Resin composition for display materials and resin parts for display materials

Abstract

To provide a resin component for a display material which contains a polycarbonate-polyorganosiloxane copolymer and achieves, at a high level, transparency, impact resistance, flowability, heat resistance and chemical resistance to an aromatic agent.SOLUTION: A resin component for a display material contains a polycarbonate-polyorganosiloxane copolymer (A) containing a polycarbonate block (A-1) and a polyorganosiloxane block (A-2), wherein the content of the polyorganosiloxane block in the resin composition is 10.0-16.0 wt.%, and the viscosity average molecular weight thereof is 14,500-19,000.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin composition for use as a display material and a resin part for use as a display material. [Background technology]

[0002] Polycarbonate, with its high transparency and excellent heat resistance, is widely used in optical components, electrical and electronic equipment, and automotive applications. Furthermore, to meet the recent expansion of application fields, development of copolymer polycarbonates, in which various copolymerizable monomer units are introduced into common monomer raw materials such as bisphenol A (hereinafter abbreviated as BPA), is underway. In particular, polycarbonate-polyorganosiloxane copolymers composed of BPA and polyorganosiloxane comonomers are known to combine high levels of transparency, heat resistance, and impact resistance, and numerous publications have documented their use (Patent Documents 1 to 9). Meanwhile, resin components for display materials require not only the above physical properties but also high fluidity and chemical resistance. In recent years, in-vehicle displays, such as car navigation systems, have become larger, requiring high fluidity to enable large-scale molding of resin components for display materials, such as large front panels and screens. Furthermore, commercially available car air fresheners are often installed in registers or dashboards above the display, and may contain components that corrode resins. Therefore, high chemical resistance to fragrances is required so that the appearance of the display material is not marred even if the display material comes into contact with the fragrance due to dripping. Generally, adding a resin modifier is effective in improving fluidity and chemical resistance, but it significantly reduces transparency and impact resistance, making it difficult to meet all the required properties. For these reasons, it has been difficult to apply copolymer polycarbonates to this application. Furthermore, since contact with sunscreens and fragrances at high temperatures is expected, even higher chemical resistance is also required. No resin display parts that meet all of these requirements have yet been offered. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent Publication No. 2021-031500 [Patent Document 2] Japanese Patent Publication No. 2020-122073 [Patent Document 3] Japanese Patent Application Laid-Open No. 2016-102219 [Patent Document 4] Japanese Patent Application Laid-Open No. 2015-137308 [Patent Document 5] Japanese Patent Application Laid-Open No. 2015-137307 [Patent Document 6] Japanese Patent Application Laid-Open No. 2015-034191 [Patent Document 7] Japanese Patent Application Laid-Open No. 2014-105276 [Patent Document 8] Japanese Patent Application Laid-Open No. 2012-246390 [Patent Document 9] Japanese Patent Application Laid-Open No. 2012-153824 Summary of the Invention [Problem to be solved by the invention]

[0004] An object of the present invention is to provide a resin composition for use as a display material, which contains a polycarbonate-polyorganosiloxane copolymer and which has a high degree of transparency, impact resistance, flowability, heat resistance, and chemical resistance to aromatic substances. [Means for solving the problem]

[0005] As a result of extensive research conducted by the present inventors to achieve this object, they discovered that the above problems can be solved by the following constitution, and arrived at the present invention.

[0006] (Configuration 1) A resin composition for display materials, comprising a polycarbonate-polyorganosiloxane copolymer (A) containing a polycarbonate block (A-1) and a polyorganosiloxane block (A-2), wherein the content of the polyorganosiloxane block in the resin composition is 10.0 to 16.0% by weight and the viscosity average molecular weight is 14,500 to 19,000.

[0007] (Configuration 2) 2. The resin composition for display materials according to claim 1, wherein the polycarbonate block (A-1) is represented by the following general formula [1]:

[0008] [ka]

[0009] [(In the above general formula [1], R 1 and R 2 each independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group; when there are multiple of each, they may be the same or different; e and f each represent an integer of 1 to 4; and W represents a single bond or at least one group selected from the group consisting of groups represented by the following general formula [2]:

[0010] [ka]

[0011] (In the above general formula [2], R 11 ,R 12 ,R 13 ,R 14 ,R 15,R 16 ,R 17 and R 18 each independently represents a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms; R 19 and R 20 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a represents a group selected from the group consisting of an aryl group having 6 to 14 atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group, and when there are a plurality of groups, they may be the same or different, g is an integer of 1 to 10, and h is an integer of 4 to 7.)

[0012] (Configuration 3) 3. The resin composition for display materials according to claim 1 or 2, wherein the polyorganosiloxane block (A-2) is represented by the following general formula [3]:

[0013] [ka]

[0014] (In the above general formula [3], R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and R 9 and R 10 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, p is a natural number, q is 0 or a natural number, and the average chain length p+q is a natural number from 30 to 100. X is a divalent aliphatic group having 2 to 8 carbon atoms.

[0015] (Configuration 4) 4. The resin composition for display materials according to configuration 3, wherein the average chain length p+q in the general formula [3] is 30 to 70. (Configuration 5) A resin composition for display materials according to the structure 3 or 4, wherein the polyorganosiloxane block represented by the general formula [3] is derived from a (2-allylphenol)-terminated polyorganosiloxane or a (2-methoxy-4-allylphenol)-terminated polyorganosiloxane. (Configuration 6) In general formula [3], R 3 , R 4 , R 5 , R 6 , R 7 and R 8 6. The resin composition for display materials according to any one of configurations 3 to 5, wherein is a methyl group.

[0016] (Configuration 7) 3. The resin composition for display materials according to claim 2, wherein the polycarbonate block represented by the general formula [1] is derived from 2,2-bis(4-hydroxyphenyl)propane. (Configuration 8) 8. The resin composition for display materials according to any one of configurations 1 to 7, wherein the viscosity average molecular weight of the resin composition is 14,500 to 18,000. (Configuration 9) 9. The resin composition for display materials according to any one of configurations 1 to 8, wherein the content of the polyorganosiloxane block in the resin composition is 11.0 to 15.0% by weight. (Configuration 10) The resin composition for display materials according to any one of Aspects 1 to 9, wherein an ISO dumbbell tensile test piece having a width of 10 mm, a length of 80 mm, a total length of 150 mm, and a thickness of 4 mm obtained by injection molding using the resin composition is heat-treated at 100°C for 90 minutes, and then fixed to a three-point bending jig. An arbitrary strain is applied to the center of the molded piece, and the applied strain is covered with a small piece of bleached paper. 0.5 mL of an aromatic agent is applied, and the piece is then kept in a constant temperature bath kept at 60°C for 10 minutes. In this chemical resistance test, the limit value of strain at which cracks of 3 mm or more do not occur in the chemically exposed part is 0.3% or more.

[0017] (Configuration 11) 11. The resin composition for display materials according to any one of configurations 1 to 10, wherein a molded piece having a thickness of 2 mm obtained by injection molding the resin composition has a haze value of 2.0 or less. (Configuration 12) 12. The resin composition for display materials according to any one of Aspects 1 to 11, wherein a molded piece having a thickness of 2 mm obtained by injection molding using the resin composition has a maximum impact energy of 15 J or more in a high-speed surface impact test measured in accordance with ISO 6603, and the fracture mode is ductile fracture. (Configuration 13) 13. The resin composition for display materials according to any one of Aspects 1 to 12, wherein the resin composition is melt-kneaded to obtain pellets, which are then dried with hot air at 100°C for 5 hours. The pellets are then measured in accordance with ISO 11443 (JIS K 7199) using a capillary rheometer (Capillograph 1D, manufactured by Toyo Seiki Seisaku-sho, Ltd.) with a capillary model EF (diameter: 1.0 mm, length: 10.0 mm, L / D: 10), manufactured by Toyo Seiki Seisaku-sho, Ltd., at a furnace temperature of 300°C and a shear rate of 1220 sec-1.

[0018] (Configuration 14) 14. The resin composition for display materials according to any one of configurations 1 to 13, wherein the resin composition has a deflection temperature under load of 100° C. or higher as measured in accordance with ISO178. (Configuration 15) A resin part for a display material obtained by molding the resin composition for a display material according to any one of Configurations 1 to 14. (Configuration 16) 16. A resin part for display materials according to configuration 15, which is mounted on an automobile. [Effects of the Invention]

[0019] The resin composition for display materials of the present invention has excellent transparency, impact resistance, fluidity, heat resistance, and chemical resistance to aromatic substances, and therefore has exceptional industrial effects. [Brief explanation of the drawings]

[0020] [Figure 1] FIG. 1 is a diagram of a three-point bending chemical resistance evaluation jig. DETAILED DESCRIPTION OF THE INVENTION

[0021] The present invention will be described in more detail below.

[0022] The resin composition for display materials of the present invention contains a polycarbonate-polyorganosiloxane copolymer (A) containing a polycarbonate block (A-1) and a polyorganosiloxane block (A-2), wherein the content of the polyorganosiloxane block in the resin composition is 10.0 to 16.0% by weight and the viscosity average molecular weight is 14,500 to 19,000.

[0023] <<Polycarbonate-polyorganosiloxane copolymer (A)>> In the present invention, polycarbonate-polyorganosiloxane copolymer (hereinafter referred to as PC-P The copolymer (A) (sometimes abbreviated as OS copolymer) comprises a polycarbonate block (A-1) and a polyorganosiloxane block (A-2), and preferably the polycarbonate block (A-1) is represented by the following formula [1], and the polyorganosiloxane block (A-2) is represented by the following formula [3].

[0024] <Polycarbonate block (A-1)> In the present invention, the polycarbonate block (A-1) is a polycarbonate-based portion contained in the PC-POS copolymer, and the type thereof is not particularly limited. For example, such a polycarbonate-based portion may be an aromatic polycarbonate-based portion. For example, the polycarbonate block (A-1) is represented by the following formula [1].

[0025] [ka]

[0026] In the above formula [1], R 1 and R 2 R each independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. 1 and R 2 When there are a plurality of each of the above, they may be the same or different.

[0027] Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

[0028] Examples of the alkyl group having 1 to 18 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, and a tetradecyl group. An alkyl group having 1 to 6 carbon atoms is preferred.

[0029] Examples of the alkoxy group having 1 to 18 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a hexoxy group, an octoxy group, etc. An alkoxy group having 1 to 6 carbon atoms is preferred.

[0030] Examples of the cycloalkyl group having 6 to 20 carbon atoms include a cyclohexyl group, a cyclooctyl group, etc. A cycloalkyl group having 6 to 12 carbon atoms is preferred.

[0031] Preferred examples of the cycloalkoxy group having 6 to 20 carbon atoms include a cyclohexyloxy group, a cyclooctyloxy group, etc. A cycloalkyl group having 6 to 12 carbon atoms is preferred.

[0032] Examples of the alkenyl group having 2 to 10 carbon atoms include a methenyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, etc. An alkyl group having 1 to 6 carbon atoms is preferred.

[0033] Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group, a naphthyl group, etc. Examples of the aryloxy group having 6 to 14 carbon atoms include a phenyloxy group, a naphthyloxy group, etc.

[0034] Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group, a phenylethyl group, etc. Examples of the aralkyloxy group having 7 to 20 carbon atoms include a benzyloxy group, a phenylethyloxy group, etc.

[0035] e and f each independently represent an integer of 1 to 4.

[0036] W is a single bond or at least one group selected from the group consisting of groups represented by the following formula [2]:

[0037] [ka]

[0038] In the above formula [2], R 11, R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 each independently represents a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms.

[0039] Examples of the alkyl group having 1 to 18 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and a dodecyl group. An alkyl group having 1 to 6 carbon atoms is preferred.

[0040] Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group and a naphthyl group. These may be substituted. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group.

[0041] Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group and a phenylethyl group.

[0042] R 19 and R 20 each independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. When there are multiple groups, they may be the same or different.

[0043] Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

[0044] Examples of the alkyl group having 1 to 18 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, and a tetradecyl group. An alkyl group having 1 to 6 carbon atoms is preferred.

[0045] Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, etc. An alkyl group having 1 to 6 carbon atoms is preferred.

[0046] Examples of the cycloalkyl group having 6 to 20 carbon atoms include a cyclohexyl group, a cyclooctyl group, etc. A cycloalkyl group having 6 to 12 carbon atoms is preferred.

[0047] Examples of the cycloalkoxy group having 6 to 20 carbon atoms include a cyclohexyloxy group, a cyclooctyl group, etc. A cycloalkyl group having 6 to 12 carbon atoms is preferred.

[0048] Examples of the alkenyl group having 2 to 10 carbon atoms include a methenyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, etc. An alkyl group having 1 to 6 carbon atoms is preferred.

[0049] Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group and a naphthyl group.

[0050] Examples of the aryloxy group having 6 to 14 carbon atoms include a phenyloxy group and a naphthyloxy group.

[0051] Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group and a phenylethyl group.

[0052] Examples of the aralkyloxy group having 7 to 20 carbon atoms include a benzyloxy group and a phenylethyloxy group.

[0053] g is an integer of 1 to 10, preferably an integer of 1 to 6. h is an integer of 4 to 7, preferably an integer of 4 to 5.

[0054] The polycarbonate block represented by the above formula [1] is selected from the group consisting of 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-allyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4-biphenol, 4,4'-sulfonyldiphenol, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 9,9-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane ... Preferred are 2,2-bis(4-hydroxyphenyl)fluorene, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene, etc., more preferred are 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane (BPZ), 4,4-biphenol, 4,4'-sulfonyldiphenol, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, and particularly preferred are blocks derived from 2,2-bis(4-hydroxyphenyl)propane.

[0055] The length of the polycarbonate block (A-1) is preferably 10 to 100, more preferably 30 to 100, and even more preferably 50 to 70, in terms of the average number of repeating units of the formula [1].

[0056] The content of the polycarbonate block (A-1), particularly the content of the polycarbonate block represented by formula [1], is preferably 84.0 to 90.0% by weight, more preferably 85.0 to 89.0% by weight, and even more preferably 85.0 to 88.0% by weight, based on the total weight of the copolymer.

[0057] <Polyorganosiloxane block (A-2)> In the present invention, the polyorganosiloxane block (A-2) is a polyorganosiloxane-based portion contained in the PC-POS copolymer, and the type thereof is not particularly limited. For example, the polyorganosiloxane block is represented by the following formula [3]:

[0058] [ka]

[0059] In the above formula [3], R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms.

[0060] Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, etc. Preferred are alkyl groups having 1 to 6 carbon atoms.

[0061] Examples of the substituted or unsubstituted aryl group having 6 to 12 carbon atoms include a phenyl group, a naphthyl group, etc. Examples of the substituent include an alkyl group having 1 to 12 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.

[0062] R 3 , R 4 , R 5 , R 6 , R 7 , R 8 is preferably a phenyl group, a propyl group, an ethyl group, or a methyl group, and more preferably a methyl group.

[0063] R 9 and R 10 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.

[0064] Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

[0065] Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, etc. Preferred are alkyl groups having 1 to 6 carbon atoms.

[0066] Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a hexoxy group, a heptoxy group, an octoxy group, etc. An alkoxy group having 1 to 6 carbon atoms is preferred.

[0067] R 9 and R 10 is preferably a hydrogen atom, a methoxy group, or an ethoxy group, more preferably a hydrogen atom or a methoxy group, and even more preferably a hydrogen atom.

[0068] p is a natural number, preferably 20 to 100, more preferably 30 to 90, and even more preferably 35 to 70.

[0069] q is 0 or a natural number, preferably 0 to 80, and more preferably 0 to 50.

[0070] The average chain length p+q is 30 to 100, preferably 30 to 90, and more preferably 30 to 70. Within the above range, sufficient impact resistance and chemical resistance are obtained, and further, the appearance (color unevenness, peeling failure) is improved.

[0071] X is a divalent aliphatic group having 2 to 8 carbon atoms. Examples of the divalent aliphatic group include alkylene groups having 2 to 8 carbon atoms. Examples of the alkylene group include an ethylene group, a trimethylene group, and a tetramethylene group, with a trimethylene group being preferred.

[0072] The polyorganosiloxane block represented by the above formula [3] is preferably a block derived from an alkenylphenol-terminated polyorganosiloxane, more preferably a block derived from an allylphenol-terminated polyorganosiloxane, and even more preferably a block derived from a (2-allylphenol)-terminated polyorganosiloxane or a (2-methoxy-4-allylphenol)-terminated polyorganosiloxane. That is, in formula [3], X is a trimethylene group and R 9 and R 10 is a hydrogen atom, or X is a trimethylene group and R 9 and R 10 is preferably a methoxy group.

[0073] The content of the polyorganosiloxane block in the PC-POS copolymer (A) used in the present invention is preferably 10.0 to 16.0 wt %, more preferably 11.0 to 15.0 wt %, and even more preferably 12.0 to 15.0 wt %, based on the total weight of the PC-POS copolymer. Within the above ranges, sufficient impact resistance, heat resistance, and chemical resistance are obtained, and the appearance (color unevenness, peeling failure) is also improved.

[0074] The viscosity-average molecular weight of the PC-POS copolymer (A) used in the present invention is preferably 14,500 to 19,000, more preferably 14,500 to 18,000, and even more preferably 14,500 to 17,000. Within the above ranges, sufficient mechanical strength and flowability for practical use can be obtained. Furthermore, since molding at high temperatures is not required, problems caused by heat, such as thermal degradation of the resin, are reduced. Furthermore, the separation ability in the water washing step is high, allowing high productivity to be achieved.

[0075] <<Resin composition for display materials>> The resin composition for display materials of the present invention contains a polycarbonate-polyorganosiloxane copolymer (A) containing a polycarbonate block (A-1) and a polyorganosiloxane block (A-2).

[0076] The content of the polyorganosiloxane block in the resin composition for display materials of the present invention is preferably 10.0 to 16.0 wt %, more preferably 11.0 to 15.0 wt %, and even more preferably 12.0 to 15.0 wt %, based on the total weight of the resin composition. Within the above ranges, sufficient impact resistance, heat resistance, and chemical resistance are obtained, and further, the appearance (color unevenness, peeling failure) is improved.

[0077] The viscosity average molecular weight of the resin composition for display materials of the present invention is preferably 14,500 to 19,000, more preferably 14,500 to 18,000, and even more preferably 14,500 to 17,000. Within the above range, sufficient impact resistance, chemical resistance, and fluidity can be obtained. Within the above range, sufficient impact resistance, chemical resistance, and fluidity can be obtained.

[0078] <Raw materials for polycarbonate-polyorganosiloxane copolymer (A)> (Dihydroxy Compound Component of Polycarbonate Block (A-1)) The dihydroxy compound serving as the raw material for the polycarbonate block (A-1) may be derived mainly from a dihydric phenol (I) represented by the following general formula [4].

[0079] [ka]

[0080] (In the formula, R 1 , R 2 , e, f and W are the same as in formula [1] above.)

[0081] Examples of the dihydric phenol include 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxy-3,3'-biphenyl)propane, 2,2-bis(4-hydroxy- 2,2-bis(3-isopropylphenyl)propane, 2,2-bis(3-t-butyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, 2,2-bis(3-bromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl) 1,1-bis(4-hydroxyphenyl)methane, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 2,2'-dimethyl -4,4'-Sulfonyldiphenol, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 2,2'-diphenyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfide, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,Examples include 4-bis(4-hydroxyphenyl)cyclohexane, 1,3-bis(4-hydroxyphenyl)cyclohexane, 4,8-bis(4-hydroxyphenyl)tricyclo[5.2.1.02,6]decane, 4,4'-(1,3-adamantanediyl)diphenol, and 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane.

[0082] Among them, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1 Preferred are 1,3-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-sulfonyldiphenol, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, and 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene, with 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane (BPZ), 4,4'-sulfonyldiphenol, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene being particularly preferred. Among these, 2,2-bis(4-hydroxyphenyl)propane is the most suitable due to its excellent strength and durability. These may be used alone or in combination.

[0083] (Dihydroxy Compound Component of Polyorganosiloxane Block (A-2)) The dihydroxy compound used as the raw material for the polyorganosiloxane block (A-2) is a polyorganosiloxane having a specific average chain length. Specifically, a raw material represented by the following general formula [5], hydroxyaryl-terminated polyorganosiloxane (II), is used.

[0084] [ka]

[0085] (In the formula, R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , p, q and X are the same as those in the general formula [3] above.)

[0086] In the general formula [5], the average chain length p+q is preferably 30 to 100, more preferably 30 to 90, and even more preferably 30 to 70. If it is less than 30, sufficient impact resistance is not achieved, and if it is greater than the upper limit, the appearance deteriorates (color unevenness, poor peeling). To satisfy this specific chain length range, two or more different hydroxyaryl-terminated polyorganosiloxane (II) raw materials having average chain lengths p+q may be mixed to prepare the polyorganosiloxane. In this case, polyorganosiloxane (B-1) having an average chain length p+q of 1 or more but less than 60 and polyorganosiloxane (B-2) having an average chain length p+q of 60 or more but less than 200 are used as raw materials. The polyorganosiloxane raw material can be prepared by mixing appropriate hydroxyaryl-terminated polyorganosiloxane raw materials together, or by premixing polyorganosiloxane precursors having an appropriate average chain length before the end is hydroxyaryl-modified, and then modifying the end with hydroxyaryl. The average chain length (p + q) of the polyorganosiloxane blocks in the PC-POS copolymer obtained by reacting the polyorganosiloxane raw material with a dihydric phenol and a polycarbonate precursor is, as described above, preferably 30 to 100, more preferably 30 to 90, and even more preferably 30 to 70. The average chain length (p + q) is calculated by nuclear magnetic resonance (NMR) measurement.

[0087] When the polyorganosiloxane (B-1) and the polyorganosiloxane (B-2) are mixed, the weight ratio of (B-1):(B-2) is preferably 1:99 to 99:1, and more preferably 10:90 to 90:10.

[0088] As the polyorganosiloxane raw material, the above polyorganosiloxane (B-1) and (B- It is more preferable to use a polyorganosiloxane (C) obtained by previously blending (B-1):(B-2), and the blending ratio is preferably 1:99 to 99:1 by weight, more preferably 10:90 to 90:10, similar to the weight ratio of (B-1):(B-2) described above.

[0089] When blended in advance, the lower limit of the average chain length p + q of the polyorganosiloxane (B-1) is preferably 1 or more, more preferably 20 or more, and even more preferably 30 or more, and the upper limit is preferably less than 60, more preferably less than 50, and even more preferably less than 45. The lower limit of the average chain length p + q of the polyorganosiloxane (B-2) is preferably 60 or more, more preferably 70 or more, and even more preferably 90 or more, and the upper limit is preferably 200 or less, more preferably 100 or less. As the hydroxyaryl-terminated polyorganosiloxane (II) represented by the general formula [5], for example, the following compounds are preferably used.

[0090] [ka]

[0091] The hydroxyaryl-terminated polyorganosiloxane (II) is a phenol having an olefinic unsaturated carbon-carbon bond, and is preferably vinylphenol, 2-allylphenol, isopropenylphenol, or 2-methoxy-4-allylphenol, and is easily produced by subjecting the end of a polyorganosiloxane chain having a predetermined degree of polymerization to a hydrosilylation reaction. Among these, (2-allylphenol)-terminated polyorganosiloxane and (2-methoxy-4-allylphenol)-terminated polyorganosiloxane are preferred, and (2-allylphenol)-terminated polydimethylsiloxane and (2-methoxy-4-allylphenol)-terminated polydimethylsiloxane are particularly preferred.

[0092] <Method for producing polycarbonate-polyorganosiloxane copolymer> The polycarbonate-polyorganosiloxane copolymer of the present invention can be produced by the following steps.

[0093] (PC-POS copolymer manufacturing process) The process is a process of reacting a dihydric phenol (I) represented by the above formula [4] with phosgene in a mixed solution of a water-insoluble organic solvent and an alkaline aqueous solution to prepare a solution containing a carbonate oligomer having a terminal chloroformate group.

[0094] As described above, the method for producing the PC-POS copolymer used in the present invention uses a polyorganosiloxane having a specific average chain length as a raw material, and the hydroxyaryl-terminated polyorganosiloxane (II) may be one type or two or more types. Specifically, a raw material represented by the hydroxyaryl-terminated polyorganosiloxane (II) represented by the general formula [5] and having an average chain length p + q of 30 to 100 is used. In addition, two or more different types of hydroxyaryl-terminated polyorganosiloxane (II) raw materials having an average chain length p + q may be mixed and used to satisfy such a specific chain length range. In this case, it can be prepared using a polyorganosiloxane (B-1) having an average chain length p + q of 1 or more and less than 60 and a polyorganosiloxane (B-2) having an average chain length p + q of 60 or more and 200 or less as raw materials, or it can be prepared by pre-mixing polyorganosiloxane precursors having an appropriate average chain length before the terminals are hydroxyaryl-modified, and then using a raw material obtained by modifying the terminals with hydroxyaryl. Furthermore, before reacting with the carbonate precursor and the dihydric phenol, the polyorganosiloxane (B-1) and the polyorganosiloxane (B-2) can be pre-blended, or they can be added to the reaction solution in parallel without being pre-blended, or (B-1) and (B-2) can be divided and added sequentially to the reaction solution to react with the carbonate precursor and the dihydric phenol. More preferably, the polyorganosiloxane (B-1) is added to the reaction solution, and then the polyorganosiloxane (B-2) is added to the reaction solution to react with the carbonate precursor and dihydric phenol. This is desirable from the viewpoint of efficiency and cost effectiveness due to simplified manufacturing process equipment. The weight ratio of the polyorganosiloxanes (B-1) and (B-2) used as raw materials is as described above, and the carbonate precursor and dihydric phenol will be described later.

[0095] In the interfacial polycondensation method for obtaining the PC-POS copolymer used in the present invention, the amount of the water-insoluble organic solvent per mole of the total amount of the dihydric phenols represented by the general formulas [4] and [5] is preferably 8 moles or more and less than 16 moles.

[0096] Here, the total amount of dihydric phenols means the total amount of bisphenols and polyorganosiloxane monomers, which are raw materials for polycarbonate.

[0097] The amount of the insoluble organic solvent is the total amount used up to the point at which the catalyst is added and the polycondensation reaction is started, and is the total amount of the amount used in producing the polycarbonate oligomer, the amount used to dissolve the polyorganosiloxane monomer and the terminal terminator, and the amount added to adjust the emulsified state during the interfacial polycondensation reaction.

[0098] In the interfacial polycondensation method for obtaining the PC-POS copolymer used in the present invention, if the amount of water-insoluble organic solvent per mole of the total amount of dihydric phenols represented by general formulas [4] and [5] is less than the lower limit, the polymer quality will deteriorate due to poor emulsion during polymerization, and productivity will decrease due to excessively high solution viscosity. If the amount exceeds the upper limit, the poor emulsion state makes it difficult to introduce polyorganosiloxane blocks into the copolymer, resulting in poor appearance. Furthermore, a water-insoluble organic solvent may be added immediately after the reaction between the carbonate precursor, dihydric phenol, and polyorganosiloxane proceeds. Specifically, when the proportion of unreacted polyorganosiloxane in the reaction solution reaches 10% or less of the polyorganosiloxane used, it is desirable to add at least 2 moles of water-insoluble organic solvent per mole of the total amount of dihydric phenols represented by general formulas [4] and [5]. This ensures sufficient reaction progress while also reducing the risk of precipitation of polymer components due to high concentration.

[0099] In addition, other comonomers than the dihydric phenol (I) and hydroxyaryl-terminated polyorganosiloxane (II) can be used in combination in an amount of up to 10% by weight based on the total weight of the copolymer, provided that this does not interfere with the production method of the present invention.

[0100] In the production method of the present invention, a mixed solution containing an oligomer having a terminal chloroformate group is prepared in advance by reacting a dihydric phenol (I) with a carbonate ester-forming compound in a mixed solution of a water-insoluble organic solvent and an alkaline aqueous solution.

[0101] In producing an oligomer of the dihydric phenol (I), the entire amount of the dihydric phenol (I) used in the method of the present invention may be converted into an oligomer at once, or a part of the oligomer may be added as a post-added monomer as a reaction raw material to the interfacial polycondensation reaction in the subsequent stage. The post-added monomer is added to rapidly proceed with the polycondensation reaction in the subsequent stage, and there is no need to add it if it is not necessary.

[0102] The method for this oligomer formation reaction is not particularly limited, but it is usually preferable to carry out the reaction in a solvent in the presence of an acid binder.

[0103] The proportion of the carbonate ester-forming compound used may be adjusted appropriately in consideration of the stoichiometric ratio (equivalents) of the reaction. When a gaseous carbonate ester-forming compound such as phosgene is used, it is preferable to blow it into the reaction system.

[0104] Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures of these.

[0105] The proportion of the acid binder used may be determined appropriately in consideration of the stoichiometric ratio (equivalents) of the reaction, as described above. Specifically, it is preferable to use 2 equivalents or a slight excess of the acid binder relative to the number of moles of the dihydric phenol (I) used to form the oligomer (usually 1 mole corresponds to 2 equivalents).

[0106] The solvent may be any of various inert solvents used in the production of known polycarbonates, either singly or in combination. Typical examples include hydrocarbon solvents such as xylene, and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. Halogenated hydrocarbon solvents such as methylene chloride are particularly preferred.

[0107] The reaction pressure for oligomer formation is not particularly limited and may be normal, elevated, or reduced pressure, but it is usually advantageous to carry out the reaction under normal pressure. The reaction temperature is selected from the range of -20 to 50°C, and since heat is often generated during polymerization, water or ice cooling is desirable. The reaction time depends on other conditions and cannot be specified in general, but is usually 0.2 to 10 hours.

[0108] The pH range of the oligomer formation reaction is the same as that of known interfacial reactions, and the pH is always adjusted to 10 or higher.

[0109] In the present invention, after obtaining a mixed solution containing an oligomer of a dihydric phenol (I) having terminal chloroformate groups, the hydroxyaryl-terminated polyorganosiloxane (II) is added to the dihydric phenol (I) while stirring the mixed solution, and the hydroxyaryl-terminated polyorganosiloxane (II) and the oligomer are subjected to interfacial polycondensation to obtain a polycarbonate-polyorganosiloxane copolymer.

[0110] When carrying out the interfacial polycondensation reaction, an acid binder may be added appropriately taking into account the stoichiometric ratio (equivalent) of the reaction. Examples of acid binders include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof. Specifically, when the hydroxyaryl-terminated polyorganosiloxane (II) used or a portion of the dihydric phenol (I) as described above is added as a post-added monomer to this reaction stage, it is preferable to use 2 equivalents or more of alkali relative to the total moles of the post-added dihydric phenol (I) and hydroxyaryl-terminated polyorganosiloxane (II) (usually 1 mole corresponds to 2 equivalents).

[0111] The polycondensation by interfacial polycondensation reaction between the oligomer of the dihydric phenol (I) and the hydroxyaryl-terminated polyorganosiloxane (II) is carried out by vigorously stirring the above mixture.

[0112] In such polymerization reactions, a terminal terminator or a molecular weight modifier is usually used. Examples of terminal terminators include compounds having a monovalent phenolic hydroxyl group, such as ordinary phenol, p-tert-butylphenol, p-cumylphenol, tribromophenol, etc., as well as long-chain alkylphenols, aliphatic carboxylic acid chlorides, aliphatic carboxylic acids, hydroxybenzoic acid alkyl esters, hydroxyphenyl alkyl acid esters, and alkyl ether phenols. The amount used is in the range of 100 to 0.5 mol, preferably 50 to 2 mol, per 100 mol of the total dihydric phenol compounds used, and it is of course possible to use two or more compounds in combination.

[0113] To accelerate the polycondensation reaction, a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt may be added.

[0114] The reaction time for this polymerization reaction must be relatively long to reduce unreacted polyorganosiloxane blocks. It is preferably 30 minutes or more, more preferably 50 minutes or more. On the other hand, since prolonged stirring of the reaction solution can cause polymer precipitation, it is preferably 180 minutes or less, more preferably 90 minutes or less.

[0115] If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfide may be added.

[0116] The polycarbonate resin composition used in the present invention can be made into a branched polycarbonate by using a branching agent in combination with the above-mentioned dihydric phenol compound. Examples of trifunctional or higher polyfunctional aromatic compounds used in such branched polycarbonate resins include phloroglucin, phloroglucside, 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-2,2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 4-[4-[1,1-bis(4- Examples of the 4-hydroxyphenyl ether include trisphenols such as {4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and acid chlorides thereof. Among these, 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred.

[0117] The reaction pressure can be reduced, normal, or increased, but is usually preferably normal pressure or the inherent pressure of the reaction system. The reaction temperature is selected from the range of -20 to 50°C, and in many cases, water or ice cooling is desirable because heat is generated during polymerization. The reaction time cannot be generally determined because it varies depending on other conditions such as the reaction temperature, but is usually 0.5 to 10 hours.

[0118] In some cases, the obtained polycarbonate copolymer may be subjected to a suitable physical treatment (mixing, fractionation, etc.) and / or chemical treatment (polymer reaction, crosslinking treatment, partial decomposition treatment, etc.) to obtain a desired reduced viscosity [η SP It can also be obtained as a polycarbonate copolymer of [(2-hydroxybenzoyl)-2-methylbenzoyl)-1,2-diol / c].

[0119] The resulting reaction product (crude product) can be subjected to various post-treatments such as known separation and purification methods, and recovered as a polycarbonate-polyorganosiloxane copolymer of the desired purity (degree of purification).

[0120] Furthermore, the polycarbonate-polyorganosiloxane copolymer used in the present invention can be blended with various flame retardants, reinforcing fillers, and additives that are usually blended with polycarbonate resins, as long as the effects of the present invention are not impaired.

[0121] The polycarbonate-polyorganosiloxane copolymer of the present invention can be pelletized by melt-kneading using an extruder such as a single-screw extruder or a twin-screw extruder.

[0122] Furthermore, the resin composition of the present invention may further contain other thermoplastic resins (e.g., polyarylate resins, fluororesins, polyester resins, etc.), antioxidants (e.g., hindered phenol compounds, etc.), impact modifiers, ultraviolet absorbers, light stabilizers, mold release agents, lubricants, colorants, inorganic fillers (talc, mica, wollastonite, kaolin, etc.), etc., within the scope of the present invention.

[0123] The resin parts for display materials of the present invention can be manufactured into various products by injection molding the pellets produced as described above. Furthermore, it is also possible to directly manufacture sheets, films, profile extrusion molded products, direct blow molded products, and injection molded products from the resin melt-kneaded in an extruder without going through the pelletizing process.

[0124] Injection molding can be used to obtain resin parts for display materials using not only conventional molding methods but also injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including injection of supercritical fluids), insert molding, in-mold coating molding, heat-insulating mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultra-high-speed injection molding, depending on the purpose. The advantages of these various molding methods are already widely known. Furthermore, molding can be performed using either a cold runner system or a hot runner system.

[0125] The resin parts for display materials of the present invention may be used in the form of various profile extrusion molded products, sheets, films, etc. by extrusion molding. Sheets and films can also be molded using methods such as inflation, calendaring, and casting. Furthermore, by subjecting the resin parts to a specific stretching operation, they can also be molded into heat-shrinkable tubing. The resin parts for display materials of the present invention can also be obtained by rotational molding, blow molding, etc.

[0126] Furthermore, in the present invention, molded articles made of polycarbonate-polyorganosiloxane copolymers can be subjected to various surface treatments. Surface treatments here refer to the formation of a new layer on the surface of a resin molded article, such as vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot-dip plating, etc.), painting, coating, and printing, and methods commonly used for polycarbonate resins can be applied. Specific examples of surface treatments include hard coating, water-repellent and oil-repellent coating, ultraviolet-absorbing coating, infrared-absorbing coating, and metallizing (vapor deposition, etc.).

[0127] The resin component for display materials of the present invention is preferably a resin component for display materials mounted on an automobile.

[0128] <<Characteristic values of the resin composition for display materials containing a PC-POS copolymer>> (Transparency) For the resin composition used in the present invention, the haze value of a molded piece with a thickness of 2 mm obtained by injection molding is preferably 2.0 or less, more preferably 1.5 or less, and even more preferably 1.0 or less. If the transparency is within the above range, the visibility and decorativeness of the display will be high, so it can be applied to resin components for display materials.

[0129] (Impact resistance) For the resin composition used in the present invention, the maximum impact energy in the high-speed surface impact test measured in accordance with ISO6603 of a molded piece with a thickness of 2 mm obtained by injection molding is preferably 15 J or more, more preferably 17 J or more, and the fracture mode is ductile fracture. If the impact resistance is within the above range, it is difficult to be damaged by the impact of dropping, so it can be applied to resin components for display materials.

[0130] (Fluidity) For the resin composition used in the present invention, the pellets obtained by melt kneading are dried by hot air at 100 °C for 5 hours, and then in accordance with ISO11443 (JIS K 7199), using a capillary rheometer (Capilograph 1D manufactured by Toyo Seiki Seisakusho Co., Ltd.), and as the capillary, Capillary type EF (diameter: 1.0 mm, length: 10.0 mm, L / D: 10) manufactured by Toyo Seiki Seisakusho Co., Ltd. is used. At a furnace temperature of 300 °C and a shear rate of 1220 sec-1, the shear viscosity value is preferably 280 Pa·S or less, more preferably 250 Pa·S or less, even more preferably 200 Pa·S or less, and particularly preferably 160 Pa·S or less. If the fluidity is within the above range, it is possible to mold thin-walled parts, so it can be applied to resin components for display materials.

[0131] (Heat resistance) The resin composition used in the present invention preferably has a deflection temperature under load measured in accordance with ISO 178 of 100° C. or higher, more preferably 102° C. or higher, and even more preferably 104° C. or higher. If the heat resistance is within the above range, the composition can be used in high-temperature environments and is therefore applicable to resin parts for display materials.

[0132] (chemical resistance) The resin composition used in the present invention is an ISO dumbbell-shaped tensile test piece obtained by injection molding and having a width of 10 mm, a length of 80 mm, a total length of 150 mm, and a thickness of 4 mm, which is heat-treated at 100°C for 90 minutes, then fixed to a three-point bending jig, and a chemical resistance test is conducted in which an arbitrary strain is applied to the center of the molded piece, the applied area is covered with a small piece of bleached paper, 0.5 mL of an aromatic agent is applied, and the piece is kept in a constant temperature bath kept at 60°C for 10 minutes.In this test, the limit of strain at which cracks of 3 mm or more do not occur in the chemically exposed area is preferably 0.3% or more, more preferably 0.4% or more, and even more preferably 0.5% or more.

[0133] In the chemical resistance test, arbitrary strains are applied in 0.1% increments: 0.1%, 0.2%, 0.3%. For example, if no cracks of 3 mm or larger are present at 0.3% strain and cracks of 3 mm or larger are present at 0.4% strain, the limit value for strain at which no cracks of 3 mm or larger are present is 0.3%. Within the above range, the material can be used in applications where contact with aromatics is anticipated, and therefore can be applied to resin parts for display materials. Examples of air fresheners include Clear Forest for Car Air Conditioner Louvers (manufactured by S.T. Corporation) and Febreze Car Premium Clip Woody Concerto (manufactured by P&G). [Example]

[0134] The present invention will be described in more detail below with reference to examples, but these examples are not intended to limit the scope of the present invention. Unless otherwise specified, parts in the examples are parts by weight and % is % by weight. Evaluations were made according to the following methods.

[0135] (1) Viscosity average molecular weight (Mv) The specific viscosity (ηSP) calculated by the following formula was determined using an Ostwald viscometer from a solution of 0.7 g of polycarbonate pellet resin dissolved in 100 ml of methylene chloride at 20°C. Specific viscosity (ηSP)=(t-t0) / t0 [t0 is the number of seconds that methylene chloride falls, and t is the number of seconds that the sample solution falls] The viscosity average molecular weight Mv is calculated from the determined specific viscosity (ηSP) using the following formula. ηSP / c=[η]+0.45×[η] 2 c (where [η] is the intrinsic viscosity) [η]=1.23×10 -4 Mv 0.83 c=0.7

[0136] (2) Polyorganosiloxane block content and average polyorganosiloxane repeat number (p + q) The H-NMR spectrum of the polycarbonate-polyorganosiloxane copolymer was measured using a JEOL NMR JNM-AL400, and the average chain length p + q was calculated by comparing the integral ratio of the peak derived from the dihydric phenol (I) with the integral ratio of the peak derived from the hydroxyaryl-terminated polyorganosiloxane (II). Similarly, the average chain length p + q was calculated by comparing the integral ratio of the peak derived from the hydroxyaryl-terminated peak with the integral ratio of the peak derived from the polyorganosiloxane.

[0137] (3) Transparency evaluation (haze measurement) The resulting pellets were dried with hot air at 100°C for 5 hours and then injection molded (Japan Steel Works, Ltd., JSW J-75EIII) to produce a three-layer plate at a molding temperature of 290°C, a mold temperature of 80°C, and a molding cycle of 40 seconds. The haze of the 2.0 mm-thick portion of the three-layer plate was measured in accordance with ISO 17482n using a haze meter NDH-2000 manufactured by Nippon Denshoku Industries Co., Ltd.

[0138] (4) Impact resistance evaluation (high-speed surface impact test) The resulting pellets were dried with hot air at 100°C for 5 hours and then injection molded (Japan Steel Works, Ltd., JSW J-75EIII) to produce a three-stage plate at a molding temperature of 290°C, a mold temperature of 80°C, and a molding cycle of 40 seconds. The fracture morphology and maximum impact energy were evaluated in accordance with ISO 6603 for a 2.0 mm thick specimen.

[0139] (5) Fluidity evaluation (shear viscosity measurement) The pellets obtained were dried with hot air at 100°C for 5 hours, and then subjected to shear rate measurement at a furnace temperature of 300°C and a shear rate of 1220 sec-1 in accordance with ISO11443 (JIS K 7199) using a capillary rheometer (Capillograph 1D manufactured by Toyo Seiki Seisaku-sho Co., Ltd.) and a capillary model EF manufactured by Toyo Seiki Seisaku-sho Co., Ltd. (diameter: 1.0 mm, length: 10.0 mm, L / D: 10). -1 The shear viscosity was measured.

[0140] (6) Heat resistance evaluation (deflection temperature under load measurement) The pellets were dried with hot air at 100°C for 5 hours and then injection molded (Japan Steel Works, Ltd., JSW J-75EIII) to prepare test specimens measuring 80 mm in length, 10 mm in width, and 4 mm in thickness at a molding temperature of 290°C, a mold temperature of 80°C, and a molding cycle of 40 seconds. The deflection temperature under load was measured at a load of 1.80 MPa in accordance with ISO 178.

[0141] (7) Chemical resistance evaluation (three-point bending test) The resulting pellets were dried with hot air at 100°C for 5 hours and then molded into ISO dumbbell-shaped tensile test specimens (Type A) measuring 10 mm in width at the center, 80 mm in length, 150 mm in total length, and 4 mm in thickness using an injection molding machine (Japan Steel Works, Ltd., JSW J-75EIII) at a molding temperature of 290°C, a mold temperature of 80°C, and a molding cycle of 50 seconds. The resulting molded specimens were heat-treated at 100°C for 90 minutes, then fixed to the three-point bending jig shown in Figure 1, and an arbitrary strain was applied to the center of the molded specimen. The applied area was covered with a small piece of bleached paper, 0.5 mL of fragrance was applied, and the specimens were then kept in a constant temperature bath maintained at 60°C for 10 minutes. The appearance of the exposed area of ​​the molded specimen was observed, and the limiting strain at which cracks of 3 mm or more did not appear was determined. The arbitrary strain is applied in 0.1% increments, i.e., 0.1%, 0.2%, and 0.3%. For example, if no cracks of 3 mm or larger are present when 0.3% strain is applied, and cracks of 3 mm or larger are present when 0.4% strain is applied, the limit value of strain at which no cracks of 3 mm or larger are present is 0.3%.

[0142] (Air freshener: Clear Forest for car air conditioner louvers [manufactured by S.T. Corporation]) [Both-end phenol-modified polyorganosiloxane] In the examples and comparative examples, a polyorganosiloxane compound having the following structure was used as the dihydric phenol (II) having a polyorganosiloxane structure. (II): p + q = 37 (KF-2201 manufactured by Shin-Etsu Chemical Co., Ltd.) The average repeating number p+q of the dimethylsiloxane unit was evaluated by 1H-NMR measurement.

[0143] [Production of polycarbonate-polyorganosiloxane copolymer] (PC-POS-1 manufacturing method) A reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 17,890 parts of ion-exchanged water and 7,003 parts of a 25% aqueous sodium hydroxide solution, and 3,812 parts of 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) as the dihydric phenol (I) represented by the general formula [4] and 7.5 parts of hydrosulfite were dissolved therein. Then, 14,310 parts of methylene chloride was added, and 1,900 parts of phosgene was blown in over 70 minutes at 22 to 30°C with stirring. 7150 parts of methylene chloride was added, and a solution of 1347 parts of 25% aqueous sodium hydroxide and 149 parts of p-tert-butylphenol dissolved in 850 parts of methylene chloride was added. While stirring, a solution of 428 parts of the above KF-2201 (as dihydric phenol (II) represented by the general formula [5]) dissolved in 800 parts of methylene chloride (0.55 molar equivalents relative to the total amount of dihydric phenol) was added at a rate of 0.0008 molar equivalents / min relative to the dihydric phenol (I) to emulsify, and then vigorously stirred again. With stirring, 4.3 parts of triethylamine was added when the reaction solution was at 26 ° C., and the reaction was continued by stirring at a temperature of 26 to 31 ° C. for 1 hour to complete the reaction. After the reaction was complete, the organic phase was separated, diluted with methylene chloride, washed with water, and then acidified with hydrochloric acid and washed again. When the conductivity of the aqueous phase reached nearly the same level as that of ion-exchanged water, the mixture was placed in a kneader filled with warm water and the methylene chloride was evaporated while stirring to obtain a polycarbonate-polyorganosiloxane copolymer powder. After dehydration, the mixture was dried at 100°C for 12 hours in a hot air circulating dryer. The resulting polycarbonate-polyorganosiloxane copolymer had a viscosity-average molecular weight of 16,000 and a polyorganosiloxane block content of 8.4 wt%.

[0144] (PC-POS-2 manufacturing method) The same production method as for PC-POS-1 was used, except that the amount of p-tert-butylphenol was changed to 109 parts. The viscosity average molecular weight of the obtained polycarbonate-polyorganosiloxane copolymer was 20,000, and the polyorganosiloxane block content was 8.4 wt%.

[0145] (PC-POS-3 manufacturing method) The production method was the same as for PC-POS-1, except that the amount of 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) was changed to 3796 parts, the amount of p-tert-butylphenol to 149 parts, and the amount of KF-2201 to 648 parts. The viscosity average molecular weight of the resulting polycarbonate-polyorganosiloxane copolymer was 15,500, and the polyorganosiloxane block content was 12.0 wt%.

[0146] (PC-POS-4 manufacturing method) The production method was the same as for PC-POS-1, except that the amount of 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) was changed to 3796 parts, the amount of p-tert-butylphenol to 121 parts, and the amount of KF-2201 to 648 parts. The viscosity average molecular weight of the resulting polycarbonate-polyorganosiloxane copolymer was 18,000, and the polyorganosiloxane block content was 12.0 wt%.

[0147] (PC-POS-5 manufacturing method) The production method was the same as for PC-POS-1, except that the amount of 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) was changed to 3786 parts, the amount of p-tert-butylphenol to 149 parts, and the amount of KF-2201 to 776 parts. The viscosity average molecular weight of the resulting polycarbonate-polyorganosiloxane copolymer was 15,500, and the polyorganosiloxane block content was 14.0 wt%.

[0148] (PC-POS-6 manufacturing method) The production method was the same as for PC-POS-1, except that the amount of 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) was changed to 3786 parts, the amount of p-tert-butylphenol to 121 parts, and the amount of KF-2201 to 776 parts. The viscosity average molecular weight of the resulting polycarbonate-polyorganosiloxane copolymer was 18,000, and the polyorganosiloxane block content was 14.0 wt%.

[0149] (PC-POS-7 manufacturing method) The production method was the same as for PC-POS-1, except that the amount of 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) was changed to 3774 parts, the amount of p-tert-butylphenol to 149 parts, and the amount of KF-2201 to 945 parts. The viscosity average molecular weight of the resulting polycarbonate-polyorganosiloxane copolymer was 15,500, and the polyorganosiloxane block content was 17.0 wt%.

[0150] (PC-POS-8 manufacturing method) The production method was the same as for PC-POS-1, except that the amount of 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) was changed to 3774 parts, the amount of p-tert-butylphenol to 121 parts, and the amount of KF-2201 to 945 parts. The viscosity average molecular weight of the resulting polycarbonate-polyorganosiloxane copolymer was 18,000, and the polyorganosiloxane block content was 17.0 wt%.

[0151] (PC-1) Linear aromatic polycarbonate resin powder with a solution viscosity of 17,000 and a molecular weight of 17,000, which has a repeating skeleton of 2,2-bis(4-hydroxyphenyl)propane (Panlite, manufactured by Teijin Limited) .

[0152] (Stabilizer-1) Irganox 1076 (BASF) (Stabilizer-2) Hostanox P-EPQ (OG Corporation) (UV absorber) Tinuvin 234 (BASF Ltd.) (mold release agent) Roxiol VPG861 (BASF Ltd.) (rust inhibitor) Marproof G-0250SP (NOF Corporation)

[0153] [Production of polycarbonate resin composition containing PC-POS copolymer] [Examples 1 to 5 and Comparative Examples 1 to 5] The PC-POS, PC, stabilizer, UV absorber, mold release agent, and rust inhibitor obtained in the above Production Example were blended in the proportions shown in the table. The blend was then melt-kneaded and pelletized using a vented twin-screw extruder (Technovel Corporation, KZW15-25MG) at a discharge rate of 2.5 kg / h, a screw rotation speed of 200 rpm, and an extrusion temperature of 270°C from the first feed port to the die. The resulting pellets were then dried with hot air at 100°C for 5 hours and molded into various evaluation specimens using an injection molding machine (The Japan Steel Works, Ltd., JSW J-75EIII). The polyorganosiloxane block content, viscosity-average molecular weight Mv, haze, maximum impact energy and fracture behavior in high-speed surface impact tests, shear viscosity, deflection temperature under load, and critical strain in three-point bending tests were evaluated. The evaluation results are shown in Table 1.

[0154] [Table 1]

[0155] It has been found that by using the resin composition of the present invention, it is possible to achieve a high level of transparency, impact resistance, fluidity, and heat resistance, while also exhibiting high chemical resistance to aromatics that are expected to come into contact with resin parts for display materials. [Industrial Applicability]

[0156] The resin composition for display materials of the present invention has excellent transparency, impact resistance, fluidity, heat resistance, and chemical resistance to aromatic substances, and is therefore highly practical as a resin part for display materials. [Explanation of symbols]

[0157] 1 y: Deflection (mm) 2 h: Test piece thickness (4 mm) 3 L: Measurement width (150mm)

Claims

1. A resin composition for display materials, which is a front panel or a screen, comprising a polycarbonate-polyorganosiloxane copolymer (A) containing a polycarbonate block (A-1) and a polyorganosiloxane block (A-2), wherein the polycarbonate block (A-1) is represented by the following general formula [1], the polyorganosiloxane block (A-2) is represented by the following general formula [3], the content of the polyorganosiloxane block in the resin composition is 10.0 to 16.0 wt %, the viscosity average molecular weight is 14,500 to 18,000, and a molded piece having a thickness of 2 mm obtained by injection molding using the resin composition has a haze value of 1.0 or less. 【Chemistry 1】 (In the above general formula [1], R １ and R ２ each independently represents a group selected from the group consisting of a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group; when there are a plurality of each, they may be the same or different; e and f each represent an integer of 0 to 4; and W is a single bond or at least one group selected from the group consisting of groups represented by the following general formula [2]: 【Chemistry 2】 (In the above general formula [2], R １１ , R １２ , R １３ , R １４ , R １５ , R １６ , R １７ and R １８ each independently represents a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms; R １９ and R ２０ each independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group; when there are a plurality of groups, they may be the same or different; g is an integer from 1 to 10, and h is an integer from 4 to 7. 【Transformation 3】 (In the above general formula [3], R ３ , R ４ , R ５ , R ６ , R ７ and R ８ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and R ９ and R １０ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, p is a natural number, q is 0 or a natural number, and the average chain length p+q is a natural number of 30 to less than 70, and X is a divalent aliphatic group having 2 to 8 carbon atoms.

2. The polyorganosiloxane block represented by the general formula [3] is derived from a (2-allylphenol)-terminated polyorganosiloxane or a (2-methoxy-4-allylphenol)-terminated polyorganosiloxane. A resin composition for display materials, which is a front panel or a screen, according to claim 1.

3. In general formula [3], R ３ , R ４ , R ５ , R ６ , R ７ and R ８ 3. The resin composition for a display material, which is a front panel or a screen, according to claim 1 or 2, wherein is a methyl group.

4. 2. The resin composition for a display material, which is a front panel or a screen, according to claim 1, wherein the polycarbonate block represented by the general formula [1] is derived from 2,2-bis(4-hydroxyphenyl)propane.

5. The resin composition for display materials, which is a front panel or a screen, according to any one of claims 1 to 4, wherein the content of the polyorganosiloxane block in the resin composition is 11.0 to 15.0 wt%.

6. 6. The resin composition for display materials, which is a front panel or a screen, according to any one of claims 1 to 5, wherein a chemical resistance test is conducted in which an ISO dumbbell-shaped tensile test piece, obtained by injection molding using the resin composition and having a width of 10 mm, a length of 80 mm, a total length of 150 mm, and a thickness of 4 mm, is heat-treated at 100°C for 90 minutes, and then fixed to a three-point bending jig. An arbitrary strain is applied to the center of the molded piece, the applied strain is covered with a small piece of bleached paper, 0.5 mL of an aromatic agent is applied, and the piece is kept in a constant temperature bath kept at 60°C for 10 minutes. The limit value of strain at which cracks of 3 mm or more do not occur in the chemically exposed portion is 0.3% or more.

7. The resin composition for display materials, which is a front panel or a screen according to any one of claims 1 to 6, wherein a molded piece having a thickness of 2 mm obtained by injection molding using the resin composition has a maximum impact energy of 15 J or more in a high-speed surface impact test measured in accordance with ISO 6603, and the fracture mode is ductile fracture.

8. The resin composition for a display material, which is a front panel or a screen, according to any one of claims 1 to 7, wherein the resin composition is melt-kneaded to obtain pellets, which are then dried with hot air at 100°C for 5 hours, and the pellets have a shear viscosity of 280 Pa S or less at a furnace temperature of 300°C and a shear rate of 1220 sec-1, as measured in accordance with ISO 11443 (JIS K 7199) using a capillary rheometer (Capillograph 1D, manufactured by Toyo Seiki Seisaku-sho, Ltd.) and a capillary model EF (diameter: 1.0 mm, length: 10.0 mm, L / D: 10), manufactured by Toyo Seiki Seisaku-sho, Ltd.

9. The resin composition for display materials, which is a front panel or a screen, according to any one of claims 1 to 8, wherein the resin composition has a deflection temperature under load of 100°C or higher as measured in accordance with ISO 178.

10. A resin part for a display material, which is a front panel or a screen, obtained by molding the resin composition for a display material, which is a front panel or a screen, according to any one of claims 1 to 9.

11. A resin part for a display material, which is the front panel or screen according to claim 10, mounted on an automobile.

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