Polycarbonate resin composition, molded article, projector for XR, and film for XR

Abstract

A polycarbonate resin composition containing 16-63% by mass of a repeating unit (a) represented by formula (1) and 37-84% by mass of a repeating unit (d) represented by formula (6), the polycarbonate resin composition having a viscosity average molecular weight of 15000 or more, and having a viscosity average molecular weight of 15000 or more. (In formula (1), R1 and R2 each independently represent a hydrogen atom or a methyl group) (in formula (6), R15-R18 each independently represent a hydrogen atom, a C1-10 alkyl group, or a C6-12 group including an aryl group, and W represents at least one selected from the group consisting of a single bond, an oxygen atom, a sulfur atom, a sulfinyl group, a sulfonyl group, and a divalent organic group).

Description

Technical Field

[0001] This invention relates to a polycarbonate resin composition with high refractive index, excellent transparency, and superior strength, and to molded articles using the polycarbonate resin composition. The invention also relates to a projector for XR with high refractive index, excellent transparency, and superior strength, and to a film for XR. Background Technology

[0002] Polycarbonate resin is used as a molding material for optics due to its excellent transparency, dimensional stability, and mechanical properties.

[0003] Patent Document 1 discloses a high-refractive-index, low-birefractive-index polycarbonate resin comprising repeating units having 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (abbreviated: BPEF). In an embodiment of Patent Document 1, a polycarbonate resin comprising only repeating BPEF units is specifically shown.

[0004] Patent Document 2 discloses a polycarbonate resin composition containing polycarbonate resin (A) and polycarbonate resin (B) as an environmentally resistant, low birefringence polycarbonate resin composition. The polycarbonate resin (A) comprises repeating units having 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (abbreviation: BPEF), and the polycarbonate resin (B) comprises repeating units having 2,2-bis(4-hydroxyphenyl)propane (abbreviation: BPA). In the embodiments of Patent Document 2, polycarbonate resin compositions specifically showing polycarbonate resin (A) containing only BPEF repeating units and polycarbonate resin (B) containing only BPA repeating units are specifically shown.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2007-57916

[0008] Patent Document 2: International Publication No. 2010 / 010703 Summary of the Invention

[0009] The problem that the invention aims to solve

[0010] The viscosity-average molecular weight of the polycarbonate resin disclosed in Patent Document 1, which only contains BPEF repeating units, cannot be increased, and its refractive index and strength are insufficient.

[0011] The polycarbonate resin (A) containing only BPEF repeating units and the polycarbonate resin (B) containing only BPA repeating units disclosed in Patent Document 2 have poor compatibility. As shown in Comparative Example 1 described later, their blends have poor transparency, flexural strength and impact resistance due to poor compatibility.

[0012] The problem of the present invention is to provide a polycarbonate resin composition with high refractive index, transparency and excellent strength, and a molded article using the polycarbonate resin composition.

[0013] Another problem with the present invention is to provide a projector for XR with high refractive index, excellent transparency and strength, and a film for XR.

[0014] Solution for solving the problem

[0015] The inventors discovered that a polycarbonate resin composition having a specific amount of specific repeating units and a viscosity-average molecular weight of a specific value or higher, particularly a polycarbonate resin composition each comprising a specific amount of a polycarbonate copolymer containing specific repeating units and a specific polycarbonate resin, and a molded body using the polycarbonate resin composition having a high refractive index, excellent transparency, and excellent strength, thereby completing the present invention.

[0016] The inventors also discovered that XR projectors and XR films using polycarbonate resin compositions having specific repeating units and a viscosity-average molecular weight of a specific value or higher have high refractive index, excellent transparency, and excellent strength, thus completing the present invention.

[0017] The main idea of ​​this invention is as follows [1] to

[19] .

[0018] [1] A polycarbonate resin composition comprising 16 to 63% by mass of repeating unit (a) of formula (1) below and 37 to 84% by mass of repeating unit (d) of formula (6) below, wherein the polycarbonate resin composition has a viscosity-average molecular weight of 15,000 or more.

[0019] [Chemical Formula 1]

[0020]

[0021] (In equation (1), R) 1 and R 2 Each can be used independently to represent a hydrogen atom or a methyl group.

[0022] [Chemical Formula 2]

[0023]

[0024] (In equation (6), R) 15 ~R 18 Each of the following is independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a group containing an aryl group having 6 to 12 carbon atoms. W represents at least one selected from single bonds, oxygen atoms, sulfur atoms, sulfinyl groups, sulfonyl groups, and divalent organic groups.

[0025] [2] A polycarbonate resin composition comprising 30-70% by weight of a polycarbonate copolymer (A) and 70-30% by weight of a polycarbonate resin (B), wherein,

[0026] The polycarbonate copolymer (A) contains repeating units (a) as shown in formula (1) and repeating units (b) as shown in formula (2) in a ratio of repeating unit (a): repeating unit (b) = (50-85% by mass): (50-15% by mass).

[0027] The polycarbonate resin (B) contains more than 95% by mass of the repeating unit (c) shown in the following formula (3).

[0028] The content of the repeating unit (a) shown in the following formula (1) is 16 to 63% by mass, and the viscosity-average molecular weight of the polycarbonate resin composition is 15,000 or more.

[0029] [Chemical Formula 3]

[0030]

[0031] (In equation (1), R) 1 and R 2 Each can be used independently to represent a hydrogen atom or a methyl group.

[0032] [Chemical Formula 4]

[0033]

[0034] (In equation (2), R) 3 and R 4 Each can be used independently to represent a hydrogen atom or a methyl group.

[0035] [Chemical Formula 5]

[0036]

[0037] (In equation (3), R) 5 and R 6 Each can be used independently to represent a hydrogen atom or a methyl group.

[0038] [3] The polycarbonate resin composition according to [1] or [2], wherein the unnotched Charpy impact strength of the polycarbonate resin composition, as determined according to ISO 179, is NB.

[0039] [4] The polycarbonate resin composition according to any one of [1] to [3], wherein the refractive index nD of the polycarbonate resin composition is 1.595 or higher.

[0040] [5] The polycarbonate resin composition according to [1], [3] or [4] is a polycarbonate resin composition containing two or more polycarbonate resins in different proportions of repeating unit (a) shown in formula (1), which can be read from above through the membrane in the following membrane transparency test.

[0041] <Membrane Transparency Test>

[0042] Approximately 4g of resin sample, vacuum dried at 100℃ for 2 hours, was used with spacers 8cm wide, 8cm long, and 1.0mm thick. The sample was preheated for 2 minutes at a hot pressing temperature of 230℃ and then pressurized for 1 minute at a pressure of 20MPa. The sample was then removed along with the spacers and cooled at room temperature to produce a 900μm thick membrane.

[0043] The film made using this method is laid on paper with printed text, and it is confirmed whether the text printed on the paper can be read from above through the film.

[0044] [6] The polycarbonate resin composition according to any one of [2] to [4], wherein, in the following film transparency test, text can be read from above through the film.

[0045] <Membrane Transparency Test>

[0046] Approximately 4g of resin sample, vacuum dried at 100℃ for 2 hours, was used with spacers 8cm wide, 8cm long, and 1.0mm thick. The sample was preheated for 2 minutes at a hot pressing temperature of 230℃ and then pressurized for 1 minute at a pressure of 20MPa. The sample was then removed along with the spacers and cooled at room temperature to produce a 900μm thick membrane.

[0047] The film made using this method is laid on paper with printed text, and it is confirmed whether the text printed on the paper can be read from above through the film.

[0048] [7] A polycarbonate resin composition according to any one of [1] to [6], wherein, in formula (1), R 1 and R 2 It is a hydrogen atom.

[0049] [8] A polycarbonate resin composition according to any one of [1], [3] to [5] and [7], wherein, in the formula (6), W is -CR 19 R 20 -(R) 19 and R 20 Each of the following is independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms, or a cycloalkane group having 3 to 10 carbon atoms.

[0050] [9] A polycarbonate resin composition according to any one of [2] to [4], [6] and [7], wherein, in formula (2), R 3 and R 4 It is a hydrogen atom.

[0051]

[10] A polycarbonate resin composition according to any one of [2] to [4], [6], [7] and [9], wherein, in formula (3), R 5 and R 6 It is a hydrogen atom.

[0052]

[11] The polycarbonate resin composition according to any one of [1] to

[10] , wherein the viscosity-average molecular weight is 26,000 or less.

[0053]

[12] The polycarbonate resin composition according to any one of [1] to

[11] , wherein the polycarbonate resin composition comprises 16 to 53% by mass of the repeating unit (a) shown in formula (1).

[0054]

[13] The polycarbonate resin composition according to

[12] , wherein the polycarbonate resin composition comprises 18 to 47% by mass of the repeating unit (a) shown in formula (1).

[0055]

[14] A molded body made using a polycarbonate resin composition according to any one of [1] to

[13] .

[0056]

[15] An XR projector is made of a polycarbonate resin composition comprising repeating unit (a) as shown in formula (1) and having a viscosity-average molecular weight of 15,000 or more.

[0057] [Chemical Formula 6]

[0058]

[0059] (In equation (1), R) 1 and R 2 Each can be used independently to represent a hydrogen atom or a methyl group.

[0060]

[16] The XR projector according to

[15] , wherein the polycarbonate resin composition is the polycarbonate resin composition according to any one of [1] to

[13] .

[0061]

[17] An XR membrane is made using a polycarbonate resin composition comprising repeating unit (a) as shown in formula (1) and having a viscosity-average molecular weight of 15,000 or more.

[0062] [Chemical Formula 7]

[0063]

[0064] (In equation (1), R) 1 and R 2 Each can be used independently to represent a hydrogen atom or a methyl group.

[0065]

[18] The XR membrane according to

[17] , wherein the polycarbonate resin composition comprises 16 to 63% by mass of the repeating unit (a) shown in formula (1).

[0066]

[19] The XR membrane according to

[17] , wherein the polycarbonate resin composition comprises more than 63% by mass and less than 100% by mass of the repeating unit (a) shown in formula (1).

[0067] Invention Effects

[0068] According to the present invention, a polycarbonate resin composition with high refractive index, excellent transparency and strength can be provided, as well as a molded article using the polycarbonate resin composition.

[0069] According to the present invention, XR projectors and XR films with high refractive index, excellent transparency and strength can also be provided. Detailed Implementation

[0070] The present invention will now be described in detail with reference to embodiments and examples. However, the present invention is not to be construed as being limited to the embodiments and examples shown below.

[0071] In this specification, unless otherwise specified, “~” is used to mean the lower limit and upper limit values, including the values ​​listed before and after it.

[0072] [Polycarbonate resin composition]

[0073] The polycarbonate resin composition of the first embodiment of the present invention (hereinafter, sometimes referred to as "polycarbonate resin composition I") is a polycarbonate resin composition comprising 16 to 63% by mass of the repeating unit (a) shown in the following formula (1), 37 to 84% by mass of the repeating unit (d) shown in the following formula (6), and a viscosity-average molecular weight of 15,000 or more.

[0074] [Chemical Formula 8]

[0075]

[0076] (In equation (1), R) 1 and R 2 Each can be used independently to represent a hydrogen atom or a methyl group.

[0077] [Chemical Formula 9]

[0078]

[0079] (In equation (6), R) 15 ~R 18 Each of the following is independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a group containing an aryl group having 6 to 12 carbon atoms. W represents at least one selected from single bonds, oxygen atoms, sulfur atoms, sulfinyl groups, sulfonyl groups, and divalent organic groups.

[0080] The polycarbonate resin composition of the second embodiment of the present invention (hereinafter, sometimes referred to as "polycarbonate resin composition II") comprises 30 to 70% by mass of a polycarbonate copolymer (A) and 70 to 30% by mass of a polycarbonate resin (B), wherein the polycarbonate copolymer (A) comprises repeating unit (a) shown in formula (1) and repeating unit (b) shown in formula (2) in a ratio of repeating unit (a): repeating unit (b) = (50 to 85% by mass): (50 to 15% by mass), the polycarbonate resin (B) comprises 95% by mass or more of repeating unit (c) shown in formula (3) shown below, the content of repeating unit (a) shown in formula (1) is 16 to 63% by mass, and the viscosity-average molecular weight of the polycarbonate resin composition is 15,000 or more.

[0081] [Chemical Formula 10]

[0082]

[0083] (In equation (1), R) 1 and R 2 Each can be used independently to represent a hydrogen atom or a methyl group.

[0084] [Chemical Formula 11]

[0085]

[0086] (In equation (2), R) 3 and R 4 Each can be used independently to represent a hydrogen atom or a methyl group.

[0087] [Chemical Formula 12]

[0088]

[0089] (In equation (3), R) 5 and R 6 Each can be used independently to represent a hydrogen atom or a methyl group.

[0090] Hereinafter, the polycarbonate resin composition I of the first embodiment and the polycarbonate resin composition II of the second embodiment will be collectively referred to as "the polycarbonate resin compositions of the present invention".

[0091] In this invention, polycarbonate homopolymers consisting of only one repeating unit and polycarbonate copolymers containing two or more repeating units are collectively referred to as "polycarbonate resins".

[0092] The polycarbonate resin composition I may contain only a polycarbonate copolymer containing repeating units (a) shown in formula (1) and repeating units (d) shown in formula (6) above, or it may contain a polycarbonate resin containing repeating units (a) shown in formula (1) above and a polycarbonate resin containing repeating units (d) shown in formula (6) above. In the case where the polycarbonate resin composition I contains only a polycarbonate copolymer containing repeating units (a) shown in formula (1) above and repeating units shown in formula (6) above, the polycarbonate resin composition I may also be referred to as "polycarbonate resin", but in this invention, the term "polycarbonate resin composition" is used in conjunction with such polycarbonate resins.

[0093] From the viewpoint of balancing transparency, refractive index, and strength, the polycarbonate resin composition II, which comprises a polycarbonate copolymer (A) and a polycarbonate resin (B), as described below, is preferred as the polycarbonate resin composition of the present invention.

[0094] It should be noted that the content ratio of repeating unit (a), repeating unit (d), and other repeating units described later in the polycarbonate resin composition I of this invention is a mass ratio of 100% by mass of polycarbonate resin composition I. The content ratio of each repeating unit in polycarbonate resin composition I can be determined according to... 1 The H-NMR value can also be calculated based on the amount of dihydroxy compound added during the manufacturing of the polycarbonate resin in the polycarbonate resin composition.

[0095] Similarly, in the polycarbonate resin composition II of the present invention, the content ratio of repeating units (a), (b), and other repeating units (described later) in the polycarbonate copolymer (A) is based on a mass ratio of 100% by mass of the polycarbonate copolymer (A). Furthermore, the content ratio of repeating units (c) in the polycarbonate copolymer (B) and other repeating units (described later) is based on a mass ratio of 100% by mass of the polycarbonate copolymer (B). The content ratio of these repeating units can be determined according to... 1 The H-NMR values ​​can also be calculated based on the amount of dihydroxy compounds added during the manufacturing of polycarbonate copolymer (A) and polycarbonate copolymer (B).

[0096] [Repeating unit of polycarbonate resin]

[0097] First, the repeating units constituting polycarbonate resin contained in the polycarbonate resin composition of the present invention will be described below.

[0098] <Repeating Unit (a)>

[0099] In equation (1) representing the repeating unit (a), R 1 and R 2 Each can be independently a hydrogen atom or a methyl group. From the viewpoint of availability, R is preferred. 1 and R 2 It is a hydrogen atom.

[0100] The repeating unit (a) can be introduced into the polycarbonate resin composition by using a dihydroxy compound (hereinafter, sometimes referred to as "dihydroxy compound (1A)") as a polycarbonate resin raw material.

[0101] [Chemical Formula 13]

[0102]

[0103] (In formula (1A), R) 1 and R 2 Each can be used independently to represent a hydrogen atom or a methyl group.

[0104] As dihydroxy compounds (1A), examples include 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (abbreviation: BPEF) and 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)fluorene. R is preferred. 1 and R 2 Both of these are 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (BPEF) with hydrogen atoms.

[0105] Dihydroxy compound (1A) can be used alone or in combination with two or more.

[0106] <Repeating Unit (d)>

[0107] In equation (6) representing the repeating unit (d), R 15 ~R 18 Each of the following is independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a group containing an aryl group having 6 to 12 carbon atoms. W represents at least one selected from single bonds, oxygen atoms, sulfur atoms, sulfinyl groups, sulfonyl groups, and divalent organic groups.

[0108] As R 15 ~R 18 Specific examples of alkyl groups having 1 to 10 carbon atoms can be listed as follows:

[0109] Methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl;

[0110] Methyl ethyl, methyl propyl, methyl butyl, methyl pentyl, methyl hexyl, methyl heptyl, methyl octyl, methyl nonyl;

[0111] Dimethylethyl, dimethylpropyl, dimethylbutyl, dimethylpentyl, dimethylhexyl, dimethylheptyl, dimethyloctyl;

[0112] Trimethylpropyl, trimethylbutyl, trimethylpentyl, trimethylhexyl, trimethylheptyl;

[0113] Ethylbutyl, ethylpentyl, ethylhexyl, ethylheptyl, ethyloctyl;

[0114] Cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, tetramethylcyclohexyl, ethylcyclohexyl, diethylcyclohexyl, methylethylcyclohexyl, etc.

[0115] As R 15 ~R 18 Specific examples of aryl groups containing 6 to 12 carbon atoms include phenyl, tolyl, and naphthyl.

[0116] R 15 ~R 18 In these, it is preferable that each is independently a hydrogen atom or a methyl group, more preferably R. 15 ~R 18 It consists entirely of hydrogen atoms.

[0117] In the formula (6), W represents at least one selected from single bonds, oxygen atoms, sulfur atoms, sulfinyl groups, sulfonyl groups, and divalent organic groups.

[0118] As a divalent organic group of W, there are no particular restrictions as long as it is a previously known group, and it can be appropriately selected and used. Specific examples of divalent organic groups of W can be listed as the organic groups shown in the following formulas (6a) to (6f).

[0119] [Chemical Formula 14]

[0120]

[0121] In the above formula (6a), R 19 and R 20 Each can independently represent a hydrogen atom, a monovalent hydrocarbon group with 1 to 24 carbon atoms, or an alkoxy group with 1 to 24 carbon atoms. Regarding R... 19 and R 20 In particular, a monovalent hydrocarbon group with 1 to 24 carbon atoms is preferred.

[0122] Examples of monovalent hydrocarbon groups having 1 to 24 carbon atoms include: alkyl groups having 1 to 24 carbon atoms, alkenyl groups having 2 to 24 carbon atoms, aryl groups having 6 to 24 carbon atoms optionally having substituents, and aralkyl groups having 7 to 24 carbon atoms.

[0123] Examples of alkyl groups having 1 to 24 carbon atoms include straight-chain alkyl groups, branched alkyl groups, and alkyl groups having a partially cyclic structure, with straight-chain alkyl groups being preferred. Examples of such alkyl groups having 1 to 24 carbon atoms include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl.

[0124] Examples of alkenyl groups with 2 to 24 carbon atoms include: straight-chain alkenyl groups, branched alkenyl groups, and alkenyl groups with partially cyclic structures, with straight-chain alkenyl groups being preferred. Examples of such alkenyl groups with 2 to 24 carbon atoms include: vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, and octenyl.

[0125] Examples of aryl groups with 6 to 24 carbon atoms include phenyl, naphthyl, methylphenyl, dimethylphenyl, trimethylphenyl, and other aryl groups that optionally have alkyl or other substituents.

[0126] Aryl groups, such as benzyl groups, can be listed as aralkyl groups with 7 to 24 carbon atoms.

[0127] Examples of alkoxy groups with 1 to 24 carbon atoms include linear, branched, and partially cyclic alkoxy groups, with linear alkoxy groups being preferred. Specific examples include methoxy, ethoxy, propoxy, and butoxy groups.

[0128] In the above formula (6b), X 1 Represents oxygen atom or NR a Here, R a With the above R 19 and R 20 The definitions are the same.

[0129] In the above formula (6c), X 2 This indicates a divalent hydrocarbon group with 3 to 18 carbon atoms. Regarding X... 2 Examples of substituents include: propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, and dodecylene, each optionally further having substituents. Examples of substituents include: methyl, ethyl, propyl, butyl, pentyl, and phenyl. 2 It can also have a partially cross-linked structure.

[0130] In the above equation (6f), the two X's 3Each alkylene group, having 1 to 7 carbon atoms, is independently represented. This alkylene group can be straight-chain, branched, or have a cyclic structure. As X 3 Examples of such compounds include methylene, ethylene, propylene, and butylene. Furthermore, m represents an integer from 1 to 500. Preferably, m is from 5 to 300, and more preferably from 10 to 100.

[0131] In formula (6) above, W is preferably a single bond or a group represented by formula (6a), i.e., -CR. 19 R 20 - or the annular skeleton shown in formula (6c). In formula (6a), R 19 and R 20 Preferably, each is independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms. In formula (6c), X 2 Preferably, it has 5 or 11 carbon atoms, i.e., pentylene or undecylene, and may optionally have 1 to 3 methyl or other substituents. More preferably, W is a single bond, methylene, ethylene, or isopropylene.

[0132] The repeating unit (d) can be introduced into the polycarbonate resin composition by using a dihydroxy compound (hereinafter sometimes referred to as "dihydroxy compound (6A)") as a polycarbonate resin raw material.

[0133] [Chemical Formula 15]

[0134]

[0135] (In formula (6A), R) 15 ~R 18 Each of the following is independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a group containing an aryl group having 6 to 12 carbon atoms. W represents at least one selected from single bonds, oxygen atoms, sulfur atoms, sulfinyl groups, sulfonyl groups, and divalent organic groups.

[0136] As a dihydroxy compound (6A), specifically, examples include: 2,2-bis(4-hydroxyphenyl)propane (bisphenol A, abbreviated as BPA), 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, with R being preferred. 15 ~R 18 2,2-bis(4-hydroxyphenyl)propane (BPA) consisting entirely of hydrogen atoms.

[0137] Dihydroxy compound (6A) can be used alone or in combination with two or more.

[0138] <Repeating Unit (b)>

[0139] In equation (2) representing the repeating unit (b), R 3 and R 4 Each is independently a hydrogen atom or a methyl group. From the viewpoint of improving compatibility with polycarbonate resin (B) and enhancing the impact resistance and flexural strength of the polycarbonate resin composition, R... 3 and R 4 Hydrogen atoms are preferred.

[0140] The repeating unit (b) can be introduced into the polycarbonate copolymer (A) by using the dihydroxy compound shown in the following formula (2A) (hereinafter, sometimes referred to as "dihydroxy compound (2A)") as a raw material for the polycarbonate copolymer.

[0141] [Chemical Formula 16]

[0142]

[0143] (In equation (2A), R) 3 and R 4 Each can be used independently to represent a hydrogen atom or a methyl group.

[0144] As a dihydroxy compound (2A), specific examples include: 2,2-bis(4-hydroxyphenyl)propane (bisphenol A, abbreviated as BPA), 2,2-bis(4-hydroxy-3-methylphenyl)propane, with R being preferred. 3 and R 4 Both of these are 2,2-bis(4-hydroxyphenyl)propane (BPA) with hydrogen atoms.

[0145] Dihydroxy compound (2A) can be used alone or in combination with two or more.

[0146] <Repeating Unit (c)>

[0147] In equation (3) representing the repeating unit (c), R 5 and R 6 Each can be independently a hydrogen atom or a methyl group. From the perspective of improving impact resistance and flexural strength, R... 5 and R 6 Hydrogen atoms are preferred.

[0148] The repeating unit (c) can be introduced into the polycarbonate resin (B) by using the dihydroxy compound shown in the following formula (3A) (hereinafter, sometimes referred to as "dihydroxy compound (3A)") as a polycarbonate resin raw material.

[0149] [Chemical Formula 17]

[0150]

[0151] (In formula (3A), R)5 and R 6 Each can be used independently to represent a hydrogen atom or a methyl group.

[0152] As dihydroxy compounds (3A), specifically, examples include 2,2-bis(4-hydroxyphenyl)propane (bisphenol A, abbreviated: BPA), 2,2-bis(4-hydroxy-3-methylphenyl)propane, with R preferred. 5 and R 6 Both of these are 2,2-bis(4-hydroxyphenyl)propane (BPA) with hydrogen atoms.

[0153] Dihydroxy compound (3A) can be used alone or in combination with two or more.

[0154] <Other repeating units>

[0155] The polycarbonate resin composition I may also contain other repeating units besides the repeating units (a) and (d) described above.

[0156] In addition, polycarbonate resin composition II may also contain other repeating units besides the repeating units (a) to (c) described above.

[0157] Hereinafter, these repeating units will sometimes be referred to as "other repeating units".

[0158] Other repeating units optionally present in polycarbonate resin composition I may include repeating units derived from one or more dihydroxy compounds selected from the following other dihydroxy compound groups.

[0159] Other repeating units optionally present in polycarbonate resin composition II may include repeating units contained in repeating unit (d) but not in repeating units (b) and (c), and repeating units derived from one or more dihydroxy compounds selected from the group consisting of other dihydroxy compounds.

[0160] (Other dihydroxy compounds group)

[0161] 9,9-bis(4-(2-hydroxyethoxy)-3-tert-butylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-isopropylphenyl)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, and other 9,9-bis(4-(2-hydroxyethoxy)-3,5-dimethylphenyl)fluorene compounds other than the dihydroxy compound (1A) described above;

[0162] Dihydroxybenzene derivatives such as 1,2-dihydroxybenzene, 1,3-dihydroxybenzene (i.e., resorcinol), and 1,4-dihydroxybenzene;

[0163] Dihydroxybiphenyls such as 2,5-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, and 4,4'-dihydroxybiphenyl;

[0164] Dihydroxynaphthalenes, such as 2,2'-dihydroxy-1,1'-binaphthyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, and 2,7-dihydroxynaphthalene;

[0165] Dihydroxy diaryl ethers such as 2,2'-dihydroxydiphenyl ether, 3,3'-dihydroxydiphenyl ether, and 1,4-bis(3-hydroxyphenoxy)benzene.

[0166] [The proportion of repeating unit (a) in the polycarbonate resin composition of the present invention]

[0167] The polycarbonate resin compositions of the present invention, namely polycarbonate resin composition I and polycarbonate resin composition II, contain repeating unit (a) of formula (1) in a proportion of 16 to 63 by mass.

[0168] If the content of repeating unit (a) is less than 16% by mass, a high-refractive-index polycarbonate resin composition cannot be prepared.

[0169] If the content of repeating unit (a) exceeds 63% by mass, the strength of the polycarbonate resin composition will decrease.

[0170] From the viewpoint of seeking a balance between refractive index and strength, the content of repeating unit (a) in the polycarbonate resin composition of the present invention is preferably 16 to 53% by mass, more preferably 18 to 47% by mass, and even more preferably 20 to 43% by mass.

[0171] The polycarbonate resin composition of the present invention may contain only one repeating unit (a) or may contain two or more repeating units.

[0172] [The proportion of repeating unit (d) in polycarbonate resin composition I]

[0173] The polycarbonate resin composition I contains a repeating unit (d) of formula (6) in a proportion of 37 to 84 by mass.

[0174] If the content of repeating unit (d) exceeds 84% ​​by mass, it cannot be a high-refractive-index polycarbonate resin composition.

[0175] If the content of repeating unit (d) is less than 37% by mass, the strength of the polycarbonate resin composition will decrease.

[0176] From the viewpoint of seeking a balance between refractive index and strength, the content of repeating unit (d) in polycarbonate resin composition I is preferably 47-84% by mass, more preferably 53-82% by mass, and even more preferably 57-80% by mass.

[0177] The polycarbonate resin composition I may contain only one repeating unit (d) or more than two repeating units.

[0178] [The proportion of other repeating units in polycarbonate resin composition I]

[0179] The polycarbonate resin composition I may contain only repeating units (a) and repeating units (d), or it may contain one or more other repeating units besides repeating units (a) and repeating units (d).

[0180] In the case where the polycarbonate resin composition I contains other repeating units, from the viewpoint of more effectively obtaining the effects brought about by the presence of repeating units (a) and repeating units (d), the content of other repeating units in the polycarbonate resin composition I is preferably 30% by mass or less, more preferably 15% by mass or less, and most preferably 0% by mass (excluding other repeating units other than repeating units (a) and repeating units (d)).

[0181] Here, other repeating units refer to repeating units derived from the other dihydroxy compounds.

[0182] [Polycarbonate copolymer (A)]

[0183] The polycarbonate copolymer (A) contained in the polycarbonate resin composition II is a polycarbonate copolymer containing the repeating unit (a) shown in formula (1) and the repeating unit (b) shown in formula (2) in a content ratio of repeating unit (a): repeating unit (b) = (50-85% by mass): (50-15% by mass).

[0184] In the polycarbonate copolymer (A), a high-refractive-index polycarbonate resin composition II can be obtained as long as the content of repeating unit (a) is 50% or more by mass and the content of repeating unit (b) is 50% or less by mass.

[0185] In the polycarbonate copolymer (A), as long as the content of repeating unit (a) is less than 85% by mass and the content of repeating unit (b) is more than 15% by mass, the polycarbonate copolymer (A) and polycarbonate resin (B) can be well compatible, and a polycarbonate resin composition II with excellent transparency can be obtained.

[0186] From these perspectives, the repeating unit (a): repeating unit (b) in the polycarbonate copolymer (A) is preferably (60-84% by mass): (40-16% by mass), more preferably (70-83% by mass): (30-17% by mass).

[0187] The polycarbonate copolymer (A) may contain only one repeating unit (a) or more than two repeating units. Furthermore, the repeating unit (b) may contain only one repeating unit or more than two repeating units.

[0188] The polycarbonate copolymer (A) may contain only repeating units (a) and repeating units (b), or it may contain one or more other repeating units besides repeating units (a) and repeating units (b).

[0189] In the case where the polycarbonate copolymer (A) contains other repeating units, from the viewpoint of more effectively obtaining the effects brought about by the presence of repeating units (a) and repeating units (b), the content of other repeating units in the polycarbonate copolymer (A) is preferably 30% by mass or less, more preferably 15% by mass or less, and most preferably 0% by mass (excluding other repeating units other than repeating units (a) and repeating units (b)).

[0190] Here, other repeating units refer to repeating units derived from the other dihydroxy compounds mentioned above, as well as repeating units derived from the dihydroxy compound (6A) that are not equivalent to repeating unit (b).

[0191] The polycarbonate copolymer (A) may contain only one of these other repeating units, or it may contain two or more.

[0192] The viscosity-average molecular weight of the polycarbonate copolymer (A) is not particularly limited as long as it can meet the viscosity-average molecular weight described later when used together with the polycarbonate resin (B) as polycarbonate resin composition II. However, from the viewpoint of achieving good high refractive index, high strength, high flowability, and excellent transparency when used with polycarbonate resin (B), it is preferably 10,000 to 26,000, more preferably 12,000 to 25,000, and even more preferably 14,000 to 24,000.

[0193] Polycarbonate copolymer (A) can be a single type or a combination of two or more copolymers containing different types, contents, and viscosity-average molecular weights of repeating units.

[0194] [Polycarbonate resin (B)]

[0195] The polycarbonate resin (B) contained in polycarbonate resin composition II is a polycarbonate resin containing more than 95% by mass of the repeating unit (c) shown in formula (3).

[0196] In polycarbonate resin (B), a polycarbonate resin composition II with excellent strength can be obtained as long as the content of repeating unit (c) is 95% by mass or more. From the viewpoint of strength, the content of repeating unit (c) in polycarbonate resin (B) is preferably 96% by mass or more, more preferably 97% by mass or more, and even more preferably 98 to 100% by mass.

[0197] In the case where the polycarbonate resin (B) contains repeating units other than repeating unit (c), the repeating unit (a) and other repeating units optionally present in the polycarbonate copolymer (A) can be listed as other repeating units other than repeating unit (c).

[0198] The polycarbonate resin (B) may contain only one of these other repeating units, or it may contain two or more.

[0199] The viscosity-average molecular weight of the polycarbonate resin (B) is not particularly limited as long as it can meet the viscosity-average molecular weight described later when used together with the polycarbonate copolymer (A) as polycarbonate resin composition II. However, from the viewpoint of achieving good high refractive index, high strength, high flowability, and excellent transparency when used in combination with the polycarbonate copolymer (A), it is preferably 9,000 to 26,000, more preferably 11,000 to 25,000, and even more preferably 13,000 to 24,000.

[0200] Furthermore, from the viewpoint of ensuring good compatibility between the polycarbonate copolymer (A) and the polycarbonate resin (B) and improving the transparency of the polycarbonate resin composition II, it is preferable that the difference between the viscosity-average molecular weight of the polycarbonate copolymer (A) and the viscosity-average molecular weight of the polycarbonate resin (B) is 10,000 or less, particularly 8,000 or less.

[0201] Commercially available polycarbonate resin (B) can be used. Examples of commercially available polycarbonate resin (B) include "IUPILON (registered trademark) H-4000" (manufactured by Mitsubishi Engineering-Plastics, Mv: 15000), "IUPILON (registered trademark) S-3000" (manufactured by Mitsubishi Engineering-Plastics, Mv: 20400), "XANTAR (registered trademark) 7022PJ" (manufactured by Mitsubishi Chemical, Mv: 20850), and "XANTAR (registered trademark) 7022PJ3LV" (manufactured by Mitsubishi Chemical, Mv: 17130), etc.

[0202] Polycarbonate resin (B) can be used alone or in combination with two or more polycarbonate resins that contain different types, contents, and viscosity-average molecular weights of repeating units.

[0203] [Ratio of polycarbonate copolymer (A) to polycarbonate resin (B)]

[0204] In the polycarbonate resin composition II, which is a second embodiment of the present invention, containing polycarbonate copolymer (A) and polycarbonate resin (B), the polycarbonate copolymer (A) is contained in proportions of 30 to 70% by mass, and the polycarbonate resin (B) is contained in proportions of 70 to 30% by mass.

[0205] If the polycarbonate copolymer (A) is greater than the above range and the polycarbonate resin (B) is less than the above range, there is a tendency for poor strength. Conversely, if the polycarbonate copolymer (A) is less than the above range and the polycarbonate resin (B) is more than the above range, there is a tendency for a decrease in refractive index.

[0206] From these perspectives, polycarbonate resin composition II preferably contains 35 to 68% by mass of polycarbonate copolymer (A) and 65 to 32% by mass of polycarbonate resin (B), and more preferably contains 40 to 65% by mass of polycarbonate copolymer (A) and 60 to 35% by mass of polycarbonate resin (B).

[0207] Polycarbonate resin composition II, which contains polycarbonate copolymer (A) and polycarbonate resin (B), optionally contains other polycarbonate resins besides polycarbonate copolymer (A) and polycarbonate resin (B).

[0208] Examples of polycarbonate resins other than polycarbonate copolymer (A) and polycarbonate resin (B) include polycarbonate copolymers containing repeating units (a) and repeating units (b) in proportions exceeding those of the polycarbonate copolymer (A), polycarbonate resins containing repeating units (c) in proportions less than 95% by mass, and polycarbonate resins containing one or more repeating units derived from the other dihydroxy compounds.

[0209] In the case where the polycarbonate resin composition II contains these other polycarbonate resins, from the viewpoint of more effectively obtaining the effects brought about by the polycarbonate copolymer (A) and polycarbonate resin (B), the content of the other polycarbonate resins in the polycarbonate resin composition II of the present invention is preferably 30% by mass or less, particularly preferably 15% by mass or less, and most preferably 0% by mass (excluding other polycarbonate resins).

[0210] [Viscosity-average molecular weight]

[0211] The polycarbonate resin compositions of the present invention, namely polycarbonate resin composition I and polycarbonate resin composition II, have a viscosity-average molecular weight of 15,000 or more.

[0212] If the viscosity-average molecular weight is less than 15,000, high strength cannot be achieved. From the viewpoint of strength, the viscosity-average molecular weight of the polycarbonate resin composition of the present invention is preferably 15,500 or more, more preferably 16,000 or more, and particularly preferably 16,500 or more.

[0213] On the other hand, if the viscosity-average molecular weight of the polycarbonate resin composition is too high, the moldability may be impaired due to reduced flowability. Therefore, the viscosity-average molecular weight of the polycarbonate resin composition of the present invention is preferably 26,000 or less, particularly 25,000 or less, more preferably 24,000 or less, and especially preferably 23,000 or less.

[0214] In this invention, the viscosity-average molecular weight (Mv) of the polycarbonate resin composition refers to the intrinsic viscosity (limiting viscosity) [η] (unit: dL / g) at 20°C, determined using dichloromethane as a solvent and an Ubbelohde viscometer, according to the Schnell viscosity formula, i.e., η = 1.23 × 10⁻⁶. -4 Mv 0.83 The calculated value.

[0215] The intrinsic viscosity (limiting viscosity) [η] is the specific viscosity [ηsp] at various solution concentrations [C] (g / dL), calculated according to the following formula.

[0216] [Formula 1]

[0217]

[0218] Charpy impact strength

[0219] From the viewpoint of solving the problem of providing polycarbonate resin compositions with excellent strength, the unnotched Charpy impact strength of the polycarbonate resin compositions of the present invention, namely polycarbonate resin composition I and polycarbonate resin composition II, is preferably 300 kJ / m as measured according to ISO 179. 2 The above or NB.

[0220] From this perspective, the unnotched Charpy impact strength of the polycarbonate resin composition of the present invention is preferably NB.

[0221] The method for determining the unnotched Charpy impact strength in this invention is as described in the embodiments described later.

[0222] [Refractive index (nD)]

[0223] From the viewpoint of solving the problem of providing a polycarbonate resin composition with a high refractive index, it is preferable that the polycarbonate resin compositions of the present invention, namely polycarbonate resin composition I and polycarbonate resin composition II, have a refractive index nD of 1.595 or higher.

[0224] From this perspective, the refractive index nD of the polycarbonate resin composition of the present invention is preferably 1.597 or higher, more preferably 1.599 or higher.

[0225] The upper limit of the refractive index nD of the polycarbonate resin composition of the present invention is not particularly limited, but is generally below 1.630.

[0226] The method for determining the refractive index nD in this invention is specifically described in the embodiments described below.

[0227] [Membrane transparency]

[0228] Preferably, in the polycarbonate resin compositions of the present invention, particularly in the polycarbonate resin composition I of the present invention, polycarbonate resin compositions containing two or more repeating units (a) with different proportions of polycarbonate resin, particularly in the polycarbonate resin composition II of the present invention, have excellent transparency in the following film transparency test, allowing text to be read from above through the film.

[0229] <Membrane Transparency Test>

[0230] Approximately 4g of resin sample, vacuum dried at 100℃ for 2 hours, was used with spacers 8cm wide, 8cm long, and 1.0mm thick. The sample was preheated for 2 minutes at a hot pressing temperature of 230℃ and then pressurized for 1 minute at a pressure of 20MPa. The sample was then removed along with the spacers and cooled at room temperature to produce a 900μm thick membrane.

[0231] The film made using this method is laid on paper with printed text, and it is confirmed whether the text printed on the paper can be read from above through the film.

[0232] The specific method for testing membrane transparency in this invention is described in the embodiments described below.

[0233] [Manufacturing method of polycarbonate resin]

[0234] Including the polycarbonate resin composition for XR described later, the polycarbonate copolymer (A), polycarbonate resin (B), and other polycarbonate resins contained in the polycarbonate resin composition of the present invention can be manufactured by conventionally known polymerization methods, which are not particularly limited.

[0235] Examples of polymerization methods include: interfacial polymerization, melt transesterification, pyridine polymerization, ring-opening polymerization of cyclic carbonate compounds, and solid-phase transesterification of prepolymers.

[0236] The following section provides a detailed description of the most preferred method among these methods.

[0237] (Interface aggregation method)

[0238] In interfacial polymerization, the pH is typically maintained above 9 in the presence of an inactive organic solvent and an alkaline aqueous solution. This allows the dihydroxy compound of the raw material to react with the carbonate-forming compound, followed by interfacial polymerization in the presence of a polymerization catalyst, thereby obtaining polycarbonate resin.

[0239] In the reaction system, molecular weight adjusters (terminators) can be added as needed, or antioxidants can be added to prevent oxidation of the dihydroxy compound in the raw material.

[0240] There are no particular limitations on the organic solvents that are inactive in the reaction. Examples include: dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene, dichlorobenzene and other chlorinated hydrocarbons; benzene, toluene, xylene and other aromatic hydrocarbons; etc.

[0241] One organic solvent may be used, or two or more may be used in any combination and ratio.

[0242] The alkaline compounds contained in the alkaline aqueous solution are not particularly limited, but can include, for example, alkali metal compounds and alkaline earth metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium bicarbonate. Among them, sodium hydroxide and potassium hydroxide are preferred.

[0243] One base compound may be used, or two or more may be used in any combination and ratio.

[0244] There is no limit to the concentration of alkaline compounds in alkaline aqueous solutions. Usually, in order to control the pH of alkaline aqueous solutions to 10-12, the concentration of alkaline compounds is used at 5-10% by mass.

[0245] For example, when blowing in phosgene, in order to control the pH of the aqueous phase to 10 to 12, preferably 10 to 11, the molar ratio of the raw material dihydroxy compound to the base compound is usually set to 1:1.9 or more, particularly 1:2.0 or more, usually 1:3.2 or less, particularly 1:2.5 or less.

[0246] As a starting material, a dihydroxy compound is used that can generate repeating units (a), (b), (c), and (d) by reacting with a carbonate-forming compound.

[0247] That is, if it is a polycarbonate resin composition I, then the dihydroxy compound (1A) and dihydroxy compound (6A) are used as necessary components.

[0248] In the case of polycarbonate copolymer (A) of polycarbonate resin composition II, the dihydroxy compound (1A) and dihydroxy compound (2A) are used as necessary components.

[0249] If the polycarbonate resin (B) is polycarbonate resin composition II, then the dihydroxy compound (3A) is used as an essential component.

[0250] In the polycarbonate resin composition for XR described later, the dihydroxy compound (1A) is used as an essential component.

[0251] As a carbonate-forming compound, a carbonyl halide is preferred, and phosgene is preferred. The method using phosgene is specifically referred to as the phosgene process.

[0252] As polymerization catalysts, there are no particular limitations. Examples include: aliphatic tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, and trihexylamine; alicyclic tertiary amines such as N,N'-dimethylcyclohexylamine and N,N'-diethylcyclohexylamine; aromatic tertiary amines such as N,N'-dimethylaniline and N,N'-diethylaniline; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride, and triethylbenzylammonium chloride; pyridine; guanine; guanidine salts; etc.

[0253] The polymerization catalyst can be one type, or two or more types can be used in any combination and ratio.

[0254] As a molecular weight modifier, there are no particular limitations. Examples include: aromatic phenols with monovalent phenolic hydroxyl groups; aliphatic alcohols such as methanol and butanol; thiols; and phthalimides. Among these, aromatic phenols are preferred.

[0255] Specifically, the following aromatic phenols can be listed: phenol, o-n-butylphenol, m-n-butylphenol, p-n-butylphenol, o-isobutylphenol, m-isobutylphenol, p-isobutylphenol, o-tert-butylphenol, m-tert-butylphenol, p-tert-butylphenol, o-n-pentylphenol, m-n-pentylphenol, p-n-pentylphenol, o-n-hexylphenol, m-n-hexylphenol, p-n-hexylphenol, p-tert-octylphenol, o-cyclohexylphenol, m-cyclohexylphenol, p-cyclohexylphenol, o-phenylphenol, m-phenylphenol, p-phenylphenol, o-nonylphenol, m-nonylphenol, p-nonylphenol, o-cumylphenol, m-cumylphenol Phenol, p-cumylphenol, o-naphthylphenol, m-naphthylphenol, p-naphthylphenol, 2,5-di-tert-butylphenol, 2,4-di-tert-butylphenol, 3,5-di-tert-butylphenol, 2,5-dicumylphenol, 3,5-dicumylphenol, p-cresol, bromophenol, tribromophenol, monoalkylphenols with straight-chain or branched alkyl groups having an average carbon number of 12 to 35 at the ortho, meta, or para positions, 9-(4-hydroxyphenyl)-9-(4-methoxyphenyl)fluorene, 9-(4-hydroxy-3-methylphenyl)-9-(4-methoxy-3-methylphenyl)fluorene, 4-(1-adamantyl)phenol, etc.

[0256] Among them, p-tert-butylphenol, p-phenylphenol, and p-cumylphenol are preferred.

[0257] Molecular weight modifiers can be used alone, or in any combination and ratio of two or more.

[0258] There is no particular limitation on the amount of molecular weight adjuster used. For example, relative to 100 moles of the raw material dihydroxy compound, it is usually 0.5 moles or more, preferably 1 mole or more; usually 50 moles or less, preferably 30 moles or less.

[0259] As an antioxidant, there are no particular limitations; for example, hindered phenolic antioxidants can be listed.

[0260] Specific examples include: pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, thiodiethylidene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], 2,4-dimethyl-6-(1-methylpentadecanyl)phenol, diethyl[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphate, 3,3',3”,5,5',5”-hexa-tert-butyl-a,a',a”-(trimethyl) Benzene-2,4,6-triyl)tri-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, ethylene bis(oxoethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], hexamethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazine-2-ylamino)phenol, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, etc.

[0261] Among them, pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate are preferred.

[0262] Commercially available phenolic antioxidants include: BASF's "IRGANOX 1010" and "IRGANOX 1076", and ADEKA's "ADK STAB AO-50" and "ADK STAB AO-60".

[0263] Antioxidants can be used alone, or in any combination and ratio of two or more.

[0264] There is no particular limitation on the amount of antioxidant used, but it is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and even more preferably 0.1 parts by mass or more, relative to 100 parts by mass of the raw material dihydroxy compound. By setting the amount of antioxidant used to the above-mentioned lower limit or above, the effect as an antioxidant becomes sufficient.

[0265] Furthermore, the amount of antioxidant used is preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, relative to 100 parts by mass of the raw material dihydroxy compound. By setting the amount of antioxidant used to the above-mentioned upper limit, gas generation during injection molding can be suppressed.

[0266] During the reaction, the order in which the reaction matrix (reaction raw materials), reaction solvent (organic solvent), catalyst, additives, etc., are mixed is arbitrary as long as the desired polycarbonate resin is obtained; any appropriate order can be set. For example, when using phosgene as a carbonate-forming compound, the molecular weight modifier can be mixed at any time during the period from the reaction of the raw material dihydroxy compound with phosgene (phosgenation) to the start of the polymerization reaction.

[0267] There is no particular limitation on the reaction temperature, but it is preferably 0 to 40°C.

[0268] There is no particular limitation on the reaction time, but it is preferably from several minutes (e.g., 10 minutes) to several hours (e.g., 6 hours).

[0269] (Melted transesterification method)

[0270] In the melt transesterification process, for example, a transesterification reaction is carried out between a carbonate and a dihydroxy compound from the feedstock.

[0271] The raw material dihydroxy compound is the same as that used in interfacial polymerization.

[0272] As a carbonate, any compound shown in formula (4) below can be used, such as aryl carbonates, dialkyl carbonates, dihydroxy compounds, monohydroxy compounds, cyclic carbonates, etc.

[0273] [Chemical Formula 18]

[0274]

[0275] In equation (4) above, R 11 and R 12 Each of the following groups independently represents an alkyl, aryl, or aralkyl group having 1 to 30 carbon atoms. Hereinafter, when R... 11 and R 12 When it is alkyl or aralkyl, it is sometimes called dialkyl carbonate; when it is aryl, it is sometimes called diaryl carbonate.

[0276] From the perspective of reactivity with dihydroxy compounds, R 11 and R 12 Preferably, all are aryl, and more preferably are diaryl carbonate esters as shown in formula (5) below.

[0277] [Chemical Formula 19]

[0278]

[0279] In equation (5) above, R 13 and R 14Each group can be independently represented by a halogen atom, a nitro group, a cyano group, an alkyl group with 1 to 20 carbon atoms, an alkoxycarbonyl group with 1 to 20 carbon atoms, a cycloalkyl group with 4 to 20 carbon atoms, or an aryl group with 6 to 20 carbon atoms. p and q can independently represent integers from 0 to 5.

[0280] Examples of such carbonates include: dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, and di-tert-butyl carbonate; diphenyl carbonate (hereinafter sometimes abbreviated as "DPC"), bis(4-methylphenyl) carbonate, bis(4-chlorophenyl) carbonate, bis(4-fluorophenyl) carbonate, bis(2-chlorophenyl) carbonate, bis(2,4-difluorophenyl) carbonate, bis(4-nitrophenyl) carbonate, bis(2-nitrophenyl) carbonate, bis(methylsalicylic acid phenyl) carbonate, xylene carbonate, and other (optionally substituents) diaryl carbonates. Diphenyl carbonate is preferred.

[0281] These carbonates can be used alone or in combination of two or more.

[0282] Regarding the carbonate, preferably 50 mol% or less, more preferably 30 mol% or less, can be replaced with a dicarboxylic acid or a dicarboxylic acid ester. Representative dicarboxylic acids or dicarboxylic acid esters include terephthalic acid, isophthalic acid, diphenyl terephthalate, and diphenyl isophthalate. When such a dicarboxylic acid or dicarboxylic acid ester is used, a polyester carbonate is obtained.

[0283] The ratio of the raw material dihydroxy compound to the carbonate is arbitrary as long as the desired polycarbonate resin can be obtained. Preferably, the carbonate is used in excess of the raw material dihydroxy compound during polymerization.

[0284] That is, the amount of carbonate used is preferably 1.01 times (molar ratio) or more relative to the dihydroxy compound, and more preferably 1.02 times or more. By setting the molar ratio to the lower limit mentioned above, the thermal stability of the obtained polycarbonate resin becomes good.

[0285] The amount of carbonate used relative to the dihydroxy compound is preferably 1.30 times (molar ratio) or less, more preferably 1.20 times or less. By setting the molar ratio to the upper limit mentioned above, reactivity is improved, the production rate of polycarbonate resin with the desired molecular weight is easily improved, and the amount of residual carbonate in the polycarbonate resin is reduced. Therefore, it is preferable to suppress odor generation during molding and when forming molded articles.

[0286] When manufacturing polycarbonate resins via melt transesterification, transesterification catalysts are typically used.

[0287] The transesterification catalyst is not particularly limited, and conventionally known transesterification catalysts can be used. For example, alkali metal compounds and / or alkaline earth metal compounds are preferred. In addition, basic compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds can be used as adjuncts.

[0288] One type of transesterification catalyst can be used, or two or more can be used in any combination and ratio.

[0289] In the melt transesterification process, the reaction temperature is not particularly limited, and is usually between 100 and 320°C.

[0290] There are no particular restrictions on the pressure during the reaction; it is usually a reduced pressure of less than 2 mmHg.

[0291] As a specific operation, it is sufficient to carry out a melt polycondensation reaction while removing byproducts under the conditions described.

[0292] The polycarbonate resin of this invention is significantly affected by thermal processes and oxidation in the presence of an alkaline catalyst, tending to lead to hue deterioration. Therefore, the reaction temperature is set to below 320°C. Furthermore, to avoid oxygen infiltration into the equipment due to excessive decompression, a lower limit of approximately 0.05 mmHg is preferably selected.

[0293] The reaction can be carried out using either batch or continuous methods. In the case of batch reaction, the order in which the reaction substrate, reaction solvent, catalyst, additives, etc., are mixed is arbitrary, as long as the desired polycarbonate resin composition is obtained; any appropriate order can be set.

[0294] In the molten transesterification process, catalyst deactivators can be used as needed.

[0295] As catalyst deactivators, compounds that neutralize transesterification catalysts can be used in any way. Examples include sulfur-containing acidic compounds and their derivatives, phosphorus-containing acidic compounds and their derivatives, etc.

[0296] Catalyst deactivators can be used in one form or in any combination and ratio of two or more.

[0297] The amount of catalyst deactivator used is not particularly limited, but it is generally 0.5 equivalents or more relative to the transesterification catalyst, preferably 1 equivalent or more, more preferably 3 equivalents or more, generally 50 equivalents or less, preferably 10 equivalents or less, more preferably 8 equivalents or less.

[0298] The amount of catalyst deactivator used relative to polycarbonate resin is typically above 1 ppm and below 100 ppm, preferably below 50 ppm.

[0299] When the polycarbonate copolymer (A) manufactured as described above is mixed with polycarbonate resin (B) to produce the polycarbonate resin composition of the present invention, it is sufficient to perform melt mixing at a temperature of about 220 to 290°C using an extruder or the like.

[0300] [Other ingredients]

[0301] As long as the polycarbonate resin composition I meets the requirements of the ratio of repeating unit (a) to repeating unit (d) and the range of viscosity-average molecular weight, it may contain other components besides polycarbonate resin as needed.

[0302] As long as the polycarbonate resin composition II meets the content ratio of the polycarbonate copolymer (A), polycarbonate resin (B) and repeating unit (a) and the viscosity-average molecular weight range, it may contain other components besides polycarbonate resin as needed.

[0303] The same applies to the polycarbonate resin compositions for XR described later.

[0304] If we list other examples of ingredients, we can list resins other than polycarbonate resin, various resin additives, etc.

[0305] Other ingredients may be one, or two or more in any combination and ratio.

[0306] <Other Resins>

[0307] Other resins besides polycarbonate resins include, for example:

[0308] Thermoplastic polyester resins such as polyethylene terephthalate (PET resin), polypropylene terephthalate (PTT resin), and polybutylene terephthalate (PBT resin);

[0309] Polystyrene resin (PS resin), high-impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), acrylonitrile-ethylene-propylene rubber-styrene copolymer (AES resin), and other styrene-based resins;

[0310] Polyolefin resins such as polyethylene resin (PE resin), polypropylene resin (PP resin), and cyclic cycloolefin resin (COP resin);

[0311] Polyamide resin (PA resin); polyimide resin (PI resin); polyetherimide resin (PEI resin); polyurethane resin (PU resin); polyphenylene ether resin (PPE resin); polyphenylene sulfide resin (PPS resin); polysulfone resin (PSU resin); polymethyl methacrylate resin (PMMA resin); liquid crystal polymer (LCP), etc.

[0313] Other resins may be contained in one type, or in any combination and ratio of two or more types.

[0314] <Resin Additives>

[0315] Examples of resin additives include: heat stabilizers, antioxidants, release agents, lightfastness agents (HALS), flame retardants, antistatic agents, antifogging agents, lubricants, antiblocking agents, flow improvers, plasticizers, dispersants, antibacterial agents, dyes, and pigments.

[0316] Resin additives may contain only one type, or two or more types in any combination and ratio.

[0317] [Polycarbonate resin content ratio]

[0318] Including the polycarbonate resin composition for XR described later, the polycarbonate resin composition of the present invention optionally contains one of a resin other than polycarbonate resin, a resin additive, or two or more in any combination and ratio.

[0319] In cases where the polycarbonate resin composition of the present invention contains resins other than polycarbonate resin and resin additives, from the viewpoint of more effectively obtaining the effects of the present invention, the proportion of polycarbonate resin in all resin components contained in the polycarbonate resin composition of the present invention is preferably 70% by mass or more, more preferably 75% by mass or more, further preferably 80% by mass or more, particularly preferably 85% by mass or more, and most preferably 90% by mass or more.

[0320] [Molded body]

[0321] The molded articles of the present invention using the polycarbonate resin composition of the present invention have high refractive index, high strength, and excellent transparency. Therefore, the polycarbonate resin composition of the present invention can be used in optical materials such as lenses, optical films, and optical sheets, and is particularly useful as projectors or films for XR.

[0322] There are no particular limitations on the molding method for obtaining the molded article of the present invention by molding the polycarbonate resin composition of the present invention. Examples include: injection molding, injection compression molding, extrusion molding, profile extrusion, transfer molding, blow molding, gas-assisted blow molding, blow molding, extrusion blow molding, IMC (in-mold coating) molding, rotational molding, multilayer molding, two-color molding, insert molding, sandwich molding, foam molding, pressure molding, sheet molding, thermoforming, lamination molding, pressure molding, semi-finishing, and solvent casting. Among these, injection molding, extrusion molding, semi-finishing, and solvent casting are particularly preferred.

[0323] The molding temperature of the polycarbonate resin composition of the present invention is not particularly limited by methods such as injection molding, injection compression molding, and extrusion molding. Preferably, it is 200°C or higher, more preferably 220°C or higher, and most preferably 230°C or higher. By setting the molding temperature to the lower limit or above mentioned above, the fluidity and moldability are improved.

[0324] The molding temperature for molding the polycarbonate resin composition of the present invention is preferably 300°C or lower, and particularly preferably 280°C or lower. By setting the molding temperature below the above-mentioned upper limit, the resulting molded article can have a good appearance.

[0325] During molding, pigments, dyes, release agents, heat stabilizers, etc., may be appropriately added to the polycarbonate resin composition of the present invention without prejudice to the purpose of the present invention.

[0326] [Projector for XR]

[0327] XR is an abbreviation for AR (Augmented Reality), VR (Virtual Reality), MR (Mixed Reality), and SR (Substitutional Reality).

[0328] Projectors for XR refer to optical components used for these applications, including optical films, optical lenses, light guides, and optical waveguides.

[0329] The XR projector of the present invention can be preferably used in smart glasses such as AR glasses, AR head-up displays (HUDs), VR / MR glasses, VR / MR headsets, etc., and is particularly preferred for AR glasses.

[0330] XR films refer to optical films used for these applications. XR films are one embodiment of XR projectors.

[0331] The XR film of the present invention can be preferably used in smart glasses such as AR glasses, AR head-up displays (HUD), VR / MR glasses, VR / MR head-mounted devices, etc., and is particularly preferred for AR glasses.

[0332] The XR projector and XR film of the present invention use a polycarbonate resin composition (hereinafter, sometimes referred to as "polycarbonate resin composition for XR") comprising repeating unit (a) shown in formula (1) and having a viscosity-average molecular weight of 15,000 or more.

[0333] In the case of further pursuing strength, the content of the repeating unit (a) shown in the above-mentioned polycarbonate resin composition for XR is preferably 16 to 63% by mass, more preferably 16 to 60% by mass, and even more preferably 16 to 55% by mass.

[0334] High strength can be obtained as long as the proportion of repeating unit (a) is within the above range.

[0335] In this case, as repeating units other than repeating unit (a) contained in the polycarbonate resin composition for XR, the repeating units (d) optionally contained in the polycarbonate resin composition I or other repeating units other than repeating unit (a) optionally contained in the polycarbonate copolymer (A) of the polycarbonate resin composition II, and preferably repeating unit (b), can be listed.

[0336] In the pursuit of displaying higher-resolution images, the content of the repeating unit (a) shown in formula (1) in the above-mentioned polycarbonate resin composition for XR is preferably more than 63% by mass and less than 100% by mass, more preferably 70 to 100% by mass, and even more preferably 80 to 100% by mass.

[0337] If the proportion of repeating unit (a) is within the above range, the refractive index of the polycarbonate resin composition for XR can be increased, and higher-resolution images can be displayed.

[0338] In this case, if the polycarbonate resin composition for XR contains repeating units other than repeating unit (a), the repeating units other than repeating unit (a) contained in the polycarbonate resin composition for XR can be listed as repeating units (d) optionally contained in the polycarbonate resin composition I or other repeating units other than repeating unit (a) or repeating units (b) optionally contained in the polycarbonate copolymer (A) of the polycarbonate resin composition II, preferably repeating unit (b).

[0339] A necessary condition for polycarbonate resin compositions for XR is a viscosity-average molecular weight of 15,000 or higher. When the viscosity-average molecular weight of the polycarbonate resin composition for XR is less than 15,000, it cannot meet the high refractive index requirement for use as a projector or film for XR.

[0340] From the viewpoint of high refractive index, the viscosity-average molecular weight of the polycarbonate resin composition for XR is preferably 15,500 or more, and more preferably 16,000 or more.

[0341] On the other hand, if the viscosity-average molecular weight of the polycarbonate resin composition for XR is too high, the moldability may be impaired due to reduced flowability. Therefore, the viscosity-average molecular weight of the polycarbonate resin composition for XR is preferably 26,000 or less, particularly preferably 25,000 or less, and especially preferably 24,000 or less.

[0342] As for the polycarbonate resin composition for XR, there are no particular limitations as long as the preferred repeating unit (a) content ratio and viscosity-average molecular weight are satisfied. In particular, as an example of the polycarbonate resin composition for XR used in XR projectors, or even for XR films where strength is further pursued, the polycarbonate resin composition of the present invention, namely polycarbonate resin composition I or polycarbonate resin composition II, especially polycarbonate resin composition II, can be cited as a preferred embodiment.

[0343] When manufacturing the XR projector of the present invention using the XR polycarbonate resin composition, the XR polycarbonate resin composition can be molded using the same method as the molding method of the polycarbonate resin composition of the present invention, preferably by injection molding, extrusion molding, semi-finishing, or solvent casting.

[0344] The shape of the XR projector of the present invention manufactured in this way is not particularly limited, and can be listed as cuboid, cylindrical, pancake lens, Fresnel lens, biconvex lens, plano-convex lens, convex meniscus lens, biconcave lens, plano-concave lens, concave meniscus lens, biconvex lens, condenser lens, etc.

[0345] Furthermore, there is no particular limitation on the thickness of such XR projectors. Typically, the thickness of the thickest part is about 0.001 to 50 mm, preferably about 0.1 to 30 mm, and more preferably about 0.5 to 20 mm.

[0346] The XR projector of the present invention may also be a product made of a material formed by applying a hard coating, anti-fingerprint treatment, anti-glare treatment, anti-reflection treatment, etc., to a material formed by using an XR polycarbonate resin composition in the form of a cuboid, cylindrical, biscuit head, Fresnel lens, biconvex lens, plano-convex lens, convex meniscus lens, biconcave lens, plano-concave lens, concave meniscus lens, biconvex lens, or condenser lens.

[0347] When manufacturing the XR film of the present invention using the XR polycarbonate resin composition, the XR polycarbonate resin composition can be molded by the same method as the molding method of the polycarbonate resin composition of the present invention, preferably by injection molding or extrusion molding.

[0348] The thickness of the XR film of the present invention manufactured in this way is not particularly limited, and is usually about 0.001 to 3.000 mm.

[0349] The XR film of the present invention can also be a product made by molding an XR polycarbonate resin composition into a film and applying hard coating, anti-fingerprint treatment, anti-glare treatment, anti-reflection treatment, etc. to the molded material.

[0350] Example

[0351] The present invention will now be further described in detail based on embodiments. The present invention is not limited to the following embodiments.

[0352] The physical properties of the polycarbonate resins obtained in the following examples and comparative examples were evaluated by the methods described below.

[0353] [1] Viscosity-average molecular weight (Mv)

[0354] Polycarbonate resin was dissolved in dichloromethane (concentration 7.0 g / L), and the intrinsic viscosity (limiting viscosity) [η] (unit dL / g) at 20°C was determined using an Ubbelohde viscometer (manufactured by Moritomo Rika Co., Ltd.). The viscosity-average molecular weight (Mv) was then calculated according to Schnell's viscosity formula (the formula below).

[0355] η = 1.23 × 10 -4 Mv 0.83

[0356] [2] Transparency

[0357] Approximately 4g of resin sample, vacuum dried at 100℃ for 2 hours, was used with spacers 8cm wide, 8cm long, and 1.0mm thick. The sample was preheated for 2 minutes at a hot pressing temperature of 230℃ and then pressurized for 1 minute at a pressure of 20MPa. The sample was then removed along with the spacers and cooled at room temperature to produce a 900μm thick membrane.

[0358] The film made by this method is laid on paper printed with the letters ABC, and its transparency is evaluated according to the following criteria.

[0359] 〇: Read the letters ABC from above through the membrane.

[0360] ×: The characters ABC cannot be read from above through the membrane.

[0361] [3] Refractive index nD

[0362] Using spacers 8cm wide, 8cm long, and 0.5mm thick, the material was preheated for 2 minutes at 230°C using a hot press, and then pressurized for 1 minute at 20MPa. The material was then removed along with the spacers and cooled at room temperature. Approximately 4g of resin sample was vacuum dried at 100°C for 2 hours to produce a 200μm thick film.

[0363] A rectangular test piece with a length of 10 mm and a width of 8 mm was cut from the membrane to serve as the test sample.

[0364] The refractive index nD was determined using a multi-wavelength Abbe refractometer (ATAGO DRM4 / 1550, Inc.) with an interference filter at 589 nm (D line). The determination was performed at 20°C using monobromonaphthalene as the interfacial solution.

[0365] A higher refractive index nD is preferred; for example, in the case of XR films, a refractive index of 1.595 or higher is preferred.

[0366] [4] Bending strength

[0367] Using spacers with a width of 1.3 cm, a length of 12.5 cm, and a thickness of 0.2 mm, the material is preheated for 1 to 3 minutes at a hot pressing temperature of 200–250 °C, and then pressurized for 1 minute at a pressure of 20 MPa. The material is then removed along with the spacers and cooled at room temperature. Approximately 1 g of resin sample that has been vacuum dried at 100 °C for 2 hours is used to produce a film with a thickness of 100–200 μm.

[0368] The membrane produced by this method is bent 10 times by hand, with the crease at the center of the length direction, 62.5 mm from the end.

[0369] Using 5 test pieces, the bending strength was evaluated as follows when bent at 180°.

[0370] 〇: No cracks were generated.

[0371] ×: Cracks have formed.

[0372] [5] Charpy impact strength (unnotched)

[0373] After drying the resin samples at 120°C for 4 hours, they were injection molded using an injection molding machine (NEX80-9 EG) manufactured by Nissei Resin Industries, Ltd., under conditions of barrel temperature 280°C, mold temperature 80°C, screw speed 100 rpm, and molding cycle 50 seconds to produce ISO multipurpose test pieces (4 mm thick). The obtained test pieces were then subjected to Charpy impact testing (unnotched) based on ISO 179 at room temperature (23°C).

[0374] In this Charpy impact test, the undamaged condition is designated as "NB". The damaged condition is designated as "Break". The Charpy impact strength (unit: kJ / m²) is then calculated. 2 The value is recorded in parentheses.

[0375] [Manufacturing Examples 1-4: Polycarbonate Resin]

[0376] Examples of manufacturing PC (A1), PC (A2), PC (B3), and PC (B4) as polycarbonate resins are shown.

[0377] [Manufacturing Example 1]

[0378] A 150 ml glass reactor equipped with a reactor stirrer, reactor heating device, and reactor pressure adjustment device was prepared by adding 95.42 g (approximately 0.218 mol) of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (BPEF) (manufactured by Osaka Gas Chemicals), 21.29 g (0.093 mol) of 2,2-bis(4-hydroxyphenyl)propane (BPA) (manufactured by Mitsubishi Chemicals), 68.92 g (approximately 0.322 mol) of diphenyl carbonate (DPC) (manufactured by Mitsubishi Chemicals), and a 0.2% by mass aqueous solution of calcium acetate as a catalyst, such that the calcium acetate content is 1.0 μmol per mol of all dihydroxy compounds.

[0379] Next, the pressure inside the glass reactor was reduced to approximately 50 Pa (0.38 Torr), and this process of restoring the pressure to atmospheric pressure with nitrogen was repeated three times to perform nitrogen purging of the reactor's interior. After nitrogen purging, the external temperature of the reactor was set to 220°C, and the internal temperature of the reactor was gradually increased to dissolve the mixture. Then, the stirrer was rotated at 100 rpm. Subsequently, while distilling away the phenol byproduct from the oligomerization reaction of the dihydroxy compound with DPC occurring inside the reactor, the pressure inside the reactor was reduced from 101.3 kPa (760 Torr) to 13.3 kPa (100 Torr) using an absolute pressure gauge over 40 minutes.

[0380] Next, the pressure inside the reactor was maintained at 13.3 kPa, and the phenol was further distilled off while an 80-minute transesterification reaction was carried out. Then, the pressure inside the reactor was reduced from 13.3 kPa (100 Torr) to 399 Pa (3 Torr) using an absolute pressure gauge over 40 minutes, and the distilled phenol was discharged from the system. Subsequently, the external temperature of the reactor was raised to 260°C, and the absolute pressure inside the reactor was reduced to 30 Pa (approximately 0.2 Torr) to carry out a polycondensation reaction. The polycondensation reaction was terminated when the reactor agitator reached the predetermined stirring power.

[0381] Next, the pressure inside the reactor was restored to 101.3 kPa (absolute pressure) using nitrogen, and then increased to 0.2 MPa (gauge pressure). Polycarbonate resin was then extracted from the bottom of the reactor in strands, yielding strands of polycarbonate resin. These strands were then granulated using a rotary cutter.

[0382] The viscosity-average molecular weight of the polycarbonate resin PC (A1) thus obtained is shown in Table 1.

[0383] [Manufacturing Example 2]

[0384] A raw material mixture was prepared by adding 76.75 parts (approximately 0.175 mol) of BPEF (manufactured by Osaka Gas Chemicals), 39.96 parts (approximately 0.175 mol) of BPA (manufactured by Mitsubishi Chemical), 78.74 parts (approximately 0.368 mol) of DPC (manufactured by Mitsubishi Chemical), and a 0.2% by mass aqueous solution of calcium acetate as a catalyst, such that the calcium acetate content is 0.5 μmol per mol of all dihydroxy compounds. Otherwise, the process was carried out according to the method described in Manufacturing Example 1.

[0385] The viscosity-average molecular weight of the polycarbonate resin PC (A2) thus obtained is shown in Table 1.

[0386] [Manufacturing Example 3]

[0387] A raw material mixture was prepared by adding 116.71 parts (approximately 0.266 mol) of BPEF (manufactured by Osaka Gas Chemicals), 54.22 parts (approximately 0.253 mol) of DPC (manufactured by Mitsubishi Chemicals), and a 0.2% by mass aqueous solution of sodium bicarbonate as a catalyst to a 150 ml glass reactor equipped with a reactor stirrer, reactor heating device, and reactor pressure adjustment device, such that the sodium bicarbonate content was 6.0 μmol per mol of all dihydroxy compounds.

[0388] Next, the pressure inside the glass reactor was reduced to approximately 50 Pa (0.38 Torr), and then the process of restoring it to atmospheric pressure with nitrogen was repeated three times to purge the reactor with nitrogen. Then, the reactor was heated to 215°C and stirred for 1 hour under a nitrogen atmosphere of 760 Torr. The pressure was then adjusted to 150 Torr over 15 minutes, and the transesterification reaction was carried out at 215°C and 150 Torr for 20 minutes. The temperature was further increased to 240°C at a rate of 37.5°C / hour, and held at 240°C and 150 Torr for 10 minutes. Then, the pressure was adjusted to 120 Torr over 10 minutes, and held at 240°C and 120 Torr for 70 minutes. Then, the pressure was adjusted to 100 Torr over 10 minutes, and held at 240°C and 100 Torr for 10 minutes. Finally, the pressure was set below 1 Torr for 40 minutes, and the polymerization reaction was carried out at 240°C and below 1 Torr.

[0389] The polycondensation reaction ends when the reactor agitator reaches the preset stirring power.

[0390] Next, the pressure inside the reactor was restored to 101.3 kPa (absolute pressure) using nitrogen, and then increased to 0.2 MPa (gauge pressure). Polycarbonate resin was then extracted from the bottom of the reactor in strands, yielding strands of polycarbonate resin. These strands were then granulated using a rotary cutter.

[0391] The viscosity-average molecular weight of the polycarbonate resin PC (B3) thus obtained is shown in Table 1.

[0392] [Manufacturing Example 4]

[0393] A mixture of raw materials was prepared by adding 104.74 parts (approximately 0.239 mol) of BPEF (manufactured by Osaka Gas Chemicals), 11.97 parts (approximately 0.052 mol) of BPA (manufactured by Mitsubishi Chemicals), 64.27 parts (approximately 0.300 mol) of DPC (manufactured by Mitsubishi Chemicals), and a 0.2% by mass aqueous solution of calcium acetate as a catalyst, such that the calcium acetate content is 0.5 μmol per mol of all dihydroxy compounds. Otherwise, the method described in Example 1 was followed.

[0394] The viscosity-average molecular weight of the polycarbonate resin PC (B4) thus obtained is shown in Table 1.

[0395] [Table 1]

[0396]

[0397] [Examples 1-5, Comparative Examples 1-5: Polycarbonate Resin Compositions]

[0398] The PC(A1), PC(A2), PC(B3), and PC(B4) obtained in Manufacturing Examples 1-4, along with the raw materials listed in Tables 2 and 3, were blended in the proportions (mass ratios) shown in Table 4 below. After mixing in a drum for 20 minutes, the mixture was fed into a φ30mm twin-screw extruder (TEX30α) manufactured by Nippon Steel Works Co., Ltd., equipped with one vent, and compounded under conditions of a screw speed of 160 rpm, a discharge rate of 15 kg / h, and a barrel temperature of 260°C. The resulting molten resin was extruded into strands, rapidly cooled in a water bath, and granulated using a granulator to obtain various polycarbonate resin compositions.

[0399] For each polycarbonate resin composition thus obtained, the viscosity-average molecular weight was determined, and the transparency, flexural strength, refractive index, and unnotched Charpy impact strength were evaluated. The results are shown in Table 4.

[0400] It should be noted that Comparative Examples 1 and 4 have poor transparency, therefore their refractive index cannot be evaluated.

[0401] [Table 2]

[0402]

[0403] [Table 3]

[0404]

[0405] [Table 4]

[0406]

[0407] As shown in Table 4, the polycarbonate resin compositions of Examples 1 to 5, which conform to the present invention, have high refractive index, excellent transparency and strength.

[0408] Comparative Example 1 is equivalent to Example 4 of Patent Document 1 above, but the polycarbonate resin (B3) containing only BPEF units has poor compatibility and poor transparency with the polycarbonate resins (C3) and (C4) containing only BPA units. Furthermore, due to poor compatibility and low molecular weight, the strength is also poor.

[0409] Comparative Examples 2 and 3, which contain only BPA units, have good transparency and strength but low refractive index.

[0410] The polycarbonate resin composition of Comparative Example 4 used a polycarbonate resin (B4) containing BPEF units and BPA units. The polycarbonate resin (B4) contained a high proportion of BPEF units. The proportion of BPEF units in the polycarbonate resin composition did not meet the scope of the present invention. Therefore, it had poor transparency and poor strength, just like Comparative Example 1.

[0411] The polycarbonate resin composition of Comparative Example 5 contains BPEF units in a much larger proportion than that of the present invention, and therefore has poor strength.

[0412] The invention has been described in detail using specific methods, but it will be clear to those skilled in the art that various modifications can be made without departing from the intent and scope of the invention.

[0413] This application is based on Japanese Patent Application No. 2023-177647, filed on October 13, 2023, the entire contents of which are incorporated herein by reference.

Claims

1. A polycarbonate resin composition comprising 16-63% by mass of repeating unit (a) of formula (1) below and 37-84% by mass of repeating unit (d) of formula (6) below, wherein the polycarbonate resin composition has a viscosity-average molecular weight of 15,000 or more. [Chemical Formula 1] In equation (1), R 1 and R 2 Each can be used independently to represent a hydrogen atom or a methyl group. [Chemical Formula 2] In equation (6), R 15 ~R 18 Each of the following is independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a group containing an aryl group having 6 to 12 carbon atoms, and W represents at least one selected from a single bond, an oxygen atom, a sulfur atom, a sulfinyl group, a sulfonyl group, and a divalent organic group.

2. A polycarbonate resin composition comprising 30-70% by weight of a polycarbonate copolymer (A) and 70-30% by weight of a polycarbonate resin (B), wherein, The polycarbonate copolymer (A) contains repeating units (a) as shown in formula (1) and repeating units (b) as shown in formula (2) in a ratio of repeating unit (a): repeating unit (b) = 50-85% by mass: 50-15% by mass. The polycarbonate resin (B) contains more than 95% by mass of the repeating unit (c) shown in the following formula (3). The content of the repeating unit (a) shown in the following formula (1) is 16 to 63% by mass, and the viscosity-average molecular weight of the polycarbonate resin composition is 15,000 or more. [Chemical Formula 3] In equation (1), R 1 and R 2 Each can be used independently to represent a hydrogen atom or a methyl group. [Chemical Formula 4] In equation (2), R 3 and R 4 Each can be used independently to represent a hydrogen atom or a methyl group. [Chemical Formula 5] In equation (3), R 5 and R 6 Each can be used to represent a hydrogen atom or a methyl group independently.

3. The polycarbonate resin composition according to claim 1 or 2, wherein, The evaluation result of the unnotched Charpy impact strength of the polycarbonate resin composition, measured according to ISO 179, is NB, i.e., unbroken.

4. The polycarbonate resin composition according to claim 1 or 2, wherein, The refractive index nD of the polycarbonate resin composition is 1.595 or higher.

5. The polycarbonate resin composition according to claim 1, wherein the polycarbonate resin composition comprises two or more polycarbonate resins in different proportions, including the repeating unit (a) shown in formula (1). In the following membrane transparency test, it is possible to read text from above through the membrane. <Membrane Transparency Test> Approximately 4g of resin sample, vacuum dried at 100℃ for 2 hours, was used with spacers 8cm wide, 8cm long, and 1.0mm thick. The sample was preheated at 230℃ for 2 minutes using a hot press, and then pressurized at 20MPa for 1 minute. The sample, along with the spacers, was then removed and cooled to room temperature to produce a 900μm thick membrane. The film made by the method is laid on paper with printed text, and it is confirmed whether the text printed on the paper can be read from above through the film.

6. The polycarbonate resin composition according to claim 2, wherein, In the following membrane transparency test, it is possible to read text from above through the membrane. <Membrane Transparency Test> Approximately 4g of resin sample, vacuum dried at 100℃ for 2 hours, was used with spacers 8cm wide, 8cm long, and 1.0mm thick. The sample was preheated at 230℃ for 2 minutes using a hot press, and then pressurized at 20MPa for 1 minute. The sample, along with the spacers, was then removed and cooled to room temperature to produce a 900μm thick membrane. The film made by the method is laid on paper with printed text, and it is confirmed whether the text printed on the paper can be read from above through the film.

7. The polycarbonate resin composition according to claim 1 or 2, wherein, In the above formula (1), R 1 and R 2 It is a hydrogen atom.

8. The polycarbonate resin composition according to claim 1, wherein, In equation (6), W is -CR 19 R 20 -or a cycloalkane group having 3 to 10 carbon atoms, wherein the -CR 19 R 20 -Chinese R 19 and R 20 Each is independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms.

9. The polycarbonate resin composition according to claim 2, wherein, In the above formula (2), R 3 and R 4 It is a hydrogen atom.

10. The polycarbonate resin composition according to claim 2, wherein, In the above formula (3), R 5 and R 6 It is a hydrogen atom.

11. The polycarbonate resin composition according to claim 1 or 2, wherein, The viscosity-average molecular weight is below 26,000.

12. The polycarbonate resin composition according to claim 1 or 2, wherein, The polycarbonate resin composition comprises 16 to 53% by mass of the repeating unit (a) shown in formula (1).

13. The polycarbonate resin composition according to claim 12, wherein, The polycarbonate resin composition comprises 18 to 47% by mass of the repeating unit (a) shown in formula (1).

14. A molded article made using the polycarbonate resin composition according to claim 1 or 2.

15. A projector for XR, which is made using a polycarbonate resin composition comprising repeating units (a) as shown in formula (1) below and having a viscosity-average molecular weight of 15,000 or more. [Chemical Formula 6] In equation (1), R 1 and R 2 Each can be used to represent a hydrogen atom or a methyl group independently.

16. The XR projection body according to claim 15, wherein, The polycarbonate resin composition is the polycarbonate resin composition according to claim 1 or 2.

17. An XR membrane, which is made using a polycarbonate resin composition comprising repeating units (a) as shown in formula (1) and having a viscosity-average molecular weight of 15,000 or more, [Chemical Formula 7] In equation (1), R 1 and R 2 Each can be used to represent a hydrogen atom or a methyl group independently.

18. The XR membrane according to claim 17, wherein, The polycarbonate resin composition comprises 16 to 63% by mass of the repeating unit (a) shown in formula (1).

19. The XR membrane according to claim 17, wherein, The polycarbonate resin composition comprises more than 63% by mass and less than 100% by mass of the repeating unit (a) shown in formula (1).

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