

[0088] At this time, residual monomers may be removed under reduced pressure in the extruder, and commonly known additives such as a heat stabilizer, a neutralizing agent, an ultraviolet absorber, a mold release agent, a colorant, an antistatic agent, a lubricant, a plasticizer, a compatibilizer, and a flame retardant may be added and kneaded. The melt-kneading temperature in the extruder depends on the glass transition temperature and molecular weight of the polycarbonate resin (A), but is usually 150 to 300°C, preferably 200 to 270°C, and more preferably 230 to 260°C. By setting the melt-kneading temperature at or above the lower limit, the melt viscosity of the polycarbonate resin (A) can be prevented from becoming too high, the load on the extruder can be reduced, and productivity can be improved. By setting the temperature at or below the upper limit, increased thermal degradation of the polycarbonate can be prevented, a decrease in mechanical strength due to a decrease in molecular weight can be prevented, and discoloration, gas generation, generation of foreign matter, and even burning can be prevented. A filter for removing the foreign matter and burning is preferably installed in the extruder or at the extruder outlet.

[0089] The size (opening size) of the filter for removing foreign matter is usually 400 μm or less, preferably 200 μm or less, and particularly preferably 100 μm or less, with the goal of achieving a filtration accuracy of removing 99% or more of foreign matter. By setting the filter opening size to the above upper limit or less, foreign matter and burns can be sufficiently removed, and brittle fracture can be prevented when the polycarbonate resin (A) is molded. The opening size of the filter can also be adjusted depending on the application of the thermoplastic resin composition of the present invention. For example, when applied to film applications, the filter opening size is preferably 40 μm or less, and more preferably 10 μm or less, in order to eliminate defects.

[0090] Furthermore, a plurality of the filters may be arranged in series, or a filtration device in which a plurality of leaf disk type polymer filters are stacked may be used. Furthermore, when cooling and pelletizing the melt-extruded polycarbonate resin (A), it is preferable to use a cooling method such as air cooling or water cooling. The air used for air cooling is preferably air from which foreign matter in the air has been removed in advance using a HEPA filter (preferably a filter specified in JIS Z8112) or the like to prevent re-adhesion of foreign matter in the air. It is more preferable to carry out the cooling in a clean room with a cleanliness level higher than Class 7, and even more preferably Class 6, as defined in JIS B 9920 (2002). When using water cooling, it is preferable to remove metals from the water using an ion exchange resin or the like, and then use water from which foreign matter has been removed using a filter. The mesh size of the filter used can vary, but a filter with a mesh size of 10 to 0.45 μm is preferred.

[0091] Phosphate compounds, phosphite compounds When the polycarbonate resin (A) of the present invention is produced by melt polymerization, one or more phosphoric acid compounds and / or phosphorous acid compounds may be added during polymerization in order to prevent discoloration. As the phosphoric acid compound, one or more trialkyl phosphates such as trimethyl phosphate and triethyl phosphate are preferably used. These are preferably added in an amount of 0.0001 mol % to 0.005 mol % and more preferably 0.0003 mol % to 0.003 mol % based on the total hydroxy compounds used in the reaction. By adding the phosphorus compound in an amount equal to or greater than the lower limit, the coloring prevention effect can be effectively exerted, and by adding the phosphorus compound in an amount equal to or less than the upper limit, a decrease in transparency can be prevented, coloring can be suppressed, and heat resistance can be improved.

[0092] The phosphorous acid compound may be selected from the following heat stabilizers. In particular, one or more of trimethyl phosphite, triethyl phosphite, trisnonylphenyl phosphite, trimethyl phosphate, tris(2,4-di-tert-butylphenyl)phosphite, and bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite are preferably used. These phosphorous acid compounds are preferably added in an amount of 0.0001 mol % to 0.005 mol %, more preferably 0.0003 mol % to 0.003 mol %, based on the total amount of hydroxy compounds used in the reaction. By adding the phosphorous acid compound in an amount equal to or greater than the lower limit, sufficient coloration prevention can be achieved. By adding the phosphorous acid compound in an amount equal to or less than the upper limit, a decrease in transparency can be prevented, coloration can be suppressed, and heat resistance can be improved.

[0093] The phosphoric acid compound and the phosphorous acid compound can be added in combination, and in that case, the amount added, in terms of the total amount of the phosphoric acid compound and the phosphorous acid compound, is preferably 0.0001 mol % to 0.005 mol % and more preferably 0.0003 mol % to 0.003 mol % based on the total amount of the hydroxy compounds used in the reaction. By setting the amount added at or above the lower limit, the coloring prevention effect can be sufficient, and by setting it at or below the upper limit, a decrease in transparency can be prevented, coloring can be suppressed, and heat resistance can be improved.

[0094] The polycarbonate resin (A) thus produced may also contain one or more heat stabilizers to prevent a decrease in molecular weight or deterioration in color during molding or the like. Examples of such heat stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. Specific examples 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( Examples of the phosphate phosphate include 4,6-di-tert-butylphenyl)octyl phosphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, 4,4'-biphenylenediphosphinic acid tetrakis(2,4-di-tert-butylphenyl), dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate. Among these, trisnonylphenyl phosphite, trimethyl phosphate, tris(2,4-di-tert-butylphenyl)phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, and dimethyl benzenephosphonate are preferably used.

[0095] Such a heat stabilizer can be blended in an amount in addition to the amount added during melt polymerization. That is, by blending an appropriate amount of a phosphorous acid compound or a phosphoric acid compound to obtain polycarbonate resin (A), and then blending a phosphorous acid compound by the blending method described below, it is possible to blend a larger amount of heat stabilizer without causing a decrease in transparency, coloration, and heat resistance during polymerization, and to prevent deterioration in color.

[0096] The content of these heat stabilizers is preferably from 0.0001 to 1 part by mass, more preferably from 0.0005 to 0.5 parts by mass, and even more preferably from 0.001 to 0.2 parts by mass, relative to 100 parts by mass of the polycarbonate resin (A).

[0097] <Physical properties of polycarbonate resin (A)> Preferred physical properties of the polycarbonate resin (A) of the present invention are shown below.

[0098] (glass transition temperature) The glass transition temperature (Tg) of the polycarbonate resin (A) is usually 180°C or lower. In this case, coloration is easily suppressed and impact strength can be more easily improved. In addition, in this case, the mold temperature can be lowered when transferring the shape of the mold surface to the molded product during molding. This increases the number of temperature regulators available and improves the transferability of the mold surface.

[0099] The glass transition temperature (Tg) of the polycarbonate resin (A) is preferably 160° C. or lower, more preferably 155° C. or lower, even more preferably 150° C. or lower, still more preferably 145° C. or lower, and particularly preferably 140° C. or lower. The glass transition temperature of the polycarbonate resin (A) of the present invention is usually 60° C. or higher, preferably 70° C. or higher, more preferably 80° C. or higher, even more preferably 85° C. or higher, still more preferably 90° C. or higher, and particularly preferably 95° C. or higher.

[0100] Methods for adjusting the glass transition temperature of the polycarbonate resin (A) to the above upper limit or lower include a method of reducing the proportion of the structural unit (a1) in the polycarbonate resin (A), a method of selecting an alicyclic dihydroxy compound with low heat resistance as the dihydroxy compound used in producing the polycarbonate resin (A), and a method of reducing the proportion of structural units derived from aromatic dihydroxy compounds such as bisphenol compounds in the polycarbonate resin (A). In this specification, the glass transition temperature (Tg) of the polycarbonate resin (A) is measured in accordance with JIS K7121 (1987) using a differential scanning calorimeter (DSC6220 manufactured by SII NanoTechnology Inc.).

[0101] (reduced viscosity) The molecular weight of the polycarbonate resin (a) can be expressed by reduced viscosity, and the higher the reduced viscosity, the larger the molecular weight. The reduced viscosity of the polycarbonate resin (A) is preferably 2.0 dl / g or less, more preferably 1.7 dl / g or less, and even more preferably 1.4 dl / g or less, from the viewpoints of improving the fluidity during molding and improving the molding cycle in, for example, injection molding, as well as reducing distortion of the molded product and preventing thermal deformation. On the other hand, from the viewpoint of further improving the mechanical strength, the reduced viscosity of the polycarbonate resin (A) is preferably 0.25 dl / g or more, more preferably 0.30 dl / g or more, even more preferably 0.35 dl / g or more, and still more preferably 0.40 dl / g or more. Depending on the application of the thermoplastic resin composition of the present invention, a viscosity of 0.60 dl / g or more, and even 0.85 dl / g or more may be preferably used in some cases.

[0102] The reduced viscosity of the polycarbonate resin (a-1) is measured using an Ubbelohde viscometer at a temperature of 20.0°C ± 0.1°C, with the polycarbonate resin concentration precisely adjusted to 0.6 g / dL using methylene chloride as a solvent.

[0103] <Other resin components constituting one or more resins> As long as the effects of the present invention are not lost, the one or more resins may contain other resins in addition to the polycarbonate resin (A) described above, such as synthetic resins such as aromatic polycarbonate, aromatic polyester, aliphatic polyester, polyamide, polystyrene, polyolefin, acrylic, amorphous polyolefin, ABS, and AS, biodegradable resins such as polylactic acid and polybutylene succinate, and rubber. One or more of these other resins may be used. When the one or more resins contain other resins, the resin composition according to the present invention may be a compound of the polycarbonate resin (A) and the other resins, or a polymer alloy.

[0104] Furthermore, when the one or more resins contain other resins, the content of the polycarbonate resin (A) is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more, with the one or more resins as a whole being 100% by mass.

[0105] <Glass frit (B)> The resin composition of the present invention contains a glass frit (B). When the resin composition of the present invention contains the glass frit (B), it is possible to provide a resin composition having good scratch resistance.

[0106] As used herein, glass frit (B) refers to powdered glass with a softening point of 300°C or higher and 950°C or lower. In certain embodiments, the term refers to glass prepared by premixing glass components, melting the mixture, and quenching it in water or air. Examples of glasses constituting the glass frit include phosphate-based glass, borate-based glass, bismuth oxide-based glass, silicate-based glass, and sodium oxide-based glass. Phosphate-based glass and borate-based glass are preferred, and phosphate-based glass is more preferred. These glass frits can be obtained by adjusting the composition of B2O3, P2O5, ZnO, SiO2, Bi2O3, Al2O3, BaO, CaO, MgO, MnO2, ZrO2, TiO2, CeO2, SrO, VO5, SnO2, Li2O, Na2O, KO, CuO, and Fe2O3 in predetermined proportions. The glass frits may be used alone or in combination. In the present invention, the softening point of the glass constituting the glass frit (B) is preferably 350°C or higher, more preferably 500°C or higher, even more preferably 600°C or higher, and is preferably 900°C or lower, more preferably 850°C or lower.

[0107] (Glass frit (B) content) The content of the glass frit (B) contained in the resin composition of the present invention is usually 0.1 parts by mass or more and 4.0 parts by mass or less per 100 parts by mass of the one or more resins. The content is preferably 0.2 parts by mass or more, more preferably 0.3 parts by mass or more, even more preferably 0.4 parts by mass or more, and particularly preferably 0.5 parts by mass or more. When the content is equal to or more than the lower limit, a resin composition having good scratch resistance can be obtained. The content is preferably 3.0 parts by mass or less, more preferably 2.5 parts by mass or less, even more preferably 2.0 parts by mass or less, still more preferably 1.8 parts by mass or less, and particularly preferably 1.5 parts by mass or less. By keeping the content at or below the upper limit, a resin composition with good impact resistance can be obtained.

[0108] (Glass frit (B) particle size) The particle size of the glass frit (B) is, in terms of mass median diameter (D50), usually 10 μm or more, more preferably 12 μm or more, even more preferably 15 μm or more, particularly preferably 18 μm or more, and most preferably 20 μm, and is usually 50 μm or less, preferably 40 μm or less, more preferably 35 μm or less, even more preferably 32 μm or less, and particularly preferably 30 μm or less. When the particle size is equal to or greater than the lower limit, a resin composition having good scratch resistance can be obtained, and when the particle size is equal to or less than the upper limit, the dispersibility of the glass frit is improved, and a resin composition having high uniformity and homogeneity can be easily obtained.

[0109] The shape of the glass frit is not particularly limited as long as the effects of the present invention can be obtained, but those produced by, for example, pulverization or rapid cooling usually have a random shape.

[0110] (Difference in refractive index between resin and glass frit (B) is 1 or more) In one embodiment, the absolute value of the difference in refractive index between the one or more resins and the glass frit (B) for light with a wavelength of 589.3 nm is preferably 0.05 or less, more preferably 0.04 or less, even more preferably 0.03 or less, still more preferably 0.02 or less, and particularly preferably 0.01 or less. There is no lower limit to the absolute value of the difference in refractive index, and the smaller the better, and the closer to 0.00 in the range of 0.00 or more, the more preferable, and ideally 0.00. When the absolute value of the difference in refractive index is within the above range, a resin composition with good transparency tends to be obtained.

[0111] (Refractive index of glass frit (B)) In another embodiment, the refractive index of the glass frit (B) with respect to light having a wavelength of 589.3 nm is 1.480 or more and 1.520 or less. The refractive index is preferably 1.485 or more, more preferably 1.490 or more, even more preferably 0.195 or more, and is preferably 1.515 or less, more preferably 1.510 or less, and even more preferably 1.505 or less. When the refractive index is equal to or less than the above upper limit and equal to or greater than the above lower limit, for example, when the refractive index of the one or more resins with respect to light having a wavelength of 589.3 nm is around 1.50, a resin composition with good transparency tends to be obtained.

[0112] <Other ingredients> Various well-known additives can be added to the resin composition of the present invention within the scope of not impairing the object of the present invention, such as antioxidants, light stabilizers, ultraviolet absorbers, heat stabilizers, fillers and other fillers, neutralizing agents, antifogging agents, antiblocking agents, slip agents, dispersants, colorants, flame retardants, antistatic agents, conductivity-imparting agents, crosslinking agents, crosslinking aids, metal deactivators, molecular weight modifiers, antibacterial agents, antifungal agents, fluorescent brighteners, and light diffusing agents such as organic diffusing agents and inorganic diffusing agents.

[0113] (Ultraviolet absorber (C)) The resin composition of the present invention may contain an ultraviolet absorber. The ultraviolet absorber is not particularly limited as long as it is a compound capable of absorbing ultraviolet rays. In the present embodiment, examples of the compound capable of absorbing ultraviolet rays include organic compounds and inorganic compounds. Among them, organic compounds are preferred because they can easily ensure affinity with polycarbonate resin and are easily dispersed uniformly. The molecular weight of the organic compound having ultraviolet absorbing ability is not particularly limited, but is usually 200 or more, preferably 250 or more. Also, it is usually 600 or less, preferably 450 or less, more preferably 400 or less. By setting the molecular weight to the above lower limit or more, it is possible to prevent a decrease in ultraviolet resistance performance over long-term use. By setting the molecular weight to the above upper limit or less, it is possible to prevent a decrease in transparency of the resin composition over long-term use. Preferred ultraviolet absorbers include benzotriazole compounds, benzophenone compounds, triazine compounds, benzoate compounds, salicylic acid phenyl ester compounds, cyanoacrylate compounds, malonic acid ester compounds, and oxalic acid anilide compounds. Of these, benzotriazole compounds, hydroxybenzophenone compounds, and malonic acid ester compounds are preferably used. These may be used alone or in combination of two or more.

[0114] More specific examples of the benzotriazole compound include 2-(2'-hydroxy-3'-methyl-5'-hexylphenyl)benzotriazole, 2-(2'-hydroxy-3'-t-butyl-5'-hexylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-methyl-5'-t-octylphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-dodecylphenyl)benzotriazole, 2-(2'-hydroxy-3'-methyl-5'-t-dodecylphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-butylphenyl)benzotriazole, and methyl-3-(3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate.

[0115] Examples of the hydroxybenzophenone compounds include 2,2'-dihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and 2-hydroxy-4-octoxybenzophenone.

[0116] Examples of malonic acid ester compounds include 2-(1-arylalkylidene)malonic acid esters and tetraethyl-2,2'-(1,4-phenylene-dimethylidene)-bismalonate.

[0117] Examples of triazine compounds include 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-isooctyloxyphenyl)-s-triazine, and 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol (Tinuvin 1577FF, manufactured by Ciba-Geigy).

[0118] Examples of the cyanoacrylate compounds include ethyl-2-cyano-3,3-diphenylacrylate and 2'-ethylhexyl-2-cyano-3,3-diphenylacrylate. Examples of oxalic acid anilide compounds include 2-ethyl-2'-ethoxy-oxalanilide (manufactured by Clariant Japan, Sanduvor VSU).

[0119] The content of the ultraviolet absorber is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, and even more preferably 0.05 parts by mass or more, relative to 100 parts by mass of the one or more resins, and is preferably 5.0 parts by mass or less, more preferably 3.0 parts by mass or less, and even more preferably 1.0 part by mass or less. When the content of the ultraviolet absorber is equal to or greater than the above-mentioned lower limit, a resin composition with good weather resistance tends to be obtained, and when the content is equal to or less than the above-mentioned upper limit, it is easy to suppress poor appearance due to "bleed-out" in which the ultraviolet absorber rises to the surface when the resin composition is processed into a film, sheet, or the like.

[0120] (Light stabilizer (D)) Light stabilizers include 2,2,6,6-tetramethyl-4-piperidinol, tetrakis(2,2,6,6-tetramethyl-4-piperidyl-butane-1,2,3,4-tetracarboxylate, 1,2,3,4-butanetetracarboxylic acid tetrakis(2,2,6,6-tetramethyl-4-piperidinyl), 1,2,3,4-butanetetracarboxylic acid tetrakis(2,2,6,6-tetramethyl-4-piperidinyl), tetrakis(2,2,6,6-tetramethyl-4-piperidyl-butane-1,2,3,4-tetracarboxylate, bis(1,2,3,6,6-pentamethyl-4-piperidyl)[[ 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butyl malonate, a condensation product of 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinol, and β,β,β,β-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5,5]undecane-diethanol, and a mixed ester of 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinol, and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane.

[0121] The resin composition of the present invention preferably contains 0.001 to 5 parts by mass of a light stabilizer (D) per 100 parts by mass of one or more resins. The lower limit of the light stabilizer content is more preferably 0.005 parts by mass or more, even more preferably 0.01 parts by mass or more, and the upper limit is more preferably 3 parts by mass or less, even more preferably 1 part by mass or less, and particularly preferably 0.5 parts by mass or less. By ensuring that the content of the light stabilizer (D) is at least the above lower limit, discoloration during weather resistance testing can be sufficiently suppressed. On the other hand, by ensuring that the content is at most the above upper limit, adhesion to the mold during injection molding can be suppressed, and the surface appearance of the product tends to be easily maintained.

[0122] (Impact modifier (E)) The resin composition of the present invention may contain an impact modifier (E). By including the impact resistance modifier (E) in the resin composition, it is possible to provide a resin composition having excellent impact resistance. The impact modifier (E) is preferably an elastomer having a core-shell structure. The "elastomer having a core-shell structure" is usually a core-shell graft copolymer consisting of an innermost layer (core layer) and one or more layers (shell layers) covering the innermost layer, in which a copolymerizable monomer component is graft copolymerized with the core layer as the shell layer.

[0123] The core layer of the elastomer having a core-shell structure preferably uses a polymer component called a rubber component.

[0124] The core-shell graft copolymer may be produced by any of bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc., and the copolymerization method may be single-stage grafting or multi-stage grafting. However, in the second aspect of the present invention, commercially available core-shell elastomers can usually be used as they are. Examples of commercially available core-shell elastomers are listed below.

[0125] The polymer component forming the core layer typically has a glass transition temperature of 0°C or lower, preferably -10°C or lower, more preferably -20°C or lower, and even more preferably -30°C or lower. Specific examples of polymer components forming the core layer include polybutadiene, polyisoprene, polyalkyl acrylates such as polybutyl acrylate, poly(2-ethylhexyl acrylate), and butyl acrylate-2-ethylhexyl acrylate copolymers, silicone rubbers such as polyorganosiloxane rubber, butadiene-acrylic composites, IPN (Interpenetrating Polymer Network) composite rubbers consisting of polyorganosiloxane rubber and polyalkyl acrylate rubber, styrene-butadiene copolymers, ethylene-α-olefin copolymers such as ethylene-propylene copolymers, ethylene-butene copolymers, and ethylene-octene copolymers, ethylene-acrylic copolymers, and fluororubbers. These may be used alone or in combination. Among these, polybutadiene, polyalkyl acrylate, polyorganosiloxane, a composite of polyorganosiloxane and polyalkyl acrylate, and butadiene-styrene copolymer are preferred in terms of mechanical properties and surface appearance.

[0126] Specific examples of the monomer component constituting the shell layer that can be graft-copolymerized with the polymer component of the core layer include aromatic vinyl compounds, vinyl cyanide compounds, (meth)acrylic acid ester compounds, (meth)acrylic acid compounds, epoxy group-containing (meth)acrylic acid ester compounds such as glycidyl (meth)acrylate; maleimide compounds such as maleimide, N-methylmaleimide, and N-phenylmaleimide; α,β-unsaturated carboxylic acid compounds such as maleic acid, phthalic acid, and itaconic acid, and anhydrides thereof (e.g., maleic anhydride). These monomer components may be used alone or in combination of two or more. Among these, aromatic vinyl compounds, vinyl cyanide compounds, (meth)acrylic acid ester compounds, and (meth)acrylic acid compounds are preferred in terms of mechanical properties and surface appearance, and (meth)acrylic acid ester compounds are more preferred. Specific examples of the (meth)acrylic acid ester compound include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, and octyl (meth)acrylate. Among these, methyl (meth)acrylate and ethyl (meth)acrylate, which are relatively easily available, are preferred, and methyl (meth)acrylate is more preferred. Here, "(meth)acrylic" collectively refers to "acrylic" and "methacrylic."

[0127] Among the elastomers having a core-shell structure, core-shell graft copolymers are particularly preferred, which have a core layer made of at least one polymer component selected from polybutadiene-containing rubber, polybutyl acrylate-containing rubber, polyorganosiloxane rubber, and an IPN-type composite rubber consisting of polyorganosiloxane rubber and polyalkyl acrylate rubber, and a shell layer formed by graft copolymerization of a (meth)acrylic acid ester around the core layer. The core-shell graft copolymer preferably contains 40% by mass or more of the polymer component of the core layer, more preferably 60% by mass or more. Furthermore, the shell layer preferably contains 10% by mass or more of the (meth)acrylic acid ester component.

[0128] Preferred examples of these core-shell type graft copolymers include methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS), methyl methacrylate-butadiene copolymer (MB), methyl methacrylate-acrylic rubber copolymer (MA), methyl methacrylate-acrylic rubber-styrene copolymer (MAS), methyl methacrylate-acrylic-butadiene rubber copolymer, methyl methacrylate-acrylic-butadiene rubber-styrene copolymer, and methyl methacrylate-(acrylic-silicone complex) copolymer.

[0129] Examples of such core-shell type graft copolymers include "Paraloid (registered trademark) EXL2602", "Paraloid (registered trademark) EXL2603", "Paraloid (registered trademark) EXL2655", "Paraloid (registered trademark) EXL2311", "Paraloid (registered trademark) EXL2313", "Paraloid (registered trademark) EXL2315", "Paraloid (registered trademark) KM330", "Paraloid (registered trademark) KM336P", and "Paraloid (registered trademark) KCZ201" manufactured by Rohm and Haas Japan Co., Ltd.; Examples include "Metablen (registered trademark) C-223A," "Metablen (registered trademark) E-901," "Metablen (registered trademark) S-2001," "Metablen (registered trademark) W-450A," "Metablen (registered trademark) SRK-200," and Kaneka Corporation's "Kane Ace (registered trademark) M-511," "Kane Ace (registered trademark) M-600," "Kane Ace (registered trademark) M-400," "Kane Ace (registered trademark) M-580," "Kane Ace (registered trademark) M-590," "Kane Ace (registered trademark) M-591," and "Kane Ace (registered trademark) MR-01."

[0130] The impact strength modifiers having a core-shell structure, such as these core-shell type graft copolymers, may be used singly or in combination of two or more kinds.

[0131] The amount of the impact resistance modifier (E) contained in the resin composition of the present invention is not particularly limited, but is usually 0.1 parts by mass or more, preferably 0.5 parts by mass or more, more preferably 1.0 parts by mass or more, and even more preferably 5.0 parts by mass or more, based on 100 parts by mass of the total mass of the one or more resins, and is usually 50 parts by mass or less, preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 25 parts by mass or less. When the content of the impact resistance modifier (E) is equal to or greater than the lower limit, it is possible to provide a resin composition and a molded article having good surface impact resistance and good impact resistance. Furthermore, by using a resin composition in which the content of the impact resistance modifier (E) is equal to or less than the upper limit, it is possible to suppress poor appearance and a decrease in heat resistance when a molded article is produced.

[0132] <Other additives> In addition to the above-mentioned additives, the resin composition of the present invention may be a resin composition containing various well-known additives, such as a mold release agent, a lubricant, an antioxidant, a flame retardant, a flame retardant aid, a hydrolysis inhibitor, an antistatic agent, a foaming agent, a filler, a dye or pigment, etc., within the scope of not impairing the object of the present invention.

[0133] (antioxidant) As the antioxidant, any antioxidant commonly used in resins can be used, but from the viewpoints of oxidation stability, thermal stability, jet-black color, etc., phosphite-based antioxidants, sulfur-based antioxidants, and phenol-based antioxidants are preferred. When an antioxidant is added to the resin composition of the present invention, the amount added is usually preferably 0.001 part by mass or more, more preferably 0.002 part by mass or more, and even more preferably 0.005 part by mass or more, based on 100 parts by mass of one or more resins, and is usually preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 2 parts by mass or less. By adding an antioxidant in an amount equal to or less than the upper limit, it is possible to prevent mold contamination during molding and produce molded articles with excellent surface appearance, while by adding an amount equal to or more than the lower limit, it is possible to achieve a sufficient improvement in weather resistance tests.

[0134] (Phosphite antioxidant) Examples of the phosphite antioxidant include triphenyl phosphite, tris(nonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, and distearyl pentaerythritol diphosphite. Among these, trisnonylphenyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, and bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite are preferably used. These compounds may be used alone or in combination of two or more.

[0135] (sulfur-based antioxidant) Examples of sulfur-based antioxidants include dilauryl-3,3'-thiodipropionic acid ester, ditridecyl-3,3'-thiodipropionic acid ester, dimyristyl-3,3'-thiodipropionic acid ester, distearyl-3,3'-thiodipropionic acid ester, laurylstearyl-3,3'-thiodipropionic acid ester, pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-laurylthiopropionate), glycerol-3-stearylthiopropionate, bis[2-methyl-4-(3-laurylthiopropionyloxy)-5-tert-butylphenyl]sulfide, octadecyl disulfide, mercaptobenzimidazole, 2-mercapto-6-methylbenzimidazole, and 1,1'-thiobis(2-naphthol). Among these, pentaerythritol tetrakis(3-laurylthiopropionate) is preferred. These compounds may be used alone or in combination of two or more.

[0136] (phenolic antioxidant) Examples of phenolic antioxidants include 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, and 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzyl. Examples of compounds include 2,4-di-tert-butylphenyl) 4,4'-biphenylenediphosphinate, 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylenediphosphinate, 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, and 2,6-di-tert-butyl-4-ethylphenol. Among these compounds, aromatic monohydroxy compounds substituted with one or more alkyl groups having 5 or more carbon atoms are preferred. Specifically, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, pentaerythritol-tetrakis[3-(3,5-di-tert-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, etc. are preferred, with pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] being more preferred. These compounds may be used alone or in combination of two or more.

[0137] (coloring agent) Examples of colorants include inorganic pigments, organic pigments, and organic dyes and pigments such as organic dyes. Examples of inorganic pigments include carbon black; and oxide pigments such as titanium oxide, zinc white, red iron oxide, chromium oxide, iron black, titanium yellow, zinc-iron brown, copper-chromium black, and copper-iron black. Examples of organic dyes and pigments such as organic pigments and organic dyes include phthalocyanine dyes and pigments; condensed polycyclic dyes and pigments such as azo-based, thioindigo-based, perinone-based, perylene-based, quinacridone-based, dioxazine-based, isoindolinone-based, and quinophthalone-based; and anthraquinone-based, perinone-based, perylene-based, methine-based, quinoline-based, heterocyclic, and methyl-based dyes and pigments. These colorants may be used alone or in combination of two or more. Among the inorganic pigments, organic pigments, and organic dyes and pigments such as organic dyes, inorganic pigments are preferred. By using an inorganic pigment as a colorant, the molded product can maintain its image clarity for a long period of time even when used outdoors. When a colorant is added to the resin composition of the present invention, the amount of the colorant added is usually 0.05 parts by mass or more and 5 parts by mass or less, preferably 0.05 parts by mass or more and 3 parts by mass or less, and more preferably 0.1 parts by mass or more and 2 parts by mass or less, based on 100 parts by mass of the total of the one or more resins and the glass frit (B) in the resin composition. By adding a colorant in an amount equal to or greater than the lower limit, a stencil-dyed molded article with good image clarity can be obtained, whereas by adding a colorant in an amount equal to or less than the upper limit, the surface roughness of the molded article can be reduced, resulting in a stencil-dyed molded article with good image clarity. The colored resin composition of the present invention, when toned to a jet black tone, has a lightness L * is preferably 0.1 or more and 10 or less, and particularly preferably 0.1 or more and 6 or less. The gloss level is preferably 85% or more, and particularly preferably 88% or more.

[0138] (Inorganic filler) The resin composition of the present invention may also contain an inorganic filler different from the glass frit (B). The amount of inorganic filler blended is usually 1 part by mass or more and 100 parts by mass or less, relative to 100 parts by mass of polycarbonate resin, with the lower limit being preferably 2 parts by mass or more, more preferably 3 parts by mass or more, and the upper limit being preferably 80 parts by mass or less, more preferably 60 parts by mass or less, and even more preferably 50 parts by mass or less. By blending the inorganic filler in an amount equal to or greater than the lower limit, a sufficient reinforcing effect can be achieved, and by blending the amount equal to or less than the upper limit, a good appearance can be achieved.

[0139] Examples of inorganic fillers include glass fiber, milled glass fiber, glass flakes, glass beads, carbon fiber, silica, alumina, titanium oxide, calcium sulfate powder, gypsum, gypsum whiskers, barium sulfate, talc, mica, calcium silicates such as 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, whiskers, etc. Among these, glass fibrous fillers, glass powder fillers, glass flake fillers, carbon fibrous fillers, carbon powder fillers, carbon flake fillers, various whiskers, mica, and talc are preferred. More preferred are glass fiber, glass flakes, milled glass fiber, carbon fiber, wollastonite, mica, and talc.

[0140] <Physical properties of resin composition> The resin composition of the present invention preferably has the following physical properties. (Total light transmittance) The polycarbonate resin composition of the present invention preferably has a total light transmittance of 80% or more at a thickness of 2 mm. In this case, the transparency of the polycarbonate resin composition is more excellent. From the same viewpoint, the total light transmittance is more preferably 85% or more. The total light transmittance is measured by the method described below.

[0141] (YI) The YI (Yellowing Index) of the polycarbonate resin composition of the present invention is preferably 10 or less. In this case, the transparency of the polycarbonate resin composition is more excellent. From the same viewpoint, the YI is more preferably 8.0 or less. The YI is measured by the method described below.

[0142] (Charpy impact strength) The polycarbonate resin composition of the present invention preferably has a Charpy impact strength of 2 or more. In this case, the impact resistance of the polycarbonate resin composition is superior. From the same viewpoint, the Charpy impact strength is more preferably 5 or more. The Charpy impact strength is measured by the method described below. (Pencil hardness) The polycarbonate resin composition of the present invention preferably has a pencil hardness of F or more. In this case, the polycarbonate resin composition has better scratch resistance. From the same viewpoint, the pencil hardness is more preferably 2H or more. The pencil hardness is measured by the method described below.

[0143] <Blending method> Methods for blending the various additives and the like described above into the resin composition of the present invention include, for example, a method of mixing and kneading using a tumbler, a V-type blender, a super mixer, a Nauta mixer, a Banbury mixer, a kneading roll, an extruder, or the like, or a solution blending method in which the additives are dissolved in a common good solvent such as methylene chloride and mixed, but the method is not particularly limited thereto, and any commonly used blending method may be used. The resin composition of the present invention thus obtained can be mixed with various additives and molded into a desired shape directly or after being pelletized in a melt extruder by a commonly known molding method such as extrusion molding, injection molding, or compression molding.

[0144] <Method of manufacturing resin composition> In an embodiment of the present invention, the timing and method of mixing the ultraviolet absorber, light stabilizer, and mono-hindered phenol-based antioxidant that can be blended into the resin composition are not particularly limited. Regarding the timing of mixing, for example, when the polycarbonate resin (A) is produced by a transesterification method, they may be mixed during the polymerization reaction or at the end of the polymerization reaction. Regardless of the polymerization method, mixing may be performed using a kneading extruder or the like when the polycarbonate resin (A) is in a molten state, such as during the kneading of the polycarbonate resin (A) with other compounding ingredients. Furthermore, a mixture of the polycarbonate resin (A) in a solid state, such as pellets or powder, with the compounding ingredients may be further heated and mixed.

[0145] The resin composition of the present invention can be produced by mixing the above-mentioned components simultaneously or in any order using a mixer such as a tumbler, V-blender, Nauta mixer, Banbury mixer, kneading roll, or extruder. As a mixing method, the above-mentioned compounding components may be directly mixed or kneaded with the polycarbonate resin (A), or a high-concentration masterbatch may be prepared in advance using a small amount of the polycarbonate resin (A) or other resin, etc., and the above-mentioned compounding components, and the masterbatch may be mixed with the polycarbonate resin (A) according to the present invention. [Example]

[0146] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples as long as the gist of the invention is not exceeded. In the following, the physical properties and characteristics of resin compositions, molded articles, etc. were evaluated by the following methods.

[0147] [Test specimen preparation method and various evaluations] <How to prepare test specimens> The resin composition pellets were dried for 10 hours at 90 to 100°C under a nitrogen atmosphere. Next, the dried resin composition pellets were fed into an injection molding machine (J75EII model manufactured by The Japan Steel Works, Ltd.) and molded into injection-molded specimens (100 mm wide x 100 mm long x 2 mm thick) and ISO test specimens for evaluating mechanical properties under conditions of a resin temperature of 240°C and a molding cycle of 40 seconds.

[0148] <Various evaluations> (Total light transmittance) Using the injection molded articles produced by the above test piece production method, total light transmittance was measured using an NDH-7000II (manufactured by Nippon Denshoku Industries Co., Ltd.) under a D65 light source in accordance with JIS K7361.

[0149] (YI) Using the injection molded product produced by the above test piece production method, YI was measured using a CM-5 (manufactured by Konica Minolta) under Illuminant C in accordance with JIS K7373.

[0150] (Scratch resistance) The test was carried out using injection molded products prepared using the above test piece preparation method and a HEIDON TYPE 30S manufactured by Shinto Scientific Co., Ltd. The abrasive element was a φ28mm holder with a Kanakin No. 3 friction cloth attached, and the test was carried out 100 times with a load of 9.8N, a stroke of 50mm, and a speed of 6000mm / min, and then the appearance was visually observed. 〇: No significant scratches △: Slight scratches ×: Scratches are visible

[0151] (Charpy impact strength) The ISO test specimen obtained above was notched with a notch tip radius of 0.25R, and the Charpy impact strength was measured in accordance with ISO-179.

[0152] (Pencil hardness) Measurements were carried out using a JIS-compliant pencil hardness tester (manufactured by Mize Testing Instruments Co., Ltd.) based on the conditions of JIS K-5600, and the hardest pencil that did not cause scratches was used for evaluation.

[0153] [Production Example 1 Polycarbonate Resin (A-1)] Polycarbonate resin polymerization was carried out using a continuous polymerization system consisting of three vertical stirred reactors, one horizontal stirred reactor, and a twin-screw extruder. Specifically, ISB, CHDM, and DPC were melted in tanks and continuously fed into the first vertical stirred reactor at flow rates of 35.2 kg / hr for ISB, 14.9 kg / hr for CHDM, and 74.5 kg / hr for DPC (molar ratio ISB / CHDM / DPC = 0.700 / 0.300 / 1.010). An aqueous solution of calcium acetate monohydrate was also fed into the first vertical stirred reactor at a catalyst concentration of 1.5 μmol per mol of total dihydroxy compounds.

[0154] The first vertical stirred reactor had a reaction temperature of 190°C, an internal pressure of 25 kPa, and a residence time of 90 minutes, the second vertical stirred reactor had a reaction temperature of 195°C, an internal pressure of 10 kPa, and a residence time of 45 minutes, the third vertical stirred reactor had a reaction temperature of 210°C, an internal pressure of 3 kPa, and a residence time of 45 minutes, and the fourth horizontal stirred reactor had a reaction temperature of 225°C, an internal pressure of 0.5 kPa, and a residence time of 90 minutes. The fourth horizontal stirred reactor was operated while finely adjusting the internal pressure so that the reduced viscosity of the resulting polycarbonate resin would be 0.42 dL / g or more and less than 0.50 dL / g.

[0155] Polycarbonate resin was extracted from the fourth horizontal stirred reactor at a rate of 60 kg / hr. The resin was then fed in a molten state into a vented twin-screw extruder (TEX30α, manufactured by The Japan Steel Works, Ltd., L / D: 42.0, L (mm): screw length, D (mm): screw diameter). The polycarbonate resin passing through the extruder was then passed through a 10 μm SUS316 candle filter while still in a molten state to filter out impurities. The polycarbonate resin was then discharged in the form of strands from the die, water-cooled, solidified, and pelletized with a rotary cutter to obtain a polycarbonate resin with an ISB / CHDM molar ratio of 70 / 30 mol%. This polycarbonate resin is designated as "A-1" as appropriate.

[0156] The extruder had three vacuum vents, through which residual low-molecular-weight components in the resin were removed by volatilization. Just before the second vent, 2000 ppm by weight of water was added to the resin, and water was poured in to remove the volatilization. Just before the third vent, 0.1 parts by weight of Irganox 1010, 0.05 parts by weight of AS2112, and 0.3 parts by weight of E-75 were added, respectively, per 100 parts by weight of polycarbonate resin. This yielded ISB / CHDM copolymer polycarbonate resin pellets. 0.65 ppm by weight of phosphorous acid (0.24 ppm by weight in terms of phosphorus atoms) was added to the polycarbonate resin as a catalyst deactivator. The phosphorous acid was added as follows: A masterbatch was prepared by mixing the polycarbonate resin pellets obtained in Production Example 1 with an ethanol solution of phosphorous acid, and the masterbatch was fed into the extruder just before the first vent port (on the resin feed port side of the extruder) so that the masterbatch was 1 part by weight per 100 parts by weight of the polycarbonate resin in the extruder.

[0157] [Production Example 2 Polycarbonate Resin (A-2)] A polycarbonate resin was produced in the same manner as in Production Example 1, except that the molar ratio of ISB to CHDM was ISB / CHDM = 0.500 / 0.500 and the reduced viscosity was adjusted to 0.50 dL / g or more and 0.63 dL / g or less. This polycarbonate resin is appropriately referred to as "A-2".

[0158] [Explanation of compounds (abbreviations) used in the examples and comparative examples] The abbreviations for compounds used in the following examples are as follows: In the examples, the "refractive index" refers to the value listed in the product information for commercially available products, and for other products, refers to the refractive index for light with a wavelength of 589.3 nm measured in accordance with JIS K7142:2014.

[0159] <Polycarbonate resin (A)> A-1: Polycarbonate resin of Production Example 1. Glass transition temperature: 122°C. Reduced viscosity: 0.44 dL / g. Refractive index: 1.50. A-2: Polycarbonate resin of Production Example 2. Glass transition temperature: 100°C. Reduced viscosity: 0.61 dL / g. Refractive index: 1.50. A-3: Bisphenol A polycarbonate resin (Mitsubishi Engineering Plastics Corporation, Iupilon S3000R) refractive index 1.59

[0160] <Glass frit (B), etc.> B-1: Glass frit CF0018 manufactured by Takara Standard Co., Ltd., refractive index 1.52, average particle size 20 μm B-2: Glass frit CF0023 manufactured by Takara Standard Co., Ltd., refractive index 1.50, average particle size 12 μm B-3: Glass frit CF0093 manufactured by Takara Standard Co., Ltd., refractive index 1.50, average particle size 40 μm Silica: Admatechs silica SM-C8, average particle size 0.3 μm

[0161] <Ultraviolet absorber (C)> C-1: Benzotriazole-based ADEKA STAB LA-29 C-2: Benzophenone-based ADEKA Adekastab LA-31 C-3: Triazine-based ADEKA Adekastab LA-46

[0162] <Light stabilizer (D)> D-1: Hindered amine type, manufactured by ADEKA, ADK STAB LA-77G D-2: Hindered amine type, ADEKA Adekastab LA-57 <Impact modifier (E)> E-1: Kaneka Core-shell structure elastomer M592

[0163] [Example 1] Polycarbonate resin (A-1), glass frit (B-1), UV absorber (C-1), and light stabilizer (D-1) were mixed to obtain the composition shown in Table 1. The mixture was extruded into strands using a twin-screw extruder (TEX-33) manufactured by The Japan Steel Works, Ltd., equipped with one vent, so that the resin temperature at the outlet reached 250°C. The mixture was then cooled and solidified with water, and pelletized using a rotary cutter. The vent was connected to a vacuum pump, and the pressure at the vent was controlled to be 10 to 50 kPa. The evaluation results of the resulting resin composition are shown in Table 1.

[0164] [Examples 2 to 7, Comparative Examples 1 to 4] A resin composition was obtained in the same manner as in Example 1, except that the formulation was changed as shown in Table 1. The obtained resin composition was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

[0165] [Table 1]

[0166] As can be seen from Table 1, Examples 1 to 7, which contain a polycarbonate resin (A) having a specific structural unit and a specific amount of glass frit (B), are excellent in transparency, scratch resistance, and mechanical properties. Comparative Example 1, which does not contain glass frit (B), is inferior in pencil hardness. Comparative Example 2, which contains more than the specified amount of glass frit, is inferior in impact strength. Comparative Example 3, which uses silica instead of glass frit (B), is inferior in scratch resistance. When the polycarbonate resin does not have a specific structure (Comparative Example 4), the pencil hardness is inferior even though it contains glass frit.

[0167] The present invention provides a resin composition that is excellent in scratch resistance, transparency, and mechanical properties, and therefore makes it possible to provide resin compositions and molded articles that can be used in a wide range of fields, such as injection molding of electrical and electronic parts, automotive parts, etc., and building materials.

Claims

1. A resin composition comprising one or more resins, The one or more resins include a polycarbonate resin (A) containing a structural unit (a1) derived from a dihydroxy compound represented by the following general formula (1): The resin composition further contains a glass frit (B), The content of the glass frit (B) is 0.1 to 4.0 parts by mass, relative to 100 parts by mass of the total amount of the one or more resins. 【Chemistry 1】

2. 2. The resin composition according to claim 1, wherein the polycarbonate resin (A) is a copolymeric polycarbonate resin further comprising a structural unit (a2) derived from one or more dihydroxy compounds selected from the group consisting of ether group-containing dihydroxy compounds, aliphatic dihydroxy compounds, and alicyclic dihydroxy compounds, which are different from the dihydroxy compound represented by formula (1).

3. 2. The resin composition according to claim 1, wherein the polycarbonate resin (A) contains 30 mol % or more and 95 mol % or less of the structural unit (a1) derived from the dihydroxy compound represented by the formula (1) relative to 100 mol % of all structural units derived from the dihydroxy compound.

4. The resin composition according to claim 1, wherein an absolute value of a difference in refractive index between the one or more resins and the glass frit (B) for light having a wavelength of 589.3 nm is 0.05 or less.

5. The resin composition according to claim 1, wherein the refractive index of the glass frit (B) for light having a wavelength of 589.3 nm is 1.480 to 1.

520.

6. The resin composition further contains an impact modifier (E), The resin composition according to claim 1, wherein the content of the impact resistance modifier (E) is 0.1 to 50 parts by mass, with the total amount of the parts by mass of the one or more resins being 100 parts by mass.

7. The resin composition according to claim 6, wherein the impact resistance modifier (E) is an elastomer having a core-shell structure.

8. A molded article obtained by molding the resin composition according to any one of claims 1 to 7.

9. 1. A method for producing a composition, comprising: The method includes mixing 100 parts by mass of a resin with 0.1 parts by mass or more and 4.0 parts by mass or less of a glass frit (B), The resin comprises a polycarbonate resin (A) containing a structural unit (a1) derived from a dihydroxy compound represented by the following general formula (1): 【Chemistry 2】

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