Polycarbonate resin and polycarbonate resin solution

Abstract

In the case of reactive polycarbonates, there was a problem that the reactivity of the crosslinking reaction was inferior. In addition, in conventional reactive polycarbonates that require secondary components such as polymerization initiators, there was a tendency for inferior versatility as they could not be used for various applications. The above problem was solved by a polycarbonate resin comprising a monomer-derived constituent unit (A) represented by the following general formula (1) and / or a monomer-derived constituent unit (B) represented by the following general formula (2) and a monomer-derived constituent unit (C) represented by the following general formula (3), wherein the ratio of the total of constituent units (A) and constituent unit (B) to the total moles of constituent units (A) to (C) constituting the polycarbonate resin is 0.5 to 25 mol% and the ratio of constituent unit (C) is 75 to 99.5 mol%. R11 to R38 in formulas (1) to (3) are as shown in the present specification.

Description

Technology Field

[0001] The present invention relates to a polycarbonate resin, a polycarbonate resin solution, etc. Background Technology

[0002] Reactive polycarbonate (reactive PC) resins containing reactive sites are known (Patent Documents 1 to 3, etc.). Reactive polycarbonate resins contain reaction-active sites for polymerization reactions, and terminal reactive polycarbonates having reactive groups at their ends are widely used. Reactive polycarbonate resins are typically used as compositions to which polymerization initiators, additives, etc. are added, and polymers are produced from such resin compositions through polymerization reactions. Prior art literature

[0003] Japanese Patent Publication No. WO2021 / 241378, Japanese Patent Publication No. Sho 54-064592, Japanese Patent Publication No. Hei 11-172003 The problem to be solved

[0004] Most existing reactive PCs are manufactured using terminal stoppers having functional groups, and only the terminal portions are reactive. In the case of terminal reactive polycarbonates obtained in this way, the reactive active sites are limited to the terminals, and the crosslinking reactivity is often inferior.

[0005] In addition, in the case of reactive PCs that require secondary components such as polymerization initiators to initiate a polymerization reaction, the range of choices for additives is limited, and it is necessary to provide for the polymerization reaction under predetermined reaction conditions. For this reason, conventional reactive PCs cannot be used for various applications and tend to have inferior versatility. means of solving the problem

[0006] The present invention includes, for example, the following.

[0007] [1] A monomer-derived constituent unit (A) represented by the following general formula (1) and / or a monomer-derived constituent unit (B) represented by the following general formula (2), and

[0008] A polycarbonate resin comprising a monomer-derived constituent unit (C) represented by the following general formula (3),

[0009] A polycarbonate resin having a ratio of the sum of the constituent units (A) and (B) to the total moles of the constituent units (A) to (C) constituting the polycarbonate resin, wherein the ratio of the sum of the constituent units (A) and (B) is 0.5 to 25 mol% and the ratio of the constituent unit (C) is 75 to 99.5 mol%.

[0010] [Chemical Formula 1]

[0011]

[0012] (of general formula (1),

[0013] R 11 ~ R 14 and R 15 ~ R 18 Each independently represents a C1-20 alkyl group, a C6-12 aryl group, a C2-12 alkenyl group, a C1-5 alkoxy group, or a C7-17 aralkyl group, which may each have hydrogen, fluorine, chlorine, bromine, or iodine, or a substituent, and

[0014] Among general formulas (2),

[0015] R 21 ~ R 25 and R 26 ~ R 28 Each represents, independently, hydrogen, fluorine, chlorine, bromine, or iodine, or a C1-20 alkyl group, a C6-12 aryl group, a C2-12 alkenyl group, a C1-5 alkoxy group, or a C7-17 aralkyl group, which may each have a substituent.

[0016] [Chemical Formula 2]

[0017]

[0018] (of general formula (3),

[0019] R 31 ~ R 34 and R 35 ~ R 38 Each independently represents a C1-20 alkyl group, a C6-12 aryl group, a C2-12 alkenyl group, a C1-5 alkoxy group, or a C7-17 aralkyl group, which may each have hydrogen, fluorine, chlorine, bromine, or iodine, or a substituent, and

[0020] X is,

[0021] [Chemical Formula 3]

[0022]

[0023] And,

[0024] Here, R5 and R6 each independently represent hydrogen, fluorine, chlorine, bromine, or iodine, or a C1 to C20 alkyl group, a C1 to C5 alkoxy group, or a C6 to C12 aryl group that may each have a substituent, or R5 and R6 represents a group that combines to form a carbon ring having 5 to 20 carbon atoms or a complex ring having 5 to 12 atoms (except where both R5 and R6 are methyl groups),

[0025] R7 and R8 each independently represent hydrogen, fluorine, chlorine, bromine, or iodine, or a C1-9 alkyl group, a C1-5 alkoxy group, a C2-12 alkenyl group, or a C6-12 aryl group, which may each have a substituent, and

[0026] c represents an integer from 0 to 20.

[0027] [2] The polycarbonate resin described in [1], wherein the ratio of the constituent unit (A) and the constituent unit (B) to the total moles of the constituent units (A) to (C) constituting the polycarbonate resin is 5 to 20 mol%, and the ratio of the constituent unit (C) is 80 to 95 mol%.

[0028] [3] In the above general formula (1),

[0029] R 11 ~ R 14 and R 15 ~ R 18 Each of these independently represents a C1- to C20 alkyl group or a C1- to C5 alkoxy group, which may each have hydrogen or a substituent, and

[0030] In general formula (2),

[0031] R 21 ~ R 25 and R 26 ~ R 28 The polycarbonate resin described in [1] or [2], for example, described in [1], which represents a carbon 1 to 20 alkyl group or a carbon 1 to 5 alkoxy group, each of which may independently have hydrogen or a substituent.

[0032] [4] A polycarbonate resin, for example, described in [3], wherein the monomer represented by the above general formula (1) is represented by the following formula (1-1), and the monomer represented by the above general formula (2) is represented by the following formula (2-1).

[0033] [Chemical Formula 4]

[0034]

[0035] [5] In the above general formula (3),

[0036] R 31 ~ R 34 and R 35 ~ R38 Each of these independently represents a C1- to C20 alkyl group or a C1- to C5 alkoxy group, which may each have hydrogen or a substituent, and

[0037] The above X,

[0038] [Chemical Formula 5]

[0039]

[0040] And,

[0041] Here, R5 and R6 each independently represent a C1 to C20 alkyl group or a C6 to C12 aryl group that may each have hydrogen or a substituent, or R5 and R6 combine to form a carbon ring with C5 to C20 or a complex ring with C5 to C12, and

[0042] R7 and R8 each independently represent hydrogen, or each may have a substituent, an alkyl group having 1 to 9 carbon atoms or an aryl group having 6 to 12 carbon atoms, any one of [1] to [4], for example, the polycarbonate resin described in [1].

[0043] [6] A polycarbonate resin, for example, described in [5], wherein the monomer represented by the above general formula (3) is selected from the group consisting of the following formulas (3-1) to (3-4).

[0044] [Chemical Formula 6]

[0045]

[0046] [7] The end structure of the above polycarbonate resin is represented by the following formula (4), any one of [1] to [6], for example, the polycarbonate resin described in [1].

[0047] [Chemical Formula 7]

[0048]

[0049] (Of general formula (4),

[0050] A is a vinyl group, an isopropenyl group, a styryl group, or a methine group, and

[0051] R1 and R2 are each independently selected from the group consisting of a single bond and a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, and

[0052] R3 is each independently selected from the group consisting of a hydrogen atom, a hydroxyl group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C10 alkoxy group, a substituted or unsubstituted C6 to C12 aryl group, and a substituted or unsubstituted C5 to C12 heteroaryl group, and

[0053] Z is each independently selected from the group consisting of a single bond, an ether group, a carbonyl group, and an ester group, and

[0054] a is an integer from 0 to 3, and

[0055] b is an integer from 1 to 4, and

[0056] Y is an ether group or an ester group.)

[0057] [8] Any one of [1] to [7], for example, the polycarbonate resin described in [1], wherein the terminal structure of the above polycarbonate resin is derived from a compound selected from the group consisting of pt-butylphenol (PTBP), 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole (MBZT), 4-hydroxybenzophenone (4-HBP), polyoxyalkylene-monoalkyl ether, and p-hydroxyphenylethanol (PHEP).

[0058] [9] Any one of [1] to [8], for example, the polycarbonate resin described in [1], which does not contain unsaturated bonds in the main chain of the polycarbonate resin.

[0059]

[10] Monomer (a) represented by the following general formula (1) and / or monomer (b) represented by the following general formula (2),

[0060] A polymerization monomer mixture for forming a constituent unit of a thermoplastic resin comprising a monomer (c) represented by the following general formula (3),

[0061] A polymerization monomer mixture, wherein, with respect to the total moles of monomers (a) to (c), the ratio of the total of monomers (a) and (b) is 0.5 to 25 mol% and the ratio of monomer (c) is 75 to 99.5 mol%.

[0062] [Chemical Formula 8]

[0063]

[0064] (of general formula (1),

[0065] R 11 ~ R 14 and R 15 ~ R 18 Each independently represents a C1-20 alkyl group, a C6-12 aryl group, a C2-12 alkenyl group, a C1-5 alkoxy group, or a C7-17 aralkyl group, which may each have hydrogen, fluorine, chlorine, bromine, or iodine, or a substituent, and

[0066] Among general formulas (2),

[0067] R 21 ~ R 25 and R 26 ~ R 28 Each represents, independently, hydrogen, fluorine, chlorine, bromine, or iodine, or a C1-20 alkyl group, a C6-12 aryl group, a C2-12 alkenyl group, a C1-5 alkoxy group, or a C7-17 aralkyl group, which may each have a substituent.

[0068] [Chemical Formula 9]

[0069]

[0070] (of general formula (3),

[0071] R 31 ~ R 34 and R 35 ~ R 38 Each independently represents a C1-20 alkyl group, a C6-12 aryl group, a C2-12 alkenyl group, a C1-5 alkoxy group, or a C7-17 aralkyl group, which may each have hydrogen, fluorine, chlorine, bromine, or iodine, or a substituent, and

[0072] X is,

[0073] [Chemical Formula 10]

[0074]

[0075] And,

[0076] Here, R5 and R6 each independently represent hydrogen, fluorine, chlorine, bromine, or iodine, or a C1 to C20 alkyl group, a C1 to C5 alkoxy group, or a C6 to C12 aryl group which may each have a substituent, or R5 and R6 combine to form a C5 to C20 carbon ring or a C5 to C12 complex ring (except where both R5 and R6 are methyl groups),

[0077] R7 and R8 each independently represent hydrogen, fluorine, chlorine, bromine, or iodine, or a C1-9 alkyl group, a C1-5 alkoxy group, a C2-12 alkenyl group, or a C6-12 aryl group, which may each have a substituent, and

[0078] c represents an integer from 0 to 20.

[0079]

[11] Any one of [1] to [9] above, for example, the polycarbonate resin described in [1] above and a polycarbonate resin solution comprising a solvent.

[0080]

[12] The above-described polycarbonate resin solution, which includes at least a (meth)acrylic acid ester solvent.

[11]

[0081]

[13] The above (meth)acrylic acid ester is tetrahydrofurfuryl methacrylate (THF-M), a polycarbonate resin solution described in

[12] .

[0082]

[14] Any one of

[11] to

[13] , for example, the polycarbonate resin solution described in

[11] , wherein the concentration of the polycarbonate resin is 1 to 20 mass% based on the total mass of the polycarbonate resin solution.

[0083]

[15] A method for manufacturing a cross-linked polycarbonate resin, characterized by performing ultraviolet irradiation on the polycarbonate resin solution described in

[11] as any one of

[11] to

[14] above.

[0084]

[16] Cross-linked polycarbonate resin obtained by the manufacturing method described in

[15] above.

[0085]

[17] A molded body comprising the cross-linked polycarbonate resin described in

[16] above. Effects of the invention

[0086] According to the present invention, it is possible to realize a polycarbonate resin in which the reactivity of polymerization and crosslinking reactions can be easily adjusted based on the number of functional groups, polymerization can be performed using the resin alone without additives such as polymerization initiators, and the degree of freedom of the physical properties of the obtained polymer can be improved. In the polycarbonate resin of the present invention, reactivity can be maintained even in a long-chain, i.e., polymeric state.

[0087] In addition, according to the present invention, a polymerization monomer mixture suitable for manufacturing the polycarbonate resin described above, a polycarbonate resin solution comprising a polycarbonate resin and a solvent, etc., can also be realized. Specific details for implementing the invention

[0088] Preferred embodiments of the present invention will be described in detail below.

[0089] <1. Polycarbonate Resin> 1-1. Constituent Units of Polycarbonate Resin and Their Content

[0090] The polycarbonate resin comprises at least one of a monomer-derived constituent unit (A) represented by general formula (1) and a monomer-derived constituent unit (B) represented by general formula (2).

[0091] [Chemical Formula 11]

[0092]

[0093] In general formula (1), R 11 ~ R 14 and R 15 ~ R 18 Each represents, independently, hydrogen, fluorine, chlorine, bromine, or iodine, or a carbon 1 to 20 alkyl group, a carbon 6 to 12 aryl group, a carbon 2 to 12 alkenyl group, a carbon 1 to 5 alkoxy group, or a carbon 7 to 17 aralkyl group, which may each have a substituent.

[0094] R in general formula (1) 11 ~ R 14 and R 15 ~ R 18 R represents, preferably, an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, which may each independently have hydrogen or a substituent. 11 ~ R 14 and R 15 ~ R 18More preferably, it represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, which may each independently have hydrogen or a substituent, and more preferably, it represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 2 carbon atoms, which may each independently have hydrogen or a substituent.

[0095] Also, R 11 ~ R 14 and R 15 ~ R 18 Of these, at least 5 are preferably hydrogen, more preferably 6 or more are hydrogen, and even more preferably 7 or more are hydrogen or all are hydrogen.

[0096] A preferred embodiment of the monomer represented by general formula (1) is represented by the following formula (1-1).

[0097] [Chemical Formula 12]

[0098]

[0099] In the general formula (2) described above, R 21 ~ R 25 and R 26 ~ R 28 Each represents, independently, hydrogen, fluorine, chlorine, bromine, or iodine, or a carbon 1 to 20 alkyl group, a carbon 6 to 12 aryl group, a carbon 2 to 12 alkenyl group, a carbon 1 to 5 alkoxy group, or a carbon 7 to 17 aralkyl group, which may each have a substituent.

[0100] R in general formula (2) 21 ~ R 25 and R 26 ~ R 28 R represents, preferably, an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, which may each independently have hydrogen or a substituent. 21 ~ R 25 and R26 ~ R 28 More preferably, it represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, which may each independently have hydrogen or a substituent, and more preferably, it represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 2 carbon atoms, which may each independently have hydrogen or a substituent.

[0101] Also, R 21 ~ R 25 and R 26 ~ R 28 Of these, at least 5 are preferably hydrogen, more preferably 6 or more are hydrogen, and even more preferably 7 or more are hydrogen or all are hydrogen.

[0102] A preferred embodiment of the monomer represented by general formula (2) is represented by the following formula (2-1).

[0103] [Chemical Formula 13]

[0104]

[0105] The constituent units (A) and (B) included in the main chain of the polycarbonate resin both function as polymerizable reaction active groups. For this reason, the polycarbonate resin can generate a polymerization reaction by irradiation with energy rays, such as ultraviolet rays, even without containing special additives for polymerization, such as polymerization initiators. This is because a cross-linking reaction similar to the benzopinacol synthesis reaction between two molecules of compounds represented by the above general formula (1) or (2) occurs.

[0106] A polycarbonate resin containing either of such constituent units (A) and (B) can maintain reactivity even though it is a long-chain polymer. In addition, in a polycarbonate resin having constituent units (A) or (B), it is possible to form crosslinking sites in a wide range of areas other than the ends, and it is also easy to adjust the reactivity according to the amount of monomer represented by general formula (1) or (2).

[0107] The polycarbonate resin additionally comprises a monomer-derived constituent unit (C) represented by the general formula (3).

[0108] [Chemical Formula 14]

[0109]

[0110] In general formula (3), R 31 ~ R 34 and R 35 ~ R 38 Each represents, independently, hydrogen, fluorine, chlorine, bromine, or iodine, or a carbon 1 to 20 alkyl group, a carbon 6 to 12 aryl group, a carbon 2 to 12 alkenyl group, a carbon 1 to 5 alkoxy group, or a carbon 7 to 17 aralkyl group, which may each have a substituent.

[0111] R in general formula (3) 31 ~ R 34 and R 35 ~ R 38 R represents, preferably, an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, which may each independently have hydrogen or a substituent. 31 ~ R 34 and R 35 ~ R 38More preferably, it represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, which may each independently have hydrogen or a substituent, and more preferably, it represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 2 carbon atoms, which may each independently have hydrogen or a substituent.

[0112] Also, R 31 ~ R 34 and R 35 ~ R 38 Of these, at least 5 are preferably hydrogen, more preferably 6 or more are hydrogen, and even more preferably 7 or more are hydrogen or all are hydrogen.

[0113] Also, in general formula (3), X is represented by any of the following formulas.

[0114] [Chemical Formula 15]

[0115]

[0116] In the above formula, R5 and R6 each independently represent a C1-20 alkyl group, a C1-5 alkoxy group, or a C6-12 aryl group, which may each have hydrogen, fluorine, chlorine, bromine, or iodine, or a substituent, or R5 and R6 combine to form a carbon ring with 5-20 carbon atoms or a complex ring with 5-12 atoms, but R5 and R6 are not both methyl groups.

[0117] In the above formula, R7 and R8 each independently represent hydrogen, fluorine, chlorine, bromine, or iodine, or each may have a substituent, an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms.

[0118] In addition, in the above formula, c represents an integer of 0 to 20, preferably 1 to 15, more preferably 1 to 10.

[0119] Also, in general formula (3), X is preferably represented by any of the following formulas.

[0120] [Chemical Formula 16]

[0121]

[0122] Here, R5 and R6 each independently represent a carbon-1 to 20 alkyl group or a carbon-6 to 12 aryl group that may each have hydrogen or a substituent, or R5 and R6 combine to form a carbon ring with 5 to 20 carbons or a complex ring with 5 to 12 atoms.

[0123] In addition, R7 and R8 each independently represent a carbon-1 to carbon-9 alkyl group or a carbon-6 to carbon-12 aryl group, which may each have hydrogen or a substituent.

[0124] In X of general formula (3), R5 and R6 are, more preferably, each independently hydrogen or an alkyl group having 1 to 12 carbon atoms that may have a substituent, or R5 and R6 are combined to form a carbon ring having 5 to 20 carbon atoms that may have a substituent, more preferably a carbon ring having 6 to 12 carbon atoms that may have a substituent.

[0125] Also, R7 and R8 in X of general formula (3) are each independently hydrogen, or carbon 1 to 5 alkyl groups or carbon 6 to 8 aryl groups that may each have a substituent.

[0126] Preferred embodiments of the monomer represented by general formula (3) are represented by the following formulas (3-1) to (3-4).

[0127] [Chemical Formula 17]

[0128]

[0129] In a polycarbonate resin, the ratio of the total of constituent unit (A) and constituent unit (B) to the total moles of constituent units (A) to (C) constituting the polycarbonate resin is 0.5 to 25 mol%. The ratio of the total moles of constituent unit (A) and constituent unit (B) to the total moles of constituent units (A) to (C) is preferably 1 to 22 mol% or 2 to 24 mol%, more preferably 3 to 18 mol%, 5 to 15 mol% (greater than 5 mol% or 5 mol% or more and 15 mol% or less), 5 to 20 mol% (greater than 5 mol% or 5 mol% or more and 20 mol% or less), or 5 to 25 mol% (greater than 5 mol% or 5 mol% or more and 25 mol% or less), and particularly preferably 5 to 20 mol%.

[0130] In the polycarbonate resin, the proportion of constituent unit (C) is 75 to 99.5 mol% with respect to the total molar amount of constituent units (A) to (C) constituting the polycarbonate resin. The proportion of the molar amount of constituent unit (C) to the total molar amount of constituent units (A) to (C) is preferably 76 to 96 mol% or 78 to 98 mol%, and more preferably 79 to 97 mol%, 75 to 95 mol% (75 mol% or more and less than 95 mol% or 95 mol% or less), 80 to 95 mol% (80 mol% or more and less than 95 mol% or 95 mol% or less), 85 to 95 mol% (85 mol% or more and less than 95 mol% or 95 mol% or less), etc.

[0131] In addition, the description of the range (mol%) regarding the content of the above-described constituent units (A) to (C) (including both the content of the sum of constituent unit (A) and constituent unit (B) and the content of constituent unit (C)) includes a range of less than or equal to the upper limit and less than the upper limit, and also includes a range of greater than or equal to the lower limit and greater than the lower limit.

[0132] In a polycarbonate resin, when a constituent unit other than constituent units (A) to (C) is included, it is preferable that the ratio of the sum of constituent unit (A) and constituent unit (B) to the total moles of all constituent units is 0.5 to 25 mol%, more preferable that it is 1 to 22 mol% or 2 to 24 mol%, more preferable that it is 3 to 18 mol%, 5 to 15 mol% (greater than 5 mol% or 5 mol% or more and 15 mol% or less), 5 to 20 mol% (greater than 5 mol% or 5 mol% or more and 20 mol% or less), or 5 to 25 mol% (greater than 5 mol% or 5 mol% or more and 25 mol% or less), and particularly preferable that it is 5 to 20 mol%.

[0133] In addition, in the case where a constituent unit other than constituent units (A) to (C) is included in the polycarbonate resin, it is preferable that the ratio of the total of constituent units (C) to the total moles of all constituent units is 75 to 99.5 mol%, more preferable that it is 76 to 96 mol% or 78 to 98 mol%, and may be 79 to 97 mol%, 75 to 95 mol% (75 mol% or more and less than 95 mol% or 95 mol% or less), 80 to 95 mol% (80 mol% or more and less than 95 mol% or 95 mol% or less), 85 to 95 mol% (85 mol% or more and less than 95 mol% or 95 mol% or less), etc.

[0134] In addition, regarding the content of the above-described constituent units (A) to (C) (including both the content of the sum of constituent unit (A) and constituent unit (B) and the content of constituent unit (C)), the range description (mol%) includes a range below the upper limit and below the upper limit, and also includes a range above the lower limit and above the lower limit.

[0135] In the case of a polycarbonate resin, it is preferable that the total moles of constituent units (A) to (C) are 50 mol% or more based on the total moles of all constituent units, more preferable that they are 70 mol% or more, even more preferable that they are 90 mol% or more, and particularly preferable that they are 95 mol% or more or substantially 100 mol%.

[0136] The substituents described above in the constituent units (A) to (C) of the polycarbonate resin are each independently selected from halogens, hydroxyl groups, cyano groups, alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 12 carbon atoms, etc., and when alkyl groups, alkenyl groups, and aryl groups are included as substituents, the R described above 11 ~ R 38 The number of carbon atoms in this case is the total number of carbon atoms including the carbons of the substituents.

[0137] Among all constituent units in the polycarbonate resin, the total moles of constituent units having unsaturated bonds are preferably 10 mol% or less based on the total moles of all constituent units, more preferably 5 mol% or less, and even more preferably 3 mol% or less. In addition, it is particularly preferable that the polycarbonate resin does not contain unsaturated bonds.

[0138] 1-2. Terminal structure of polycarbonate resin

[0139] The end structure of the polycarbonate resin is preferably represented by the following formula (4).

[0140] [Chemical Formula 18]

[0141]

[0142] In general formula (4), A is a vinyl group, an isopropenyl group, a styryl group, or a methine group, preferably a vinyl group.

[0143] In general formula (4), R1 and R2 are each independently selected from the group consisting of a single bond and a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, preferably selected from a single bond and a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, more preferably selected from a single bond and a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms, and even more preferably selected from a single bond and a substituted or unsubstituted alkylene group having 1 to 3 carbon atoms.

[0144] In general formula (4), R3 is each independently selected from the group consisting of a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and a substituted or unsubstituted heteroaryl group having 5 to 12 atoms. R3 is preferably selected from a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, more preferably selected from a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, and a substituted or unsubstituted alkoxy group having 1 to 3 carbon atoms, and particularly preferably selected from a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, and a substituted or unsubstituted alkoxy group having 1 to 2 carbon atoms.

[0145] In general formula (4), Z is each independently selected from the group consisting of a single bond, an ether group (an O atom bonded to an adjacent carbon atom), a carbonyl group, and an ester group.

[0146] In general formula (4), a is an integer from 0 to 3, preferably an integer from 0 to 2 or from 1 to 3, and more preferably an integer from 0 to 1 or from 1 to 2. Also, in general formula (4), b is an integer from 1 to 4, preferably an integer from 1 to 3, and more preferably an integer from 1 to 2. Also, b may be 0.

[0147] In general formula (4), Y is an ether group or an ester group, preferably an ether group.

[0148] The terminal structure of the polycarbonate resin is preferably derived from a compound selected from the group consisting of pt-butylphenol (PTBP), 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole (MBZT), 4-hydroxybenzophenone (4-HBP), polyoxyalkylene-monoalkyl ether, and p-hydroxyphenylethanol (PHEP).

[0149] In the case where the terminal structure of the polycarbonate resin is substituted, the substituents are each independently selected from halogens, hydroxyl groups, cyano groups, alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 12 carbon atoms, etc., and when alkyl groups, alkenyl groups and aryl groups are included as substituents, the number of carbon atoms in R1 to R3 described above is the total number of carbon atoms including the carbons of the substituents.

[0150] 1-3. Method for manufacturing polycarbonate resin

[0151] Polycarbonate resin can be manufactured according to conventional methods. For example, as follows.

[0152] The polycarbonate resin used in the present invention can be prepared by reacting, for example, a bisphenol derivative that induces constituent units (A) to (C), preferably monomers (a) to (c); a compound such as a monovalent phenol that induces a terminal structure, preferably a monomer having a molecular structure corresponding to the structure of formula (4); and a carbonate-forming compound. A known method may be employed, for example, a direct reaction between a bisphenol derivative and phosgene (phosgene method), or an ester exchange reaction between a bisphenol derivative and a bisaryl carbonate (ester exchange method).

[0153] In the phosgene method, for example, phosgene is reacted with a compound such as a bisphenol that induces constituent units (A) to (C), a monovalent phenol that induces a terminal structure, and a bisphenol that induces a terminal structure, in the presence of a conventional acid binder and a solvent. For example, pyridine or alkali metal hydroxides such as sodium hydroxide or potassium hydroxide are used as the acid binder, and for example, methylene chloride or chloroform is used as the solvent. In addition, to promote the polycondensation reaction, it is preferable to use a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt such as benzyltriethylammonium chloride.

[0154] Compounds such as monovalent phenols that induce terminal structures function as degree of polymerization regulators, but it is also possible to use other monovalent phenols, such as phenol, p-butylphenol, p-cumylphenol, and long-chain alkyl-substituted phenols, in combination at less than 50 mass% relative to the monovalent phenols that induce terminal structures. Additionally, if desired, small amounts of antioxidants such as sodium sulfite or hydrosulfite, or branching agents such as phloroglucin or isatin bisphenol, may be added. The reaction is typically appropriate to be carried out in the range of 0 to 150°C, preferably 5 to 40°C. The reaction time depends on the reaction temperature, but is typically 0.5 minutes to 10 hours, preferably 1 minute to 2 hours. Furthermore, it is desirable to maintain the pH of the reaction system at 10 or higher during the reaction.

[0155] Meanwhile, in the ester exchange method, for example, a compound such as bisphenol that induces constituent units (A) to (C), a monovalent phenol that induces a terminal structure, and a bisaryl carbonate are mixed and reacted at a high temperature under reduced pressure.

[0156] Examples of bis-allyl carbonates include diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, and dinaphthyl carbonate. It is also possible to use two or more of these compounds in combination. The reaction is typically carried out at a temperature in the range of 150 to 350°C, preferably 200 to 300°C, and the reduced pressure is preferably set to 1 mmHg or less at the end to remove phenols derived from the bis-allyl carbonate produced by the ester exchange reaction by distillation out of the system. The reaction time depends on the reaction temperature and reduced pressure, but is typically about 1 to 24 hours. It is preferable to carry out the reaction under an inert gas atmosphere such as nitrogen or argon. In addition, depending on the preference, the reaction may be carried out by adding a small amount of a molecular weight regulator other than a compound such as monovalent phenol that induces a terminal structure, or by adding an antioxidant or a branching agent.

[0157] <2. Monomer mixture for polymerization> The monomer mixture for polymerization comprises a monomer (a) represented by the general formula (1) described above and / or a monomer (b) represented by the general formula (2) described above, and a monomer (c) represented by the general formula (3) described above. The monomer mixture for polymerization is a monomer mixture for polymerization to form a constituent unit of a thermoplastic resin, and is suitably used to manufacture the polycarbonate resin described above.

[0158] A monomer mixture for polymerization can be easily prepared by mixing monomers (a) to (c) according to a conventional method.

[0159] In a monomer mixture for polymerization, for example, with respect to the total moles of monomers (a) to (c), the ratio of the total of monomers (a) and (b) is 0.5 to 25 mol%, and the ratio of monomer (c) is 75 to 99.5 mol%. Also, preferably, with respect to the total moles of monomers (a) to (c), the ratio of the total of monomers (a) and monomer (b) is 1 to 22 mol% or 2 to 24 mol%, and the ratio of monomer (c) is 78 to 99 mol% or 76 to 98 mol%, and more preferably, the ratio of the total of monomers (a) and monomer (b) may be 3 to 18 mol%, 5 to 15 mol% (more than 5 mol% or 5 mol% or more and 15 mol% or less), 5 to 20 mol% (more than 5 mol% or 5 mol% or more and 20 mol% or less), 5 to 25 mol% (more than 5 mol% or 5 mol% or more and 25 mol% or less), etc.

[0160] In addition, the proportion of monomer (c) in the total moles of monomers (a) to (c) may be, for example, 82 to 97 mol%, 85 to 95 mol% (85 mol% or more and less than 95 mol% or 95 mol% or less), 80 to 95 mol% (80 mol% or more and less than 95 mol% or 95 mol% or less), 75 to 95 mol% (75 mol% or more and less than 95 mol% or 95 mol% or less). The proportion of monomer (c) to the total moles of monomers (a) to (c) may be 76 to 96 mol%, 78 to 98 mol%, 79 to 97 mol%, etc.

[0161] In addition, for example, with respect to the total moles of monomers (a) to (c), the ratio of the total of monomers (a) and (b) is 5 to 20 mol%, and the ratio of monomer (c) is 80 to 95 mol%. It is preferable that the molar ratio of monomers (a) to (c) in the monomer mixture for polymerization is the same as the molar ratio of constituent units (A) to (C) in the polycarbonate resin described above.

[0162] In addition, the description of the range (mol%) regarding the content of monomers (a) to (c) described above includes a range below the upper limit and below the upper limit, and also includes a range above the lower limit and above the lower limit.

[0163] In the monomer mixture for polymerization, components other than monomers (a) to (c) may not be included, and preferably, in the monomer mixture for polymerization, the total moles of monomers (a) to (c) are preferably 50 mol% or more based on the total moles of all monomers, more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably 95 mol% or more or substantially 100 mol%.

[0164] <3. Polycarbonate Resin Solution>

[0165] The polycarbonate resin solution comprises the polycarbonate resin and solvent described above. The type of solvent is not particularly limited as long as it can dissolve the polycarbonate resin, but for example, a (meth)acrylate compound having a (meth)acryloyl group ((meth)acrylate group), an aromatic compound having an aromatic ring, etc. are used as a solvent.

[0166] The (meth)acrylate compound used as a solvent preferably comprises at least a (meth)acrylic acid ester. The (meth)acrylic acid ester is not particularly limited, but a mono or di(meth)acrylic acid ester having a total number of carbon atoms of 4 to 20 is preferred, a mono or di(meth)acrylic acid ester having a total number of carbon atoms of 5 to 15 is more preferred, and a mono or di(meth)acrylic acid ester having a total number of carbon atoms of 5 to 10, 5 to 12, 6 to 10, 6 to 12, etc. is even more preferred. Preferred embodiments of (meth)acrylic acid esters include methyl acrylate, methyl methacrylate (MMA), tetrahydrofurfuryl acrylate (THF-A), tetrahydrofurfuryl methacrylate (THF-M), phenyl acrylate, hydroxyphenyl acrylate, benzyl acrylate (BZA), phenoxymethyl acrylate, phenoxyethyl acrylate, 1,6-hexanediol diacrylate, etc. Among these, tetrahydrofurfuryl acrylate (THF-A), tetrahydrofurfuryl methacrylate (THF-M), benzyl acrylate (BZA), phenoxyethyl acrylate, and 1,6-hexanediol diacrylate are suitable as solvents, and particularly preferred embodiments include THF-M, etc.

[0167] In addition, (meth)acrylic acid esters include acrylic acid esters and methacrylic acid esters.

[0168] Examples of aromatic compounds used as solvents include styrene, toluene, xylene, ethylbenzene, cumene, phenol, cresol, benzyl alcohol, anisole, benzaldehyde, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, toluidine, etc. Among these, styrene, toluene, xylene, etc. are suitable as solvents.

[0169] In addition, regarding the solvent compound, for example, it is preferable to have a refractive index value of 1.40 or higher and 1.60 or lower, a refractive index value of 1.42 or higher and 1.58 or lower, and more preferable to have a refractive index value of 1.44 or higher and 1.56 or lower.

[0170] The compounds described above, such as (meth)acrylic acid esters, as solvents have excellent compatibility with polycarbonate resins, so the solubility of the polycarbonate resin is good in polycarbonate resin solutions containing (meth)acrylic acid esters, etc. as solvents. Furthermore, the polycarbonate resin solution containing the solvent described above can carry out a cross-linking reaction in the solution state. In addition, using such a polycarbonate resin solution results in good color in the cured product obtained by polymerizing the polycarbonate resin. That is, when the polycarbonate resin contained in the polycarbonate resin solution is cured using (meth)acrylic acid esters, etc. containing THF-M as a solvent, cloudiness is prevented, and a transparent cured product or molded body is obtained.

[0171] The concentration of polycarbonate resin in the polycarbonate resin solution is not particularly limited, but it is preferable that the concentration of polycarbonate resin be 1 to 20 mass% based on the total mass of the polycarbonate resin solution. The concentration of polycarbonate resin in the polycarbonate resin solution is more preferably 2 to 18 mass%, even more preferably 3 to 16 mass%, and particularly preferably 5 to 15 mass%.

[0172] A polycarbonate resin solution can be easily prepared by mixing a polycarbonate resin and a solvent according to a conventional method.

[0173] In the case of a polycarbonate resin solution, for example when used for film formation, it is desirable to maintain a balance of necessary solvent solubility, coating properties, adhesion, scratch resistance, impact resistance, etc. If the ultimate viscosity of the polycarbonate resin solution is excessively low, scratch resistance or impact resistance strength is insufficient, and if the ultimate viscosity is excessively high, a decrease in solvent solubility and an increase in solution viscosity are observed, resulting in a decrease in the coating properties of the resulting film. As a preferred range of ultimate viscosity for the polycarbonate resin solution, it is preferable that the ultimate viscosity be in the range of 0.3 to 2.0 dl / g, and furthermore, in the range of 0.35 to 1.5 dl / g.

[0174] <4. Cross-linked Polycarbonate Resin>

[0175] A cross-linked polycarbonate resin is obtained by a cross-linking reaction of the polycarbonate resin described above. The cross-linked polycarbonate resin can be prepared, for example, by irradiating the polycarbonate resin solution described above with energy rays such as ultraviolet rays to cross-link the reaction active groups contained in the molecules of a plurality of polycarbonate resins contained in the resin solution.

[0176] In this way, by polymerizing a self-polymerizable polycarbonate resin, for example, in a solution phase, a polymer of a polycarbonate resin having crosslinking sites (crosslinked polycarbonate resin) can be easily produced without requiring secondary components such as a polymerization initiator.

[0177] <5. Molded Body>

[0178] The molded article of the present invention comprises, at least, a cross-linked polycarbonate resin obtained by cross-linking a polycarbonate resin. Examples of the molded article include a molded article obtained by cross-linking a polycarbonate resin for use as various coatings or binder resins, such as a cast molded article. Specific examples of the molded article include, for example, a film such as a substrate film formed on a substrate, a coating (film); a binder resin such as an electrophotographic photosensitive material or a conductive paste; an adhesive, a resin modifier, a UV ink, etc. The substrate film is formed, for example, on a PVB (polybutyral resin) substrate or a PET (polyethylene terephthalate resin) substrate, and the film as a cross-linked film formed on these substrates has particularly excellent adhesion to the substrate. Thus, the film obtained by coating a resin solution and curing it by heating is less prone to scratches or peeling due to friction or impact during transportation or use compared to a conventional resin solution film.

[0179] A substrate film as a molded body can be manufactured, for example, by removing a solvent from a polycarbonate resin solution and irradiating the resin as a residue with energy rays, heating, etc. That is, a film is formed by the crosslinking and polymerization reaction of the polycarbonate resin by irradiating with energy rays such as ultraviolet rays or by heating. When using a heating process, the heating temperature is preferably 50 to 150 ℃, more preferably 70 to 130 ℃, and even more preferably 80 to 120 ℃.

[0180] The thickness of the substrate film is preferably in the range of 5 to 200 μm, and in particular, in the range of 10 to 120 μm, and furthermore, in the range of 15 to 60 μm. If the film is thinner than 5 μm, the strength is insufficient and scratches are likely to reach the substrate, and if it is excessively thick exceeding 200 μm, peeling due to shrinkage of the film is likely to occur, and it becomes economically disadvantageous when considering the use of the film that is ultimately peeled off and discarded.

[0181] Examples

[0182] The present invention will be explained in more detail below by way of examples, but the present invention is not limited to these examples.

[0183] (1) Solubility

[0184] The appearance of the resin solution was visually inspected and judged based on the following indicators.

[0185] Transparent resin solution with no dissolved resin residue: "Good"

[0186] The resin solution is cloudy: "Slightly defective"

[0187] The resin does not dissolve at all: "Defective"

[0188] (2) Crosslinkable (UV curable)

[0189] The obtained resin solution was poured into a silicone mold having a rectangular hole of size 65 × 10 × 3 (mm), and UV light was irradiated under the following conditions, and the time until curing was determined by the time.

[0190] Equipment used: UV lamp (ultraviolet irradiation device manufactured by Iwasaki Electric Co., Ltd.)

[0191] UV wavelength: 365 nm

[0192] UV irradiation intensity: 50 mw / cm 2 × 10 minutes

[0193] Cures within 8 minutes: "Good"

[0194] Curing within 8 to 12 minutes: "Slightly defective"

[0195] Curing within 24 minutes exceeding 12 minutes: "Possible"

[0196] In addition, it was determined that the sample derived from the resin solution had cured when it was in a state where it could be ejected from the silicone mold. That is, the time from when UV irradiation was initiated until the sample formed by the resin solution could be released from the silicone mold was measured as the “time until curing” described above.

[0197] (3) Appearance of the molded piece

[0198] The appearance of the obtained molded specimen was evaluated visually.

[0199] The resin composition is transparent to the naked eye, without cloudiness, discoloration, or cloudiness: "Good"

[0200] Cloudiness or discoloration is observed, but transparency is high: "Slightly poor"

[0201] It is strongly cloudy or turbid and lacks transparency.

[0202] (While there may be usage restrictions in fields requiring transparency,

[0203] (Available in other fields) : "Defective"

[0204] (4) Impact strength

[0205] The resin composition (resin UV cured piece) obtained in (2) above was used to measure the impact strength using an impact tester.

[0206] Impact Tester: Impact Tester IT manufactured by Toyo Seiki Seisakusho Co., Ltd.

[0207] Test conditions: The test specimen is fixed to a jig and subjected to a 150-degree drop using an Izod 2J weight.

[0208] (5) Chemical resistance

[0209] 0.5 g of molded piece and 4.5 g of methylene chloride were added to a 20 ml vial and stirred. The appearance of the obtained solution was visually inspected and judged by the following indicators.

[0210] Dissolved residue in the solution: "Good"

[0211] Transparent with no dissolved resin residue in the solution: "Defective"

[0212] In addition, molded articles that do not easily dissolve in solvents can be said to have excellent chemical resistance.

[0213] (Example 1)

[0214] In 730 ml of a 6.5 w / w% aqueous sodium hydroxide solution, 96 g (0.36 mol) of bisphenol MIBK (4,4'-(1,3-dimethylbutylidene)bisphenol; hereinafter abbreviated as "MIBK": manufactured by Honshu Chemical) and 4.0 g (0.02 mol) of 4,4'dihydroxybenzophenone (hereinafter abbreviated as "4,4'DHBP": manufactured by Tokyo Kasei Kogyo Co., Ltd.) as raw material monomers (dihydroxy compounds) were dissolved, and additionally 0.5 g of hydrosulfite (antioxidant for oxidation and discoloration) was dissolved.

[0215] 300 ml of methylene chloride was added to this and stirred, while maintaining the temperature at 15 to 25°C, and then 51.8 g of phosgene was blown into the solution over a period of 40 minutes.

[0216] After the phosgene blowing was finished, 2.20 g of pt-butylphenol (hereinafter abbreviated as “PTBP”: manufactured by Dai Nippon Ink Chemical Industry Co., Ltd.) was added as a molecular weight regulator and the reaction mixture was emulsified by vigorously stirring, and after emulsification, 0.5 ml of triethylamine was added and the mixture was stirred at 20 to 30°C for about 1 hour to carry out the polymerization reaction.

[0217] After the polymerization was completed, the reaction solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and washing was repeated until the conductivity of the wash solution (aqueous phase) became 100 μS / cm or less. The obtained polymer solution was transferred to an aluminum dish, the solvent was removed by evaporating it on a hot plate, and the obtained solid was further dried at 120°C for 24 hours to obtain a polymer solid.

[0218] As a result of analyzing the obtained polymer by infrared absorption spectrum, 1770 cm⁻¹ -1 Absorption by a carbonyl group at a nearby location, 1240 cm⁻¹ -1 Absorption by ether bonds was confirmed at a nearby location, and it was confirmed to be a polycarbonate resin having carbonate bonds.

[0219] 1 g of the polycarbonate resin described above and 9 g of tetrahydrofurfuryl methacrylate (THF-M) were added to a 20 ml vial and stirred to obtain a polycarbonate resin solution.

[0220] Next, the polycarbonate resin solution described above was poured into a silicone mold having rectangular holes measuring 65 × 10 × 3 (mm), and UV was irradiated to obtain a UV-cured piece (molded body). The UV irradiation conditions are as follows.

[0221] Equipment used: UV lamp (ultraviolet irradiation device manufactured by Iwasaki Electric Co., Ltd.)

[0222] UV wavelength: 365 nm

[0223] UV irradiation intensity: 50 mw / cm 2 × 10 minutes

[0224] The properties of the obtained polycarbonate resin, polycarbonate resin solution, and molded body are summarized in Table 1 below.

[0225] (Examples 2–14, Comparative Examples 1–5)

[0226] Polycarbonate resin, polycarbonate resin solution, and molded articles were obtained in the same manner as in Example 1, except that the raw material monomer (dihydroxy compound) and terminal stopper (hydroxy compound) were changed to the monomer species and molar ratio (mol%) shown in Table 1, and 1 mass% of 2-hydroxy-2-methylpropiophenone (hereinafter also referred to as HMP), a radical generator, was added to the resin solution in some comparative examples.

[0227] The properties of the obtained polycarbonate resin, polycarbonate resin solution, and molded body are summarized in the table below.

[0228]

[0229] As is evident from the results of the examples and comparative examples, it was confirmed that in the polycarbonate resin of each example having a DHBP structure formed in the main chain, a curing reaction can be initiated in a short time without using a photopolymerization initiator, and various physical properties can be achieved in a good balance. That is, in each example, curing by energy beam irradiation is possible even with the polycarbonate resin alone, and a molded article having excellent impact resistance, chemical resistance, etc. was formed. In addition, in some examples such as Example 1, good results regarding appearance were not necessarily observed, but since their polycarbonate resins also have excellent impact resistance values, etc., they are preferably used in applications where color is not important.

[0230] In addition, the type of suitable solvent for dissolving the polycarbonate resin to form a polycarbonate resin solution was examined. Specifically, the resin and solvent were mixed in an amount of 10% by weight in the mixture, and the compatibility and whether a cured product could be obtained upon UV irradiation were evaluated as follows. For the polycarbonate resins of each example, it was confirmed that a solution could be formed with various solvents, and that a crosslinking reaction could be carried out without using a polymerization initiator (radical generator / HMP). In evaluating the progress of the curing reaction, UV light was irradiated onto the mixture under conditions identical to the crosslinkability (UV curability) evaluation item in Table 1, and the presence or absence of a cured product was visually confirmed. Furthermore, regarding solubility, it was evaluated as "good" when a uniform solution was formed.

[0231]

[0232] In addition, the molecular structures of monomers, etc. used in the examples and comparative examples are as follows.

[0233] [Chemical Formula 19]

[0234]

[0235] Although preferred embodiments of the present invention have been described in detail with reference to the examples and the like, the present invention is not limited to these examples. It is clear to those skilled in the art to which the present invention pertains that various modifications or alterations can be made within the scope of the technical concept described in the claims, and these are also naturally understood to fall within the technical scope of the present invention.

Claims

Claim 1 A polycarbonate resin comprising a monomer-derived constituent unit (A) represented by the following general formula (1) and / or a monomer-derived constituent unit (B) represented by the following general formula (2), and a monomer-derived constituent unit (C) represented by the following general formula (3), wherein, with respect to the total moles of said constituent units (A) to (C) constituting the polycarbonate resin, the ratio of the total of said constituent unit (A) and said constituent unit (B) is 0.5 to 25 mol% and the ratio of said constituent unit (C) is 75 to 99.5 mol%. (General formula (1) of which, R 11 ~ R 14 and R 15 ~ R 18 Each represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, which may each independently have hydrogen, fluorine, chlorine, bromine, or iodine, or a substituent, and in general formula (2), R 21 ~ R 25 and R 26 ~ R 28 Each represents, independently, hydrogen, fluorine, chlorine, bromine, or iodine, or a C1-20 alkyl group, a C6-12 aryl group, a C2-12 alkenyl group, a C1-5 alkoxy group, or a C7-17 aralkyl group, which may each have a substituent. (General formula (3) of which, R 31 ~ R 34 and R 35 ~ R 38 Each represents, independently, hydrogen, fluorine, chlorine, bromine, or iodine, or a C1-20 alkyl group, a C6-12 aryl group, a C2-12 alkenyl group, a C1-5 alkoxy group, or a C7-17 aralkyl group that may each have a substituent, and X is, and, where R5 and R6 each independently represent a C1-20 alkyl group, a C1-5 alkoxy group, or a C6-12 aryl group that may each have hydrogen, fluorine, chlorine, bromine, or iodine, or a substituent, or represent a group in which R5 and R6 combine to form a C5-20 carbon ring or a C5-12 complex ring (except where both R5 and R6 are methyl groups), R7 and R8 each independently represent a C1-9 alkyl group, a C1-5 alkoxy group, a C2-12 alkenyl group, or a C6-12 aryl group that may each have hydrogen, fluorine, chlorine, bromine, or iodine, or a substituent, and c is 0 Represents an integer of ~ 20. Claim 2 A polycarbonate resin according to claim 1, wherein the ratio of the constituent unit (A) and the constituent unit (B) to the total moles of the constituent units (A) to (C) constituting the polycarbonate resin is 5 to 20 mol%, and the ratio of the constituent unit (C) is 80 to 95 mol%. Claim 3 In claim 1, in the above general formula (1), R 11 ~ R 14 and R 15 ~ R 18 Each of these represents an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, which may each independently have hydrogen or a substituent, and in general formula (2), R 21 ~ R 25 and R 26 ~ R 28 A polycarbonate resin having, respectively, hydrogen, or an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, each of which may have a substituent. Claim 4 In claim 3, the monomer represented by the general formula (1) is represented by the following formula (1-1), and the monomer represented by the general formula (2) is represented by the following formula (2-1), in a polycarbonate resin. Claim 5 In claim 1, in the above general formula (3), R 31 ~ R 34 and R 35 ~ R 38 Each of these independently represents a C1 to C20 alkyl group or a C1 to C5 alkoxy group, which may each have hydrogen or a substituent, and the above X, and, where R5 and R6 each independently represent a C1- to C20 alkyl group or a C6- to C12 aryl group that may each have hydrogen or a substituent, or R5 and R6 combine to form a C5- to C20 carbon ring or a C5- to C12 complex ring, and R7 and A polycarbonate resin in which R8 represents, independently, hydrogen, or an alkyl group having 1 to 9 carbon atoms or an aryl group having 6 to 12 carbon atoms, each of which may have a substituent. Claim 6 In claim 5, the monomer represented by the general formula (3) is selected from the group consisting of the following formulas (3-1) to (3-4), a polycarbonate resin. Claim 7 In claim 1, the polycarbonate resin is a polycarbonate resin in which the terminal structure of the polycarbonate resin is represented by the following formula (4). (In general formula (4), A is a vinyl group, an isopropen group, a styryl group, or a methine group; R1 and R2 are each independently selected from the group consisting of a single bond and a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; R3 is each independently selected from the group consisting of a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and a substituted or unsubstituted heteroaryl group having 5 to 12 atoms; Z is each independently selected from the group consisting of a single bond, an ether group, a carbonyl group, and an ester group; a is an integer from 0 to 3; b is an integer from 1 to 4; and Y is an ether group, or It is an ester group. Claim 8 The polycarbonate resin according to claim 1, wherein the terminal structure of the polycarbonate resin is derived from a compound selected from the group consisting of pt-butylphenol (PTBP), 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole (MBZT), 4-hydroxybenzophenone (4-HBP), polyoxyalkylene-monoalkyl ether, and p-hydroxyphenylethanol (PHEP). Claim 9 In claim 1, a polycarbonate resin in which unsaturated bonds are not included in the main chain of the polycarbonate resin. Claim 10 A polymerization monomer mixture for forming a constituent unit of a thermoplastic resin comprising a monomer (a) represented by the following general formula (1) and / or a monomer (b) represented by the following general formula (2), and a monomer (c) represented by the following general formula (3), wherein, with respect to the total moles of monomers (a) to (c), the ratio of the total of monomers (a) and monomer (b) is 0.5 to 25 mol% and the ratio of monomer (c) is 75 to 99.5 mol%. (General formula (1) of which, R 11 ~ R 14 and R 15 ~ R 18 Each represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, which may each independently have hydrogen, fluorine, chlorine, bromine, or iodine, or a substituent, and in general formula (2), R 21 ~ R 25 and R 26 ~ R 28 Each represents, independently, hydrogen, fluorine, chlorine, bromine, or iodine, or a C1-20 alkyl group, a C6-12 aryl group, a C2-12 alkenyl group, a C1-5 alkoxy group, or a C7-17 aralkyl group, which may each have a substituent. (General formula (3) of which, R 31 ~ R 34 and R 35 ~ R 38 Each represents, independently, hydrogen, fluorine, chlorine, bromine, or iodine, or a C1-20 alkyl group, a C6-12 aryl group, a C2-12 alkenyl group, a C1-5 alkoxy group, or a C7-17 aralkyl group that may each have a substituent, and X is, and, where R5 and R6 each independently represent a C1-20 alkyl group, a C1-5 alkoxy group, or a C6-12 aryl group that may each have hydrogen, fluorine, chlorine, bromine, or iodine, or a substituent, or represent a group in which R5 and R6 combine to form a C5-20 carbon ring or a C5-12 complex ring (except where both R5 and R6 are methyl groups), R7 and R8 each independently represent a C1-9 alkyl group, a C1-5 alkoxy group, a C2-12 alkenyl group, or a C6-12 aryl group that may each have hydrogen, fluorine, chlorine, bromine, or iodine, or a substituent, and c is 0 Represents an integer of ~ 20. Claim 11 A polycarbonate resin solution comprising the polycarbonate resin described in claim 1 and a solvent. Claim 12 In claim 11, the polycarbonate resin solution wherein the solvent comprises at least a (meth)acrylic acid ester solvent. Claim 13 In claim 12, the polycarbonate resin solution wherein the (meth)acrylic acid ester is tetrahydrofurfuryl methacrylate (THF-M). Claim 14 A polycarbonate resin solution according to claim 11, wherein the concentration of the polycarbonate resin is 1 to 20 mass% based on the total mass of the polycarbonate resin solution. Claim 15 A method for manufacturing a cross-linked polycarbonate resin, characterized by performing ultraviolet irradiation on the polycarbonate resin solution described in claim 11. Claim 16 A cross-linked polycarbonate resin obtained by the manufacturing method described in claim 15. Claim 17 A molded article comprising the cross-linked polycarbonate resin described in claim 16.

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