Resin composition, molded article and device

Abstract

To provide a resin composition having both mechanical characteristics and good appearance, especially a resin composition excellent in scratch resistance and gloss, and to provide a molded article and a device using the resin composition.SOLUTION: A resin composition comprising at least one resin (A) and a glass filler (B), wherein the at least one resin (A) comprises a polycarbonate resin (A), and the content of the glass filler is 0.01 parts by mass or more and 4.0 parts by mass or less when the total amount in parts by mass of the at least one resin is 100 parts by mass.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Molded articles made of polycarbonate resins have excellent mechanical properties such as transparency, heat resistance, and impact resistance, and are therefore widely used as industrial transparent materials in fields such as electrical, mechanical, and automotive. Furthermore, glass-based materials such as glass fibers are used as fillers to further improve the rigidity of the resin composition that constitutes the molded body and to strengthen the mechanical strength (bending strength, tensile strength, etc.) (Patent Documents 1 and 2). [Prior art documents] [Non-patent literature]

[0003] [Patent Document 1] WO2018-199033 publication [Patent Document 2] Publication No. 2009-074029 Summary of the Invention [Problem to be solved by the invention]

[0004] However, the resin compositions described in Patent Documents 1 and 2 use a large amount of glass fiber as a filler for the resin composition, which tends to impair the appearance of the resin composition, such as gloss. Moreover, in recent years, there has been a trend toward resin compositions that are excellent in scratch resistance and appearance such as gloss, as resin compositions for forming molded articles.

[0005] In view of these problems, an object of the present invention is to provide a resin composition that combines mechanical properties and good appearance, particularly a resin composition that is excellent in scratch resistance and gloss, and a molded article and device that use the resin composition. [Means for solving the problem]

[0006] As a result of intensive research into the above-mentioned problems, the present inventors have unexpectedly found that, in a resin composition containing a resin including a polycarbonate resin and a glass filler, it is possible to obtain a resin composition that has good scratch resistance and good appearance such as gloss by adding only a small amount of glass filler, contrary to conventional wisdom, whereas glass filler has conventionally been required to be added in large amounts to improve mechanical strength, and have completed the following invention.

[0007] [1] A resin composition containing one or more resins, the one or more resins include a polycarbonate resin (A), the resin composition further contains a glass filler (B), The resin composition has a content of the glass filler (B) of 0.01 parts by mass or more and 4.0 parts by mass or less, relative to 100 parts by mass of the total amount of the one or more resins.

[0008] [2] The resin composition according to [1], wherein the polycarbonate resin (A) contains at least a structural unit (a1) derived from an aliphatic dihydroxy compound having a cyclic structure.

[0009] [3] The resin composition according to [2], wherein the aliphatic dihydroxy compound having a cyclic structure is a dihydroxy compound represented by the following formula (1):

[0010] [ka]

[0011] [4] The resin composition according to [3], wherein the polycarbonate resin (A) further has a structural unit derived from at least one dihydroxy compound selected from the group consisting of an ether group-containing dihydroxy compound, an aliphatic dihydroxy compound, and an alicyclic dihydroxy compound, which is different from the dihydroxy compound represented by formula (1).

[0012] [5] The resin composition according to [3] or [4], wherein the polycarbonate resin (A) contains 20 mol % or more and 95 mol % or less of structural units derived from the dihydroxy compound represented by the above formula (1) relative to 100 mol % of all structural units derived from dihydroxy compounds.

[0013] [6] The resin composition according to any one of [1] to [5], wherein the content of the glass filler (B) relative to 100 parts by mass of the resin (A) is 0.01 parts by mass or more and less than 1 part by mass.

[0014] [7] The resin composition according to any one of [1] to [6], wherein the glass filler (B) is one or more selected from the group consisting of glass fibers and glass beads.

[0015] [8] A molded article using the resin composition according to any one of [1] to [7].

[0016] [9] The molded article according to [8], which is a part for a vehicle, an aircraft, or a ship.

[0017]

[10] A device for transporting substances, animals or humans, comprising the molded body according to [8] or [9].

[0018]

[11] The device according to

[10] , which is a vehicle, an aircraft or a ship. [Effects of the Invention]

[0019] According to the present invention, by preparing a resin composition containing a polycarbonate resin (A) and a predetermined amount of glass filler (B), it is possible to provide a resin composition that combines mechanical properties and good appearance, in particular a resin composition that combines scratch resistance and gloss, and a molded article and device using the resin composition. DETAILED DESCRIPTION OF THE INVENTION

[0020] The following describes in more detail the embodiments of the present invention. However, the description of the constituent elements described below is an example of an embodiment of the present invention, and the present invention is not limited to these contents, and can be implemented in various modifications within the scope of its gist.

[0021] [Resin composition] The resin composition of the present invention contains one or more resins and a glass filler (B).

[0022] <One or more types of resin> The one or more resins constituting the resin composition of the present invention include a polycarbonate resin (A).

[0023] (Polycarbonate resin (A)) The polycarbonate resin (A) preferably contains at least a structural unit derived from an aliphatic dihydroxy compound having a cyclic structure. Examples of the aliphatic dihydroxy compound having a cyclic structure include dihydroxy compounds represented by the following formula (1):

[0024] [ka]

[0025] Structural unit (a1) Hereinafter, the structural unit derived from the dihydroxy compound represented by formula (1) may be referred to as structural unit (a1). The polycarbonate resin (A) may be a homopolymer of the structural unit (a1), or may be a copolymer containing the structural unit (a1) and a structural unit (a2) other than the structural unit (a1). From the viewpoints of increasing the molecular weight and further improving impact resistance, the polycarbonate resin (A) is preferably a copolymer. Furthermore, since the polycarbonate resin (A) contains the structural unit (a1), a resin composition having excellent transparency and high rigidity due to its amorphous nature can be obtained. Furthermore, a resin composition having a good balance of heat resistance, moldability, and colorability in addition to the transparency and rigidity can be obtained. In particular, since the resin has both moldability and colorability, it can be mixed with a colorant and molded as is, for example, to provide a molded article with a uniform color. Furthermore, since there is no need to paint the molded article with a colorant after molding, emissions of volatile organic compounds (VOCs) can be reduced during the production of the molded article.

[0026] The dihydroxy compound represented by the above formula (1) (hereinafter referred to as "dihydroxy compound (1)") includes isosorbide, isomannide, and isoidet, which are stereoisomers. These dihydroxy compounds (1) may be used singly or in combination of two or more. Among them, isosorbide obtained by dehydration condensation of sorbitol produced from various starches, which are abundant and easily available as plant-derived resources, 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 the dihydroxy compound 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] Structural unit (a2) 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 aliphatic dihydroxy compounds, alicyclic dihydroxy compounds, and ether group-containing dihydroxy compounds other than the dihydroxy compound represented by formula (1) (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 keeping the number of carbon atoms below the above upper limit, synthesis and purification can be facilitated while maintaining heat resistance. By keeping the number of carbon atoms above the above lower limit, the ring structure is stabilized and synthesis is facilitated while maintaining the tendency for easy purification and availability.

[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] 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 (a2) 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, one or more selected from the group consisting of cyclobutanediol, cyclohexanedimethanol, and tricyclodecanedimethanol are particularly preferred.

[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 copolymer 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 the structural unit (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 the structural unit (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 the structural unit (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] Other structural units The polycarbonate resin (A) may further contain structural units other than the structural units (a1) and (a2). Examples of other dihydroxy compounds that form such structural units include dihydroxy compounds containing an aromatic group. By keeping the amount of structural units derived from dihydroxy compounds containing aromatic groups contained in the polycarbonate resin (A) low, the following three advantages are obtained, for example. First, it is easy to obtain a polycarbonate resin (A) with a high molecular weight, and it tends to be easy to obtain a resin with good impact resistance. Secondly, as will be described later, decomposition caused by the addition of an amine compound can be suppressed, and the impact resistance and color tone of the resin composition of the present invention tend to be easily maintained at a good level. Thirdly, crosslinking or cleavage due to light such as ultraviolet light, metathesis reactions, etc. can be suppressed, making it easier to obtain resins and resin compositions with excellent weather resistance.

[0043] Therefore, from the viewpoint of further improving impact resistance, color tone, and weather resistance, the content of structural units derived from dihydroxy compounds containing aromatic groups, relative to 100 mol% of all structural units derived from dihydroxy compounds, is preferably less than 50 mol%, more preferably 10 mol% or less, and even more preferably 5 mol% or less, and it is most preferable that the polycarbonate resin (A) does not contain structural units derived from dihydroxy compounds containing aromatic groups.

[0044] As the dihydroxy compound containing an aromatic group, for example, the following dihydroxy compounds can be used, but dihydroxy compounds other than these can also be used: 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-diethylphenyl)propane, 2,2-bis(4-hydroxy-(3-phenyl)phenyl)propane, 2,2-bis(4-hydroxy-(3,5-diphenyl)phenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, bis(4- 1,1-bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)diphenylmethane, 1,1-bis(4-hydroxyphenyl)-2-ethylhexane, 1,1-bis(4-hydroxyphenyl)decane, bis(4-hydroxy-3-nitrophenyl)methane, 3,3-bis(4-hydroxyphenyl)methane bis(4-hydroxyphenyl)pentane, 1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)sulfone, 2,4'-dihydroxydiphenyl sulfone, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxy-3-methylphenyl)sulfide, bis(4-hydroxyphenyl)disulfide, 4,4'-dihydroxy Aromatic bisphenol compounds such as diphenyl ether and 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether; dihydroxy compounds having an ether group bonded to an aromatic group such as 2,2-bis(4-(2-hydroxyethoxy)phenyl)propane, 2,2-bis(4-(2-hydroxypropoxy)phenyl)propane, 1,3-bis(2-hydroxyethoxy)benzene, 4,4'-bis(2-hydroxyethoxy)biphenyl, and bis(4-(2-hydroxyethoxy)phenyl)sulfone;9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-(2-hydroxypropoxy)phenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)fluorene, 9,9-bis(4-(2-hydroxypropoxy)-3-methylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-isopropylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-isobutylphenyl)fluorene Dihydroxy compounds having a fluorene ring, such as 9,9-bis(4-(2-hydroxyethoxy)-3-tert-butylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-cyclohexylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3,5-dimethylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-tert-butyl-6-methylphenyl)fluorene, and 9,9-bis(4-(3-hydroxy-2,2-dimethylpropoxy)phenyl)fluorene;

[0045] The other dihydroxy compounds can be appropriately selected depending on the properties required for the polycarbonate resin (A). One or more types of the other dihydroxy compounds may be used. By using the other dihydroxy compounds in combination with the dihydroxy compound of formula (1), it is possible to obtain an effect of improving the flexibility and mechanical properties of the polycarbonate resin (A), an effect of improving the moldability, and the like.

[0046] (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. In particular, the dihydroxy compound of formula (1) is prone to deterioration under acidic conditions. Therefore, by using a basic stabilizer in the synthesis process of the polycarbonate resin (A), deterioration of the dihydroxy compound of formula (1) can be suppressed. This can further improve the quality of the resulting polycarbonate resin composition.

[0047] 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.

[0048] 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.

[0049] The content of the basic stabilizer in the dihydroxy compound (1) (specifically, the content of the basic stabilizer relative to 100% by weight of the total of the dihydroxy compound of formula (1) and the basic stabilizer) is preferably 0.0001 to 1% by weight. In this case, the effect of preventing deterioration of the dihydroxy compound of formula (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 weight.

[0050] 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.

[0051] [ka]

[0052] 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.

[0053] 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.

[0054] The polycarbonate resin (A) may contain only the structural unit (a2) described above without containing the structural unit derived from the aliphatic dihydroxy compound having a cyclic structure, or may contain a structural unit derived from a dihydroxy compound having an aromatic group as the structural unit (a2).

[0055] The concentration of the carbonic acid diester remaining in the polycarbonate resin (A) of the present invention is preferably 200 ppm by weight or less, more preferably 100 ppm by weight or less, particularly preferably 60 ppm by weight or less, and most preferably 30 ppm by weight 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 weight. 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.

[0056] (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.

[0057] 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.

[0058] Polymerization catalysts that can be used in producing the polycarbonate resin (A) of the present invention include, for example, 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 compounds such as 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.

[0059] 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.

[0060] 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. Of 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.

[0061] Examples of the 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, a magnesium compound, a calcium compound, or a barium compound is preferred, and from the viewpoints of polymerization activity and the color tone of the resulting polycarbonate resin (A), a magnesium compound and / or a calcium compound is more preferred, and a calcium compound is most preferred.

[0062] 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 above-mentioned Group 1 metal compound and / or Group 2 metal compound as an auxiliary compound, but it is particularly preferable to use only the Group 1 metal compound and / or Group 2 metal compound.

[0063] Examples of the basic phosphorus compound include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, and quaternary phosphonium salts.

[0064] Examples of the basic ammonium compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide, and butyltriphenylammonium hydroxide.

[0065] Examples of the 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, aminoquinoline, and guanidine.

[0066] 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.

[0067] When a compound containing at least one metal selected from the group consisting of Group 2 metals in the long periodic table and lithium is used as the polymerization catalyst, particularly when a magnesium compound and / or a calcium compound is used, the amount of the polymerization catalyst used is preferably 0.1 μmol or more, more preferably 0.3 μmol or more, and particularly preferably 0.5 μmol or more, in terms of the metal atomic weight of the compound containing the metal, per mol of the total dihydroxy compounds used in the reaction. The upper limit is preferably 10 μmol or less, more preferably 5 μmol or less, and particularly preferably 3 μmol or less.

[0068] 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.

[0069] Considering the adverse effects of sodium, potassium, and 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 weight ppm or less, and more preferably 0.5 weight ppm 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.

[0070] The polycarbonate resin composition may contain one type of resin alone as the polycarbonate resin (A), or may contain a mixture of two or more resins differing in the type of structural unit (a2), copolymerization ratio, physical properties, etc.

[0071] Synthesis of polycarbonate resin (A) The polycarbonate resin (A) can be obtained, for example, by polycondensing a dihydroxy compound such as the dihydroxy compound of formula (1) with a carbonic acid diester through an ester exchange reaction in the presence of a polymerization catalyst.

[0072] 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, 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.

[0073] The operation of mixing the dihydroxy compound and the carbonic acid diester is usually 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, the color tone of the polycarbonate resin (A) can be improved, and the reactivity in polymerization can be increased.

[0074] 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.

[0075] Furthermore, by setting this molar ratio to not more than the above upper limit, it is possible to prevent a decrease in the rate of the transesterification reaction under the same conditions, facilitate the production of a polycarbonate resin (A) having a desired molecular weight, and prevent an increase in the amount of residual carbonate diester in the produced polycarbonate resin (A), thereby preventing the residual carbonate diester from causing odor during molding or in the molded product. Furthermore, it is possible to prevent an increase in the thermal history during the polymerization reaction, which tends to result in good color and weather resistance of the resulting polycarbonate resin (A).

[0076] 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.

[0077] The polycondensation of a dihydroxy compound and a carbonate diester is carried out in multiple stages using multiple reactors in the presence of the above-mentioned polymerization catalyst. The reaction may be carried out in a batchwise manner, a continuous manner, or a combination of a batchwise manner and a continuous manner. However, it is preferable to adopt a continuous manner from the viewpoint that the polycarbonate resin (A) can be obtained with less thermal history and is excellent in productivity.

[0078] 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.

[0079] 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 is present. The temperature of the refrigerant introduced into the reflux condenser can be selected appropriately 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.

[0080] In order to maintain an appropriate polymerization rate, suppress distillation of monomers, and improve the color tone of the resulting polycarbonate resin (A), it is preferable to select the type and amount of the polymerization 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.

[0081] In the production of the polycarbonate resin (A) of the present invention, the catalyst can be added to a raw material preparation tank 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 polymerization reactor, and the catalyst is preferably supplied in the form of an aqueous solution.

[0082] From the viewpoint of controlling the polymerization rate and obtaining excellent 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 according to 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 reaction. In this case, distillation of unreacted monomers is suppressed, and it becomes easier to adjust the molar ratio of the dihydroxy compound to the carbonate diester 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 with the desired molecular weight and terminal groups.

[0083] 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 reaction conditions can be adopted 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.

[0084] From the second stage onwards, it is preferable to gradually reduce the pressure of the reaction system from the pressure of the first stage, and ultimately reduce the pressure (absolute pressure) of the reaction system to 1 kPa or less while removing the monohydroxy compound that is subsequently generated from the reaction system. The maximum internal temperature of the polymerization reactor is usually set in the range of 200 to 260°C, preferably 210 to 250°C. The reaction time is usually set in the range of 0.1 to 10 hours, preferably 0.3 to 6 hours, and particularly preferably 0.5 to 3 hours.

[0085] From the viewpoint of suppressing the occurrence of discoloration, thermal degradation or "burn" of the polycarbonate resin (A) and obtaining a polycarbonate resin (A) with better color tone or higher impact resistance, the maximum internal temperature of the polymerization 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.

[0086] 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.

[0087] 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.

[0088] In continuous polymerization, in order to control the molecular weight of the polycarbonate resin (A) finally obtained at a constant level, it is preferable to adjust the polymerization rate as necessary. In this case, a method with good operability is to adjust the pressure in the polymerization reactor in the final stage.

[0089] Furthermore, as mentioned above, the polymerization rate varies depending on the ratio of hydroxyl group terminals to carbonate group terminals. Therefore, by deliberately reducing one of the terminal groups to suppress the polymerization rate and maintaining a high vacuum in the final-stage polymerization reactor, the amount of remaining low-molecular-weight components in the resin, including monohydroxy compounds, can be reduced. However, in this case, if the amount of one terminal group is too small, even a slight change in the terminal group balance can drastically reduce the reactivity, and the molecular weight of the resulting polycarbonate resin (A) may fall short of the desired molecular weight. To avoid this problem, it is preferable that the polycarbonate resin (A) obtained in the final-stage polymerization reactor contain at least 10 mol / ton of both hydroxyl group terminals and carbonate group terminals. On the other hand, if both terminal groups are too large, the polymerization rate will be too fast and the molecular weight will be too high, so it is preferable that the amount of one terminal group be 60 mol / ton or less.

[0090] In this way, by adjusting the amount of terminal groups and the pressure of the final-stage polymerization reactor within preferred ranges, the amount of monohydroxy compounds remaining in the resin at the outlet of the polymerization reactor can be reduced. The amount of monohydroxy compounds remaining in the resin at the outlet of the polymerization reactor is preferably 2000 ppm by weight or less, more preferably 1500 ppm by weight or less, and even more preferably 1000 ppm by weight or less. By reducing the content of monohydroxy compounds at the outlet of the polymerization reactor in this way, volatilization of monohydroxy compounds and the like can be easily carried out in a subsequent step.

[0091] Although it is preferable that the residual amount of the monohydroxy compound is small, in order to reduce it to less than 100 ppm by weight, it is necessary to extremely reduce the amount of one of the terminal groups and adopt operating conditions such as maintaining the pressure of the polymerization reactor at a high vacuum. In this case, as mentioned above, it becomes difficult to maintain the molecular weight of the obtained polycarbonate resin (A) at a constant level, so the amount is usually 100 ppm by weight or more, preferably 150 ppm by weight or more.

[0092] From the viewpoint of effective resource utilization, it is preferable to reuse the by-produced monohydroxy compound as a raw material for other compounds after purifying it as necessary. For example, when the monohydroxy compound is phenol, it can be used as a raw material for diphenyl carbonate, bisphenol A, etc.

[0093] Catalyst deactivator The polycarbonate resin (A) preferably contains a catalyst deactivator. The catalyst deactivator is not particularly limited as long as it is an acidic substance that has the function of deactivating the polymerization catalyst, but examples thereof include phosphoric acid, trimethyl phosphate, triethyl phosphate, phosphorous acid, phosphonium salts such as octylsulfonate tetrabutylphosphonium salt, benzenesulfonate tetramethylphosphonium salt, benzenesulfonate tetrabutylphosphonium salt, dodecylbenzenesulfonate tetrabutylphosphonium salt, and p-toluenesulfonate tetrabutylphosphonium salt; ammonium salts such as decylsulfonate tetramethylammonium salt, and dodecylbenzenesulfonate tetrabutylammonium salt; and alkyl esters such as methyl benzenesulfonate, butyl benzenesulfonate, methyl p-toluenesulfonate, butyl p-toluenesulfonate, and ethyl hexadecylsulfonate.

[0094] The catalyst deactivator preferably contains a phosphorus-based compound (hereinafter referred to as the "specific phosphorus-based compound") containing either the partial structure represented by the following formula (5) or (6). The specific phosphorus-based compound can be added after the polycondensation reaction is completed, i.e., during the kneading process, pelletization process, or the like, to deactivate the polymerization catalyst described below and inhibit the subsequent unnecessary progression of the polycondensation reaction. As a result, the progression of polycondensation when the polycarbonate resin (A) is heated in a molding process or the like can be inhibited, and thus the elimination of the monohydroxy compound can be inhibited. Furthermore, by deactivating the polymerization catalyst, discoloration of the polycarbonate resin (A) at high temperatures can be further inhibited.

[0095] [ka]

[0096] [ka]

[0097] The specific phosphorus-based compound containing the partial structure represented by the above formula (5) or (6) may be phosphoric acid, phosphorous acid, phosphonic acid, hypophosphorous acid, polyphosphoric acid, phosphonate ester, acidic phosphate ester, etc. Among the specific phosphorus-based compounds, phosphorous acid, phosphonic acid, and phosphonate ester are more effective in deactivating the catalyst and inhibiting coloration, and phosphorous acid is particularly preferred.

[0098] As the phosphonic acid, for example, the following compounds can be used: phosphonic acid (phosphorous acid), methylphosphonic acid, ethylphosphonic acid, vinylphosphonic acid, decylphosphonic acid, phenylphosphonic acid, benzylphosphonic acid, aminomethylphosphonic acid, methylenediphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, 4-methoxyphenylphosphonic acid, nitrilotris(methylenephosphonic acid), propylphosphonic anhydride, etc.

[0099] As the phosphonate ester, for example, the following compounds can be used: dimethyl phosphonate, diethyl phosphonate, bis(2-ethylhexyl) phosphonate, dilauryl phosphonate, dioleyl phosphonate, diphenyl phosphonate, dibenzyl phosphonate, dimethyl methylphosphonate, diphenyl methylphosphonate, diethyl ethylphosphonate, diethyl benzylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate, dipropyl phenylphosphonate, diethyl (methoxymethyl)phosphonate, diethyl vinylphosphonate, hydroxymethyl phosphonate, diethyl phosphonate, dimethyl (2-hydroxyethyl)phosphonate, diethyl p-methylbenzylphosphonate, diethyl phosphonoacetic acid, ethyl diethylphosphonoacetate, tert-butyl diethylphosphonoacetate, diethyl 4-chlorobenzylphosphonate, diethyl cyanophosphonate, diethyl cyanomethylphosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl phosphonoacetaldehyde diethyl acetal, diethyl (methylthiomethyl)phosphonate and the like.

[0100] Examples of acidic phosphate esters that can be used include the following compounds: phosphate diesters such as dimethyl phosphate, diethyl phosphate, divinyl phosphate, dipropyl phosphate, dibutyl phosphate, bis(butoxyethyl) phosphate, bis(2-ethylhexyl) phosphate, diisotridecyl phosphate, dioleyl phosphate, distearyl phosphate, diphenyl phosphate, and dibenzyl phosphate, or mixtures of diesters and monoesters, diethyl chlorophosphate, and zinc stearyl phosphate.

[0101] The specific phosphorus compounds may be used singly or in combination of two or more in any ratio.

[0102] The content of the specific phosphorus compound in the polycarbonate resin (A) is preferably 0.1 ppm by weight or more and 5 ppm by weight or less in terms of phosphorus atoms. In this case, the specific phosphorus compound can sufficiently suppress catalyst deactivation and coloration. In addition, in this case, coloration of the polycarbonate resin (A) can be further prevented, particularly in durability tests under high temperature and high humidity.

[0103] Furthermore, by adjusting the content of the specific phosphorus-based compound according to the amount of the polymerization catalyst, the effect of suppressing catalyst deactivation and coloration can be more reliably obtained. The content of the specific phosphorus-based compound is preferably 0.5 to 5 times the molar amount of phosphorus atoms per 1 mol of metal atoms in the polymerization catalyst, more preferably 0.7 to 4 times the molar amount, and particularly preferably 0.8 to 3 times the molar amount of phosphorus atoms per 1 mol of metal atoms in the polymerization catalyst.

[0104] (Physical properties of polycarbonate resin (A)) The preferred physical properties of the polycarbonate resin (A) are shown below.

[0105] 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.

[0106] 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. 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.).

[0107] 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. From the viewpoints of improving fluidity during molding, thereby improving the molding cycle in, for example, injection molding, and also of reducing distortion of molded articles and preventing thermal deformation, 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. On the other hand, from the viewpoint of further improving 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.

[0108] The reduced viscosity of the polycarbonate resin (A) is measured using an Ubbelohde viscometer at a temperature of 20.0°C ± 0.1°C after precisely adjusting the concentration of the polycarbonate resin to 0.6 g / dL using methylene chloride as a solvent.

[0109] <Other resin components constituting one or more types of resin (A)> As long as the effects of the present invention are not lost, the one or more resins (A) may contain other resins in addition to the polycarbonate resin (A), 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, or two or more may be used. When the one or more resins (A) 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.

[0110] Furthermore, when the one or more resins (A) 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 (A) as a whole being 100% by mass.

[0111] <Glass filler (B)> The glass filler (B) constituting the resin composition of the present invention functions as a filler for the resin composition of the present invention. The glass filler (B) is preferably one selected from the group consisting of glass fiber and glass beads, or may contain a plurality of types selected from these. By including the glass filler (B), a resin composition having improved scratch resistance can be obtained. Glass fillers have generally been used for the purpose of improving mechanical properties such as rigidity, but the present inventors have found that by including a specific glass filler (B), the resulting resin composition exhibits scratch resistance, and further, by limiting the content to a specific amount, the appearance (gloss) of the resin composition can also be improved.

[0112] (Material) As the glass material of the glass filler (B), quartz glass, soda-lime glass, borosilicate glass, alkali-free aluminoborosilicate glass, high silicate glass, aluminosilicate glass, aluminoborosilicate glass, lead glass, etc. can be used. From the viewpoint of achieving a good balance between low thermal expansion and heat resistance, it is preferable to use aluminoborosilicate glass.

[0113] (Size) In the case of glass beads, the particle size (50% diameter) measured by the Coulter method is preferably 1 μm or more and 10 μm or less, more preferably 1.5 μm or more and 7 μm or less, and even more preferably 2 μm or more and 5 μm or less. When the particle size of the glass beads is within the above range, a resin composition having good scratch resistance and gloss tends to be easily obtained.

[0114] In the case of glass fibers, the fiber length is preferably 0.05 μm or more, more preferably 0.10 μm or more, even more preferably 0.50 μm or more, still more preferably 1.0 μm or more, and particularly preferably 3.0 μm or more, and is usually 10 mm or less, preferably 5.0 mm or less, more preferably 1.0 mm or less, even more preferably 200 μm or less, still more preferably 100 μm or less, particularly preferably 30 μm or less, and most preferably 15 μm or less. When the fiber length of the glass fibers is within the above range, a resin composition with good scratch resistance and gloss tends to be easily obtained.

[0115] (Surface treatment) From the viewpoint of improving the affinity between the resin component and the glass filler (B) and increasing the adhesion, thereby suppressing a decrease in transparency of the molded article due to the formation of voids, it is preferable to surface-treat the glass filler (B) with a treatment agent containing a coupling agent.

[0116] As the coupling agent, a silane coupling agent, a borane coupling agent, an aluminate coupling agent, a titanate coupling agent, or the like can be used. In particular, from the viewpoint of improving the adhesion between the polycarbonate resin (A) and the glass filler (B), it is preferable to use a silane coupling agent. As the silane coupling agent, an aminosilane coupling agent, an epoxysilane coupling agent, an acrylic silane coupling agent, or the like can be used. Among these, an acrylic silane coupling agent is most preferable.

[0117] (refractive index) The refractive index of the glass filler (B) at a wavelength of 589.3 nm is preferably 1.40 or more and 1.70 or less. When the refractive index at a wavelength of 589.3 nm is within the above range, the refractive index difference with the polycarbonate resin (A) can be set within a specific range, and the transparency of the resulting resin composition and molded article is improved. Furthermore, from the viewpoint of improving the transparency of the resin composition and molded article, the refractive index of the glass filler (B) at a wavelength of 589.3 nm is preferably 1.45 or more, more preferably 1.50 or more, and preferably 1.65 or less, more preferably 1.60 or less.

[0118] From another perspective, from the viewpoint of obtaining a transparent resin composition and molded article, when the refractive index of the glass filler (B) at a wavelength of 589.3 nm is defined as refractive index B and the refractive index of the one or more resins at a wavelength of 589.3 nm is defined as refractive index A, the absolute value of the difference between them, |refractive index A−refractive index B|, is usually 0.10 or less, preferably 0.050 or less, more preferably 0.030 or less, even more preferably 0.020 or less, still more preferably 0.010 or less, and particularly preferably 0.0050 or less.

[0119] <Glass filler (B) content> The content of the glass filler (B) is preferably 0.01 to 4.0 parts by mass, with the total amount of the one or more resins (A) being 100 parts by mass. The upper limit is preferably 3.0 parts by mass or less, more preferably 2.0 parts by mass or less, even more preferably 1.5 parts by mass or less, even more preferably 1.2 parts by mass or less, and particularly preferably 1.0 part by mass or less. The lower limit is usually 0.01 parts by mass or more, preferably 0.05 parts by mass or more, more preferably 0.10 parts by mass or more, even more preferably 0.20 parts by mass or more, and particularly preferably 0.30 parts by mass or more. If the content of the glass filler exceeds the above range, the appearance (gloss) of the resin composition may be poor.

[0120] <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.

[0121] (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 polycarbonate 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, and 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, based on 100 parts by mass of component (A) in the polycarbonate resin composition. Adding an antioxidant in an amount of 5 parts by mass or less prevents mold contamination during molding and produces molded products with excellent surface appearance, while adding an amount of 0.001 parts by mass or more produces sufficient improvement in weather resistance tests.

[0122] Phosphite antioxidants 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.

[0123] Sulfur-based antioxidants 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.

[0124] Phenolic antioxidants 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.

[0125] Examples of the hydroxybenzophenone compounds include 2,2'-dihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and 2-hydroxy-4-octoxybenzophenone.

[0126] Examples of malonic acid ester compounds include 2-(1-arylalkylidene)malonic acid esters and tetraethyl-2,2'-(1,4-phenylene-dimethylidene)-bismalonate.

[0127] 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).

[0128] 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).

[0129] Light stabilizer (D) The polycarbonate resin composition of the present invention may contain a light stabilizer (D).

[0130] Examples of light stabilizers (D) include 2,2,6,6-tetramethyl-4-piperidinol, tetrakis(2,2,6,6-tetramethyl-4-piperidyl-butane-1,2,3,4-tetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidinyl) 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, and 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 esterification product 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.

[0131] The polycarbonate resin composition of the present invention preferably contains 0.001 to 5 parts by mass of the light stabilizer (D) per 100 parts by mass of the polycarbonate resin. 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 2 parts by mass or less, still 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.

[0132] UV absorber The polycarbonate resin composition may contain an ultraviolet absorber (i.e., UVA) within the scope of the present invention. Examples of ultraviolet absorbers include 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5-methylphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, and 2,2'-p-phenylenebis(1,3-benzoxazin-4-one).

[0133] 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 polycarbonate resin, 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.

[0134] <Physical properties of resin composition> The scratch resistance of the resin composition can be evaluated, for example, by the color difference (ΔE*) described in the evaluation method detailed in the Examples below.

[0135] (Color difference (ΔE*)) The color difference (ΔE*) is a value obtained by conducting a predetermined scratch resistance test on the surface of a molded article made of a resin composition, and determining the color values ​​L*a*b* before and after the scratch resistance test. The degree of scratches on the surface of the molded product can be evaluated from this color difference (ΔE*), thereby making it possible to evaluate the scratch resistance.

[0136] ·Scratch resistance test The scratch resistance test was performed using a reciprocating scratch tester (Model: TYPE30S, manufactured by Shinto Scientific Co., Ltd.). First, canvas No. 6 was cut into a width of 15 mm, and the resulting cut pieces were attached to a measuring jig with a 30 mm flat indenter manufactured by Shinto Scientific. Next, the cut pieces attached to the measuring jig with a 30 mm flat indenter were reciprocated 100 times on the surface of a specified test piece. The reciprocating motion was performed under the conditions of a load of 1 kgf, a stroke of 50 mm, and a speed of 6000 mm / min.

[0137] The above-mentioned predetermined test pieces were prepared as follows. The polycarbonate resin composition pellets were dried using a hot air dryer at 90°C for 6 hours or more. The pellets were then fed into an injection molding machine (NADEM20000 manufactured by The Japan Steel Works, Ltd.) and injection-molded plates (100mm wide x 100mm long x 2mm thick) were molded under conditions of a resin temperature of 240°C and a mold temperature of 60°C. These injection-molded plates were used as test specimens.

[0138] ·Method of measuring color difference A spectrophotometer (Konica Minolta, model "CM-M6") was used to irradiate the surface of the test piece before and after the scratch resistance test, and the color value L in the L*a*b* color space based on ISO11664-:2019 was calculated from the color obtained at light receiving angles of -15° and +15°. * , a * and b * obtained. From the results obtained, the color difference (ΔE * ) was measured, and the degree of scratches on the surface of the test piece was evaluated from this color difference (ΔE*).

[0139] The color difference (ΔE*) of the molded article of the resin composition of the present invention is preferably 6.0 or less, more preferably 5.0 or less, even more preferably 4.0 or less, still more preferably 3.5 or less, and particularly preferably 3.0 or less. There is no particular lower limit, and it is usually 0.0 or more.

[0140] (glossiness) Using a gloss meter (VG2000 manufactured by Nippon Denshoku Co., Ltd.), the gloss of the test piece obtained for the resin composition before the scratch resistance test was measured at a measurement angle of 20 degrees, and the smoothness of the test piece surface was evaluated from this gloss.

[0141] The gloss level is usually 50 or higher, preferably 55 or higher, more preferably 60 or higher, even more preferably 65 or higher, still more preferably 70 or higher, and particularly preferably 75 or higher. There is no particular upper limit to the gloss level, but it is usually 150 or lower, preferably 140 or lower, more preferably 130 or lower, and still more preferably 120 or lower.

[0142] In the resin composition of the present invention, the content of the glass filler (B) is limited to 4.0 parts by mass or less per 100 parts by mass of the one or more resins (A) in the resin composition. If this amount is greater than 4.0 parts by mass, the gloss level may deviate from the desired range, and the gloss of the resin composition may be poor.

[0143] (shock resistance) The impact resistance of the resin composition can be evaluated by a notched Charpy impact strength test. The notched Charpy impact strength with a notch tip radius R of 0.25 mm is preferably 5 kJ / m 2 From the viewpoint of having a higher impact resistance, it is preferable that the impact strength is 10 kJ / m or more. 2 More preferably, it is equal to or greater than this. The notched Charpy impact test was carried out as follows. The resin composition pellets were dried at 90°C for 5 hours or more using a hot air dryer. The dried pellets were then molded into an ISO mold type A (ISO527-1A) using an injection molding machine (EC-75SX manufactured by Shibaura Machine Co., Ltd.). Test pieces for Charpy impact tests were prepared by cutting the molded pieces. The test pieces for the Charpy impact test obtained above were subjected to a notched Charpy impact test in accordance with ISO 179 (2000). Measurements were carried out with a notch tip radius of R0.25 mm. The higher the notched Charpy impact strength, the better the impact resistance.

[0144] (Surface hardness) The surface hardness of the resin composition according to the present invention is not particularly limited, but from the viewpoint of obtaining a resin composition that can maintain a good appearance during use, the pencil hardness is preferably HB or higher, more preferably F or higher. The pencil hardness can be measured in accordance with JIS K5600-5-4 or the like. The pencil hardness can be obtained by adjusting the type of resin, the size, shape, amount of glass filler, etc.

[0145] (Flame retardant) The present invention has excellent flame retardancy. Flame retardancy refers to the property of instantly self-extinguishing in the event of combustion due to a fire or the property of instantly self-extinguishing the combustion of dripping resin molten during combustion. A flame retardant can also be added to obtain a resin composition with particularly excellent flame retardancy. When a flame retardant is added, the type is not particularly limited, and commercially available flame retardants can be used.

[0146] (Heat resistance) The heat resistance of a resin composition can be evaluated by measuring "HDT: deflection temperature under load." The HDT value is preferably 80°C or higher, more preferably 85°C or higher, and even more preferably 90°C or higher. When the HDT value is within this range, excellent heat resistance is obtained.

[0147] The HDT (deflection temperature under load) was measured as follows. The resin composition pellets were dried at 90°C for 5 hours or more using a hot air dryer. The dried pellets were then molded into an ISO mold type A (ISO527-1A) using an injection molding machine (EC75SX manufactured by Shibaura Machine Co., Ltd.). This test piece was cut to prepare a test piece for a heat resistance test. The heat resistance test specimens obtained above were subjected to heat deflection temperature measurement in accordance with ISO 75 (2004). The test was carried out flatwise, and the temperature at which the specimen reached the specified deflection was taken as the heat deflection temperature. The load was measured at 1.80 MPa. The higher this value, the higher the heat resistance.

[0148] (Color development) The color tone (colorability) of the polycarbonate resin composition can be evaluated, for example, by a method for measuring the yellowness index YI value, which will be described in detail in the Examples below. The yellowness index YI value is preferably 7.0 or less, more preferably 5.0 or less, and even more preferably 3.0 or less. When the yellowness index YI value is within this range, excellent transparency is obtained.

[0149] The yellowness index YI value was measured as follows. The resin composition pellets were dried at 90°C for 5 hours or more using a hot air dryer. The dried pellets were then fed into an injection molding machine (J85AD manufactured by The Japan Steel Works, Ltd.) and molded under conditions of a resin temperature of 240°C, a mold temperature of 60°C, and a molding cycle of 50 seconds to obtain an injection-molded plate (100 mm wide x 100 mm long x 2 mm thick). The YI of the injection-molded plate was measured using a Konica Minolta CM-5 spectrophotometer under Illuminant C, with reference to JIS K7373 (2006).

[0150] (weather resistance) The light resistance (weather resistance) of the resin composition can be evaluated by measuring ΔYI. The ΔYI value is preferably 9.0 or less, more preferably 5.0 or less, and even more preferably 2.0 or less. When the ΔYI value is within this range, excellent light resistance is obtained.

[0151] The light resistance test was carried out as follows. Test specimens from the injection-molded plates (100 mm x 100 mm x 2 mm) were cut into 50 mm x 50 mm x 2 mm pieces. The square surfaces of the injection-molded plates were irradiated to a radiation exposure of 300 MJ / m² using a Toyo Seiki Seisaku-sho Atlas Weatherometer Ci4000. The irradiation was performed at a black panel temperature of 89°C and a relative humidity of 50%. The light source was a xenon arc lamp, with a type S borosilicate inner filter and a soda lime outer filter attached around the lamp. The irradiance was set to 100 W / m² at wavelengths of 300 to 400 nm. The color tone of the injection-molded plates before and after irradiation was measured in accordance with ASTM D1925 using a Konica Minolta CM-5 spectrophotometer. The injection-molded plates were placed in a measurement chamber, and the YI (yellowness index) value of the transmitted light was measured. The smaller the absolute value of the difference between YI after irradiation treatment and YI before treatment (ΔYI), the less coloring due to UV irradiation there is, indicating excellent light resistance.

[0152] (Transparency (total light transmittance, Haze)) The resin composition preferably has a total light transmittance of 90% or more. Being in this range provides excellent transparency. The haze value is preferably 5.0 or less, more preferably 3.0 or less. Being in this range provides excellent transparency. The total light transmittance and haze are measured as follows. The resin composition pellets were dried at 90°C for 5 hours or more using a hot air dryer. The dried pellets were then fed into an injection molding machine (J85AD manufactured by Japan Steel Works) and molded under conditions of a resin temperature of 240°C, a mold temperature of 60°C, and a molding cycle of 50 seconds to obtain an injection-molded plate (100mm wide x 100mm long x 2mm thick). The total light transmittance of the injection-molded plate was measured using a haze meter "NDH2000" manufactured by Nippon Denshoku Industries Co., Ltd., in accordance with JIS K7136 (2000). The smaller the haze value and the higher the total light transmittance, the better the transparency.

[0153] (Moldability) The fluidity (moldability) of a resin composition can be evaluated by measuring MFR or spiral flow. The MFR value is preferably 5 g / 10 min or more, more preferably 7 g / 10 min or more, and even more preferably 8 g / 10 min or more. The spiral flow value is preferably 190 mm or more, more preferably 200 mm or more, and even more preferably 210 mm or more under the following conditions: flow channel thickness 2 mm, resin temperature 240°C, injection pressure 100 MPa, mold temperature 60°C, screw rotation 50 rpm, injection speed 50 mm / s, back pressure 10 MPa, injection time 10 sec, cooling time 10 sec, suck back 2 mm, and minimum cushion volume 10 mm. Having the spiral flow value in this range ensures excellent fluidity.

[0154] The flowability evaluation (MFR measurement) was carried out as follows. Pellets of the resin composition were dried at 90°C for 5 hours or more using a hot air dryer. Next, the MFR of the dried pellets was measured using a melt indexer (manufactured by Toyo Seiki Seisakusho) at a temperature of 230°C and a load of 2.16 kg. In the case of a polycarbonate resin composition containing a polycarbonate resin containing a structural unit derived from a dihydroxy compound containing an aromatic group, the measurement was performed at a temperature of 300°C and a load of 1.2 kg. A higher value indicates higher fluidity.

[0155] Furthermore, fluidity evaluation (spiral flow measurement) was carried out as follows. Pellets of the resin composition were dried at 90°C for at least 5 hours using a hot air dryer. The dried pellets were then fed into a 75-ton injection molding machine (Shibaura Machine Co., Ltd., EC75SX) and molded using a spiral flow mold under the following conditions: channel thickness 2mm, resin temperature 240°C, injection pressure 100MPa, mold temperature 60°C, screw rotation 50rpm, injection speed 50mm / s, back pressure 10MPa, injection time 10sec, cooling time 10sec, suckback 2mm, and minimum cushion volume 10mm. The flow length (spiral flow length) of the resulting injection-molded product was measured. A larger value indicates higher fluidity.

[0156] [Method of producing resin composition] The resin composition of the present invention can be produced, for example, by mechanically melt-kneading the above-mentioned components. Examples of melt-kneading machines that can be used here include single-screw extruders, twin-screw extruders, Brabender mixers, Banbury mixers, kneader blenders, and roll mills. Among these, twin-screw extruders are preferred, and mixing is preferably performed under reduced pressure to remove residual phenol. The lower limit of the kneading temperature is usually 100°C or higher, preferably 145°C or higher, and more preferably 160°C or higher. The upper limit of the kneading temperature is usually 350°C, preferably 300°C, and more preferably 280°C. During kneading, the components may be kneaded together, or a multi-stage division kneading method may be used in which any component is kneaded first, followed by the addition of the remaining components. The extruded kneaded product is cooled and solidified with water or the like, cut into pellets using a strand cutter or the like, and is preferably dried appropriately before use.

[0157] [Molded body] The resin composition of the present invention can be processed into various molded articles by molding methods such as injection molding (insert molding, two-color molding, sandwich molding, gas injection molding, etc.), extrusion molding, inflation molding, T-die film molding, lamination molding, blow molding, hollow molding, compression molding, and calendar molding. The shape of the molded article is not particularly limited, and examples include sheets, films, plates, particles, lumps, fibers, rods, porous bodies, and foams, with sheets, films, and plates being preferred. The molded film can also be uniaxially or biaxially stretched. Examples of stretching methods include roll, tenter, and tubular methods. Furthermore, surface treatments commonly used in industry, such as corona discharge treatment, flame treatment, plasma treatment, and ozone treatment, can also be applied.

[0158] <Uses of molded products> The use of the molded article obtained by molding the resin composition of the present invention is not particularly limited, but it is particularly preferred that it be used as a part for a vehicle, an aircraft, or a ship. In particular, it is preferably used as an automobile part, and more preferably as an automobile interior part. Examples of automotive parts include headlamp lenses, turn signal lamp lenses, tail lamp lenses, plastic window glass, meter covers, outer panels, door handles, rear panels, wheel caps, visors, roof rails, sunroofs, instrument panels, panels, control cable coverings, airbag covers, mudguards, bumpers, boots, air hoses, lamp packings, gaskets, various moldings such as window moldings, sight shields, weatherstrips, glass run channels, grommets, vibration-damping and sound-proofing materials, etc.

[0159] Other uses of molded articles obtained by molding the resin composition of the present invention include coating materials for electric wires, cords, wire harnesses, etc. in the field of electric and electronic parts, insulating sheets, displays and touch panels for office automation equipment, membrane switches, photo covers, relay parts, coil bobbins, IC sockets, fuse cases, camera pressure plates, FDD collets, floppy hubs, optical disc substrates, pickup lenses for optical discs, optical lenses, LCD substrates, PDP substrates, television screens for projection televisions, retardation films, etc. in the field of optical parts. Fog lamp lenses, illuminated switch lenses, sensor switch lenses, Fresnel lenses, protective glasses, projection lenses, camera lenses, sunglasses, light guide plates, camera strobe reflectors, LED reflectors, joint materials in the building materials field, handrails, windows, table edge materials, sashes, bathtubs, window frames, signs, lighting covers, aquariums, staircase skirting, carports, highway sound insulation walls, multi-wall sheets, steel wire coating materials, lighting globes, switch breakers, protective covers for machine tools, industrial deep-drawn vacuum formed containers, pump housings, home appliances, low-voltage electrical appliances Various packings, grips, belts, rubber feet, rollers, protectors, suction cups, gaskets for refrigerators, etc., switches, connector covers, game machine covers, pachinko machines, OA housings, notebook PC housings, HDD head trays, instrument windows, transparent housings, OA gear rollers, switch case sliders, gas cock knobs, watch frames, watch gear train center pieces, amber caps, various rolls for OA equipment, tubular molded products such as hoses and tubes, irregular extrusion products, leather-like products, articulating tools, soft-touch dolls and other toys, pen grips, straps, suction cups, watches, umbrella bones, cosmetic cases, general sundries such as toothbrush handles, housewares, containers such as Tupperware, cable ties, various bottles such as blow-molded infusion bottles, food bottles, water bottles, and bottles for personal care such as cosmetics, catheters in medical parts, syringes, syringe gaskets, drip tubes, tubing, ports, caps, rubber stoppers, dialyzers, blood connectors, dentures, disposable containers, and the like, and the material can also be used for foam molding applications.

[0160] [Device] The molded article obtained by molding the resin composition of the present invention is preferably mounted on a device for transporting substances, animals, or humans. The device for transporting substances, animals, or humans is preferably a vehicle, an aircraft, or a ship, and the molded article of the present invention is preferably mounted on a vehicle, an aircraft, or a ship as a molded article (part) for use as an automobile part. [Example]

[0161] The present invention will be described in more detail below using 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 polycarbonate resin compositions, molded articles, etc. were evaluated by the following methods.

[0162] [Test specimen preparation method and various evaluations] <How to prepare test specimens> First, pellets of the polycarbonate resin composition produced in each of the following Examples and Comparative Examples were dried at 90°C for 6 hours or more using a hot air dryer. Next, the pellets were fed into an injection molding machine (NADEM20000 manufactured by The Japan Steel Works, Ltd.) and injection-molded plates (100 mm wide x 100 mm long x 2 mm thick) were molded under conditions of a resin temperature of 240°C and a mold temperature of 60°C. These injection-molded plates were used as test specimens.

[0163] <Scratch resistance test> The scratch resistance test was performed using a reciprocating scratch tester (manufactured by Shinto Scientific Co., Ltd., model: TYPE30S). First, canvas No. 6 was cut to a width of 15 mm, and the resulting cut pieces were attached to a measuring jig with a 30 mm flat indenter manufactured by Shinto Scientific. Next, the cut pieces attached to the measuring jig with a 30 mm flat indenter were reciprocated 100 times on the surface of the test piece obtained by the above (1) test piece preparation method. The reciprocating motion was performed under the conditions of a load of 1 kgf, a stroke of 50 mm, and a speed of 6000 mm / min.

[0164] <Various evaluations> (Color difference (ΔE*)) ·Method of measuring color difference A spectrophotometer (Konica Minolta, model "CM-M6") was used to irradiate the surface of the test piece before and after the scratch resistance test, and the color value L in the L*a*b* color space based on ISO11664-:2019 was calculated from the color obtained at light receiving angles of -15° and +15°. * , a * and b * obtained. From the results obtained, the color difference (ΔE * ) was measured, and the degree of scratches on the surface of the test piece was evaluated from this color difference (ΔE*). For the sake of simplicity, in this specification, the L * , a * and b * are listed as shown in Table 1 below.

[0165] [Table 1]

[0166] Generally, color difference ΔE * The value of √(ΔL *^2 +Δa *^2 +Δb *^2 In this specification, the color difference before and after the scratch resistance test at a light receiving angle of +15° and a light receiving angle of -15° is calculated, and the average value of these two values ​​is used as the color difference ΔE of the sample. * The values ​​were evaluated. For convenience, the L * , a * and b * Value difference and color difference ΔE * In this specification, the values ​​are as shown in Table 2 below. For each color at +15° and -15° angles, the L before and after the scratch resistance test * , a * and b * From the difference, the color difference ΔE * (+15°) and ΔE * (-15°) and calculate the average ΔE * It was decided.

[0167] [Table 2]

[0168] (Evaluation of color difference) The ΔE* values ​​obtained by the above method were classified and evaluated according to the criteria shown in Table 3 below.

[0169] [Table 3]

[0170] <Glossiness> Using a gloss meter (VG2000 manufactured by Nippon Denshoku Co., Ltd.), the gloss of the test piece obtained for each example resin composition before the scratch resistance test was measured at a measurement angle of 20 degrees. The smoothness of the test piece surface was evaluated from this gloss.

[0171] [Ingredients used in the manufacturing example] The compounds used in the following production examples, their abbreviations and manufacturers are as follows: Polycarbonate resin (A): A-1, A-2, A-3 <Dihydroxy compounds> ISB: Isosorbide [Rocket Fleuret] CHDM: 1,4-cyclohexanedimethanol [SK Chemical] <Carbonate diester> DPC: Diphenyl carbonate [Mitsubishi Chemical Corporation]

[0172] <Catalyst deactivator> Phosphorous acid [Taihei Chemical Industry Co., Ltd.] (molecular weight 82.0) <Heat stabilizer (antioxidant)> Irganox 1010: Pentaerythritol tetrakis[3-3,5-di-tert-butyl-4-hydroxyphenyl)propionate [BASF] AS2112: Tris(2,4-di-tert-butylphenyl)phosphite [ADEKA] (molecular weight 646.9) <Release agent> E-275: Ethylene glycol distearate [NOF Corporation]

[0173] [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.

[0174] 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.

[0175] Polycarbonate resin was extracted from the fourth horizontal stirred reactor at a rate of 60 kg / hr. The resin was then fed in its 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 its 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 using a rotary cutter to obtain a polycarbonate resin with an ISB / CHDM molar ratio of 70 / 30 mol%. This polycarbonate resin is designated "A-1" as appropriate.

[0176] 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-275 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.

[0177] [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".

[0178] [Materials used in Examples and Comparative Examples] The abbreviations for the compounds used in the following Examples and Comparative Examples are as follows: <Polycarbonate resin (A)> As the polycarbonate resin (A) containing structural units derived from isosorbide, "A-1" and "A-2" prepared in the above manufacturing example were used, and as the polycarbonate resin which is a homopolymer having bisphenol A as a monomer, "A-3" was used. The glass transition temperatures and reduced viscosities of polycarbonate resin (A-1) and polycarbonate resin (A-2) are shown below.

[0179] A-1: Polycarbonate resin of Production Example 1. Glass transition temperature: 122°C. Reduced viscosity: 0.44 dL / g. A-2: Polycarbonate resin of Production Example 2. Glass transition temperature: 100°C. Reduced viscosity: 0.61 dL / g. A-3: S-3000R (bisphenol A homopolymer, manufactured by Mitsubishi Engineering Plastics Corporation)

[0180] <Glass beads (B)> B-1: UBS-K0005EAC (Unitika Glass Beads, Material: Aluminoborosilicate glass, Silane coupling treatment: Acrylic silane, Coulter particle size (50% diameter): 3.7 μm, Refractive index at wavelength 589.3 nm: 1.56)

[0181] [Examples 1 to 4, Comparative Examples 1 and 2] Using a twin-screw extruder (TEX-30) manufactured by The Japan Steel Works, Ltd., equipped with one vent, polycarbonate resins (A-1, A-2) and glass beads (B-1) were mixed to obtain the composition shown in Table 4, and the mixture was extruded into strands so that the resin temperature at the outlet reached 250°C. The extrudate was cooled and solidified with water, and then pelletized using a rotary cutter. The vent was connected to a vacuum pump, and the pressure at the vent was controlled to 500 Pa. Polycarbonate resin compositions were produced in this manner. The evaluation results are shown in Table 4.

[0182] [Table 4]

[0183] As can be seen from Table 4, the resins according to each example were able to reduce the color difference before and after the scratch resistance test compared to the comparative examples. Note that C is a color difference that can be recognized as a different color by the naked eye, and A is a color difference that is almost indistinguishable to the human eye (the colors appear to be the same). This shows that the present invention can provide a resin composition having excellent scratch resistance.

[0184] Moreover, it is clear that Examples 1 to 4 all exhibit a sufficient gloss level of 60 or more, and have excellent appearance.

[0185] [Reference examples 1~2] Using a twin-screw extruder (TEX-0) manufactured by Japan Steel Works, Ltd., equipped with one vent port, polycarbonate resin (A-3), a homopolymer with bisphenol A as a monomer, and appropriate glass beads (B-1) were mixed in the ratios shown in Table 5 and extruded into strands so that the resin temperature at the outlet reached 270°C. The extrudate was cooled and solidified with water, and then pelletized using a rotary cutter. During this process, the vent port was connected to a vacuum pump, and the pressure at the vent port was controlled to 500 Pa. A polycarbonate resin composition was produced in this manner, and ΔE * The following evaluation was conducted.

[0186] [Table 5]

[0187] As can be seen from Table 5, even when aromatic polycarbonate was used, the scratch resistance was improved by the addition of glass beads.

[0188] As described above, the present invention can provide a resin composition that combines mechanical properties and good appearance, and is particularly excellent in scratch resistance and gloss, as well as a molded article and device using the resin composition.

Claims

1. A resin composition comprising one or more resins, the one or more resins include a polycarbonate resin (A), the resin composition further contains a glass filler (B), the content of the glass filler (B) is 0.01 parts by mass or more and 4.0 parts by mass or less, relative to 100 parts by mass of the total amount of the one or more resins.

2. The resin composition according to claim 1, wherein the polycarbonate resin (A) contains at least a structural unit (a1) derived from an aliphatic dihydroxy compound having a cyclic structure.

3. The resin composition according to claim 2, wherein the aliphatic dihydroxy compound having a cyclic structure is a dihydroxy compound represented by the following formula (1): 【Chemistry 1】

4. 4. The resin composition according to claim 3, wherein the polycarbonate resin (A) further has a structural unit derived from at least one dihydroxy compound selected from the group consisting of an ether group-containing dihydroxy compound, an aliphatic dihydroxy compound, and an alicyclic dihydroxy compound, which is different from the dihydroxy compound represented by formula (1).

5. 4. The resin composition according to claim 3, wherein the polycarbonate resin (A) contains 20 mol % or more and 95 mol % or less of structural units derived from the dihydroxy compound represented by the formula (1) relative to 100 mol % of all structural units derived from the dihydroxy compound.

6. The resin composition according to claim 1, wherein the content of the glass filler (B) relative to 100 parts by mass of the resin (A) is 0.01 parts by mass or more and less than 1 part by mass.

7. 2. The resin composition according to claim 1, wherein the glass filler (B) comprises at least one member selected from the group consisting of glass fibers and glass beads.

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

9. The molded article according to claim 8, which is a part for a vehicle, an aircraft, or a ship.

10. A device for transporting substances, animals or humans, comprising a shaped body according to claim 8.

11. 11. The device of claim 10, which is a vehicle, aircraft or watercraft.

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