Polycarbonate resin and polycarbonate resin solution
By introducing specific structural units into polycarbonate resin and using energy rays to initiate polymerization, the problems of poor crosslinking reactivity and insufficient versatility have been solved, and the reactivity of polymers in the polymer state and the improvement of polymer properties have been achieved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- MITSUBISHI GAS CHEM CO INC
- Filing Date
- 2024-11-28
- Publication Date
- 2026-06-19
AI Technical Summary
Existing reactive polycarbonate resins have poor crosslinking reactivity and insufficient versatility, requiring additives such as polymerization initiators, making them difficult to apply to various uses.
Polycarbonate resin containing structural units of general formula (1), general formula (2) and general formula (3) in a specific ratio is used to initiate the polymerization reaction by energy rays such as ultraviolet light, avoiding the use of polymerization initiators and adjusting the reactivity and crosslinking positions.
It achieves reactivity in the polymer state, allows for free adjustment of polymerization and crosslinking reactivity, improves polymer properties, and is suitable for a variety of applications.
Smart Images
Figure CN122249488A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to polycarbonate resins and polycarbonate resin solutions, etc. Background Technology
[0002] Reactive polycarbonate (reactive PC) resins containing reactive sites are known (Patent Documents 1-3, etc.). Among reactive polycarbonate resins, terminal reactive polycarbonates containing reactive sites for polymerization reactions, etc., are particularly widely used. Reactive polycarbonate resins are usually used in the form of compositions with added polymerization initiators, additives, etc., and polymers are manufactured from such resin compositions through polymerization reactions.
[0003] Existing technical documents
[0004] Patent documents
[0005] Patent Document 1: WO2021 / 241378
[0006] Patent Document 2: Japanese Patent Application Publication No. 54-064592
[0007] Patent Document 3: Japanese Patent Application Publication No. 11-172003 Summary of the Invention
[0008] The problem that the invention aims to solve
[0009] Most existing reactive polycarbonates are manufactured using chain terminators with functional groups, resulting in reactive sites only at the ends. In such terminally reactive polycarbonates, the reactive sites are limited to the ends, and the crosslinking reactivity tends to be poor.
[0010] Furthermore, in reactive PCs that require secondary components such as polymerization initiators to initiate the polymerization reaction, the choice of additives is limited, and the polymerization reaction must be carried out under predetermined reaction conditions. Therefore, existing reactive PCs tend to be difficult to use for various applications and have poor versatility.
[0011] Technical means to solve the problem
[0012] This invention includes, for example, the following inventions.
[0013] [1] A polycarbonate resin, wherein the polycarbonate resin comprises:
[0014] Structural unit (A) derived from the monomer shown in general formula (1) below and / or structural unit (B) derived from the monomer shown in general formula (2) below; and
[0015] The structural unit (C) of the monomer is derived from the following general formula (3).
[0016] Relative to the total molar number of the structural units (A) to (C) constituting the polycarbonate resin, the total proportion of structural unit (A) and structural unit (B) is 0.5 to 25 mol%, and the proportion of structural unit (C) is 75 to 99.5 mol%.
[0017]
[0018] In general formula (1), R 11 ~R 14 and R 15 ~R 18 Each can independently represent hydrogen, fluorine, chlorine, bromine, or iodine, or can be a substituent of 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.
[0019] In general formula (2), R 21 ~R 25 and R 26 ~R 28 Each can independently represent hydrogen, fluorine, chlorine, bromine, or iodine, or can be a substituent of 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.
[0020]
[0021] In general formula (3), R 31 ~R 34 and R 35 ~R 38 Each can independently represent hydrogen, fluorine, chlorine, bromine, or iodine, or can be a substituent of 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.
[0022] X is
[0023]
[0024] or ,
[0025] In the formula, R5 and R6 independently represent hydrogen, fluorine, chlorine, bromine, or iodine, or can be alkyl groups with 1 to 20 carbon atoms, alkoxy groups with 1 to 5 carbon atoms, or aryl groups with 6 to 12 carbon atoms, respectively, or represent groups in which R5 and R6 are bonded to form a carbon ring with 5 to 20 carbon atoms or a heterocycle with 5 to 12 elements. This excludes cases where both R5 and R6 are methyl groups.
[0026] R7 and R8 can each independently represent hydrogen, fluorine, chlorine, bromine, or iodine, or can be alkyl with 1 to 9 carbon atoms, alkoxy with 1 to 5 carbon atoms, alkenyl with 2 to 12 carbon atoms, or aryl with 6 to 12 carbon atoms, respectively.
[0027] c represents an integer from 0 to 20.
[0028] [2] According to the polycarbonate resin described in [1] above, the ratio of the structural unit (A) to the structural unit (B) is 5 to 20 mol% relative to the total number of moles of the structural units (A) to (C) constituting the polycarbonate resin, and the ratio of the structural unit (C) is 80 to 95 mol%.
[0029] [3] According to the polycarbonate resin described in [1] or [2] above, for example, [1] above, wherein, in the above general formula (1), R 11 ~R 14 and R 15 ~R 18 Each can independently represent hydrogen or an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, respectively.
[0030] In general formula (2), R 21 ~R 25 and R 26 ~R 28 Each can independently represent hydrogen or an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, respectively.
[0031] [4] According to any one of [1] to [3] above, such as the polycarbonate resin described in [3] above, 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).
[0032]
[0033] [5] According to any one of [1] to [4] above, such as the polycarbonate resin described in [1] above, wherein, in the above general formula (3), R 31 ~R 34 and R 35 ~R38 Each can independently represent hydrogen or an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, respectively.
[0034] The above X is
[0035] or
[0036] In the formula, R5 and R6 each independently represent hydrogen or alkyl groups with 1 to 20 carbon atoms or aryl groups with 6 to 12 carbon atoms, which may each have substituents; or they represent groups in which R5 and R6 are bonded to form a carbon ring with 5 to 20 carbon atoms or a heterocycle with 5 to 12 elements.
[0037] R7 and R8 each independently represent hydrogen or alkyl groups having 1 to 9 carbon atoms or aryl groups having 6 to 12 carbon atoms, respectively.
[0038] [6] According to any one of [1] to [4] above, such as the polycarbonate resin described in [5] above, wherein the monomer represented by the above general formula (3) is selected from the following formulas (3-1) to (3-4).
[0039]
[0040] [7] According to any one of [1] to [6] above, such as the polycarbonate resin described in [1] above, wherein the end structure of the polycarbonate resin is represented by the following formula (4),
[0041]
[0042] In general formula (4), A is vinyl, isopropenyl, styryl, or methine.
[0043] R1 and R2 are each independently selected from alkylene groups with 1 to 20 carbon atoms, either single-bonded or substituted or unsubstituted.
[0044] R3 is independently selected from hydrogen atoms, hydroxyl groups, alkyl groups with or without substituted carbon atoms numbering 1 to 20, alkoxy groups with or without substituted carbon atoms numbering 1 to 10, aryl groups with or without substituted carbon atoms numbering 6 to 12, and heteroaryl groups with or without substituted carbon atoms numbering 5 to 12.
[0045] Z is independently selected from single bonds, ether groups, carbonyl groups, and ester groups.
[0046] a is an integer between 0 and 3.
[0047] b is an integer from 1 to 4.
[0048] Y is an ether group or an ester group.
[0049] [8] According to any one of [1] to [7] above, such as the polycarbonate resin described in [1] above, wherein the end structure of the polycarbonate resin is derived from a compound selected from p-tert-butylphenol (PTBP), 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole (MBZT), 4-hydroxybenzophenone (4-HBP), polyoxyethylene-monoalkyl ether, and p-hydroxyphenylethanol (PHEP).
[0050] [9] According to any one of [1] to [8] above, such as the polycarbonate resin described in [1] above, wherein the main chain of the polycarbonate resin does not contain unsaturated bonds.
[0051]
[10] A monomer mixture for polymerization, wherein the monomer mixture for polymerization is used to form structural units of a thermoplastic resin.
[0052] The above-mentioned monomer mixture for polymerization comprises:
[0053] The monomer (a) shown in general formula (1) below and / or the monomer (b) shown in general formula (2) below; and
[0054] The monomer (c) shown in the following general formula (3)
[0055] Relative to the total molar number of monomers (a) to (c) mentioned above, the total proportion of monomers (a) and (b) is 0.5 to 25 mol%, and the proportion of monomer (c) is 75 to 99.5 mol%.
[0056]
[0057] In general formula (1), R 11 ~R 14 and R 15 ~R 18 Each can independently represent hydrogen, fluorine, chlorine, bromine, or iodine, or can be a substituent of 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.
[0058] In general formula (2), R 21 ~R 25 and R 26 ~R 28 Each can independently represent hydrogen, fluorine, chlorine, bromine, or iodine, or can be a substituent of 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.
[0059]
[0060] In general formula (3), R 31 ~R 34 and R 35 ~R 38 Each can independently represent hydrogen, fluorine, chlorine, bromine, or iodine, or can be a substituent of 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.
[0061] X is
[0062]
[0063] or ,
[0064] In the formula, R5 and R6 independently represent hydrogen, fluorine, chlorine, bromine, or iodine, or can be alkyl groups with 1 to 20 carbon atoms, alkoxy groups with 1 to 5 carbon atoms, or aryl groups with 6 to 12 carbon atoms, respectively, or represent groups in which R5 and R6 are bonded to form a carbon ring with 5 to 20 carbon atoms or a heterocycle with 5 to 12 elements. This excludes cases where both R5 and R6 are methyl groups.
[0065] R7 and R8 can each independently represent hydrogen, fluorine, chlorine, bromine, or iodine, or can be alkyl with 1 to 9 carbon atoms, alkoxy with 1 to 5 carbon atoms, alkenyl with 2 to 12 carbon atoms, or aryl with 6 to 12 carbon atoms, respectively.
[0066] c represents an integer from 0 to 20.
[0067]
[11] A polycarbonate resin solution, wherein it contains any one of [1] to [9] above, such as the polycarbonate resin described in [1] above, and a solvent.
[0068]
[12] The polycarbonate resin solution according to
[11] above, wherein the solvent comprises at least (meth)acrylate solvent.
[0069]
[13] According to the polycarbonate resin solution described in
[12] above, wherein the (meth)acrylate is tetrahydrofurfuryl methacrylate (THF-M).
[0070]
[14] According to any one of
[11] to
[13] above, such as the polycarbonate resin solution described in
[11] above, wherein the concentration of the polycarbonate resin is 1 to 20 by mass based on the total mass of the polycarbonate resin solution above.
[0071]
[15] A method for manufacturing a cross-linked polycarbonate resin, characterized in that ultraviolet light is irradiated onto any of the above
[11] to
[14] , such as the above-described polycarbonate resin solution described in
[11] .
[0072]
[16] A crosslinked polycarbonate resin, wherein it is obtained by the manufacturing method described above
[15] .
[0073]
[17] A molded body comprising the crosslinked polycarbonate resin described above in
[16] .
[0074] Invention Effects
[0075] According to the present invention, not only can the reactivity of polymerization and crosslinking reactions be easily adjusted according to the number of functional groups, but also the polymerization of resin monomers can be achieved without additives such as polymerization initiators, resulting in polycarbonate resins with increased freedom in the physical properties of the obtained polymers. In the case of the polycarbonate resin of the present invention, reactivity can be maintained even in the long-chain, i.e., high-molecular-weight state.
[0076] Furthermore, according to the present invention, it is also possible to produce monomer mixtures suitable for manufacturing the above-mentioned polycarbonate resins, polycarbonate resin solutions containing polycarbonate resin and solvents, etc. Detailed Implementation
[0077] The preferred embodiments of the present invention will be described in detail below.
[0078] <1. Polycarbonate resin>
[0079] 1-1. Structural units and their content in polycarbonate resin
[0080] The polycarbonate resin comprises at least one of a structural unit (A) derived from a monomer of general formula (1) and a structural unit (B) derived from a monomer of general formula (2).
[0081]
[0082] In general formula (1), R 11 ~R 14 and R 15 ~R 18 Each can independently represent hydrogen, fluorine, chlorine, bromine or iodine, or can have substituents of alkyl with 1 to 20 carbon atoms, aryl with 6 to 12 carbon atoms, alkenyl with 2 to 12 carbon atoms, alkoxy with 1 to 5 carbon atoms or aralkyl with 7 to 17 carbon atoms.
[0083] R in general formula (1) 11 ~R 14 and R15 ~R 18 Preferably, each of the following groups represents hydrogen independently, or is an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, and may have substituents. R 11 ~R 14 and R 15 ~R 18 More preferably, each can be an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, each independently representing hydrogen; even more preferably, each can be an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 2 carbon atoms, each independently representing hydrogen.
[0084] Furthermore, R 11 ~R 14 and R 15 ~R 18 Preferably, at least 5 or more are hydrogen atoms, more preferably 6 or more are hydrogen atoms, and even more preferably 7 or more are hydrogen atoms or all of them are hydrogen atoms.
[0085] Preferred examples of the monomers shown in general formula (1) are represented by the following formula (1-1).
[0086]
[0087] In the above general formula (2), R 21 ~R 25 and R 26 ~R 28 Each can independently represent hydrogen, fluorine, chlorine, bromine, or iodine, or can be a substituent of 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.
[0088] R in general formula (2) 21 ~R 25 and R 26 ~R 28 Preferably, each of the following groups represents hydrogen independently, or is an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, and may have substituents. R 21 ~R 25 and R 26 ~R 28 More preferably, each can be an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, each independently representing hydrogen; even more preferably, each can be an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 2 carbon atoms, each independently representing hydrogen.
[0089] Furthermore, R 21 ~R 25 and R26 ~R 28 Preferably, at least 5 or more are hydrogen atoms, more preferably 6 or more are hydrogen atoms, and even more preferably 7 or more are hydrogen atoms or all of them are hydrogen atoms.
[0090] Preferred examples of the monomers shown in general formula (2) are represented by the following formula (2-1).
[0091]
[0092] Both structural units (A) and (B) contained in the polycarbonate resin backbone can function as reactive groups capable of polymerization. Therefore, even without special additives for polymerization, such as polymerization initiators, polycarbonate resin can undergo polymerization reactions through irradiation by energy rays, such as ultraviolet light. This is because the two molecules of the compound represented by the above general formula (1) or (2) undergo cross-linking reactions with each other according to the synthesis reaction of benzylpinacol.
[0093] Although polycarbonate resins containing either structural unit (A) or (B) are long-chain polymers, they can still maintain reactivity. Moreover, in polycarbonate resins containing structural unit (A) or (B), crosslinking sites can be designed in a wide range of locations other than the ends, and reactivity can be easily adjusted according to the amount of monomer used as represented by general formula (1) or (2).
[0094] Polycarbonate resins also contain structural units (C) derived from monomers represented by the following general formula (3).
[0095]
[0096] In general formula (3), R 31 ~R 34 and R 35 ~R 38 Each can independently represent hydrogen, fluorine, chlorine, bromine or iodine, or can have substituents of alkyl with 1 to 20 carbon atoms, aryl with 6 to 12 carbon atoms, alkenyl with 2 to 12 carbon atoms, alkoxy with 1 to 5 carbon atoms or aralkyl with 7 to 17 carbon atoms.
[0097] R in general formula (3) 31 ~R 34 and R 35 ~R 38 Preferably, each of the following groups represents hydrogen independently, or is an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, and may have substituents. R 31 ~R 34 and R 35 ~R 38More preferably, each can be an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, each independently representing hydrogen; even more preferably, each can be an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 2 carbon atoms, each independently representing hydrogen.
[0098] Furthermore, R 31 ~R 34 and R 35 ~R 38 Preferably, at least 5 or more are hydrogen atoms, more preferably 6 or more are hydrogen atoms, and even more preferably 7 or more are hydrogen atoms or all of them are hydrogen atoms.
[0099] In addition, in general formula (3), X is represented by any of the following formulas.
[0100]
[0101] or
[0102] In the above formula, R5 and R6 may each independently represent hydrogen, fluorine, chlorine, bromine or iodine, or may be alkyl with 1 to 20 carbon atoms, alkoxy with 1 to 5 carbon atoms or aryl with 6 to 12 carbon atoms respectively, or represent a group in which R5 and R6 are bonded to form a carbon ring with 5 to 20 carbon atoms or a heterocycle with 5 to 12 elements, excluding the case where both R5 and R6 are methyl.
[0103] In the above formula, R7 and R8 each independently represent hydrogen, fluorine, chlorine, bromine or iodine, or may be alkyl with 1 to 9 carbon atoms, alkoxy with 1 to 5 carbon atoms, alkenyl with 2 to 12 carbon atoms or aryl with 6 to 12 carbon atoms, respectively.
[0104] Furthermore, in the above formula, c represents an integer from 0 to 20, preferably from 1 to 15, and more preferably from 1 to 10.
[0105] In addition, in the above formula (3), X is preferably represented by any of the following formulas.
[0106] or
[0107] In the formula, R5 and R6 each independently represent hydrogen or alkyl groups with 1 to 20 carbon atoms or aryl groups with 6 to 12 carbon atoms that may have substituents, or groups that form a carbon ring with 5 to 20 carbon atoms or a heterocycle with 5 to 12 elements by bonding R5 and R6.
[0108] In addition, R7 and R8 each independently represent hydrogen or alkyl groups having 1 to 9 carbon atoms or aryl groups having 6 to 12 carbon atoms, respectively, which may have substituents.
[0109] In general formula (3), R5 and R6 in X are more preferably hydrogen or alkyl groups having 1 to 12 carbon atoms that may have substituents, or R5 and R6 are bonded to form a carbon ring having 5 to 20 carbon atoms that may have substituents, more preferably a carbon ring having 6 to 12 carbon atoms that may have substituents.
[0110] In addition, R7 and R8 in X of general formula (3) each independently represent hydrogen or alkyl with 1 to 5 carbon atoms or aryl with 6 to 8 carbon atoms, which may have substituents respectively.
[0111] Preferred examples of the monomers shown in general formula (3) are represented by the following formulas (3-1) to (3-4).
[0112]
[0113] In the polycarbonate resin, the total proportion of structural unit (A) and structural unit (B) relative to the total molar number of structural units (A) to (C) constituting the polycarbonate resin is 0.5 to 25 mol%. The total molar proportion of structural unit (A) and structural unit (B) relative to the total molar number of structural 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 more but less than 15 mol%), 5 to 20 mol% (greater than 5 mol% or more but less than 20 mol%), or 5 to 25 mol% (greater than 5 mol% or more but less than 25 mol%), and particularly preferably 5 to 20 mol%.
[0114] In the polycarbonate resin, the proportion of structural unit (C) relative to the total molar number of structural units (A) to (C) constituting the polycarbonate resin is 75 to 99.5 mol%. The proportion of structural unit (C) relative to the total molar number of structural units (A) to (C) is preferably 76 to 96 mol% or 78 to 98 mol%, more preferably 79 to 97 mol%, 75 to 95 mol% (75 mol% or more but less than 95 mol% or less), 80 to 95 mol% (80 mol% or more but less than 95 mol% or less), 85 to 95 mol% (85 mol% or more but less than 95 mol% or less), etc.
[0115] It should be noted that the range (mol%) related to the content of the above-mentioned structural units (A) to (C) (including the total content of structural units (A) and (B) and the content of structural unit (C)) includes the range below the upper limit and the range less than the upper limit, and the range above the lower limit and the range greater than the lower limit.
[0116] In the polycarbonate resin, when there are structural units other than structural units (A) to (C), the proportion of structural unit (A) and structural unit (B) to the total number of moles of all structural units is preferably 0.5 to 25 mol%, more preferably 1 to 22 mol% or 2 to 24 mol%, even more preferably 3 to 18 mol%, 5 to 15 mol% (greater than 5 mol% or more than 5 mol% but less than 15 mol%), 5 to 20 mol% (greater than 5 mol% or more than 5 mol% but less than 20 mol%), or 5 to 25 mol% (greater than 5 mol% or more than 5 mol% but less than 25 mol%), and particularly preferably 5 to 20 mol%.
[0117] Furthermore, in polycarbonate resins, when there are structural units other than structural units (A) to (C), the proportion of structural unit (C) relative to the total number of moles of all structural units is preferably 75 to 99.5 mol%, more preferably 76 to 96 mol% or 78 to 98 mol%, and may also be 79 to 97 mol%, 75 to 95 mol% (75 mol% or more but less than 95 mol% or less), 80 to 95 mol% (80 mol% or more but less than 95 mol% or less), 85 to 95 mol% (85 mol% or more but less than 95 mol% or less), etc.
[0118] It should be noted that the recorded range (mol%) of the content of the above-mentioned structural units (A) to (C) (including the total content of structural units (A) and (B) and the content of structural unit (C)) also includes the range below the upper limit and the range less than the upper limit, and the range above the lower limit and the range greater than the lower limit.
[0119] In polycarbonate resin, based on the total number of moles of all structural units, the total number of moles of structural units (A) to (C) is preferably 50 mol% or more, more preferably 70 mol% or more, further preferably 90 mol% or more, particularly preferably 95 mol% or more or substantially 100 mol%.
[0120] In the structural units (A) to (C) of the polycarbonate resin, the substituents are each independently selected from halogens, hydroxyl groups, cyano groups, alkyl groups with 1 to 20 carbon atoms, alkenyl groups with 1 to 20 carbon atoms, aryl groups with 6 to 12 carbon atoms, etc. When alkyl, alkenyl, and aryl groups are present as substituents, the aforementioned R... 11 ~R 38 The number of carbon atoms in the formula is the total number of carbon atoms, including the number of carbon atoms in the substituents.
[0121] Of all the structural units in the polycarbonate resin, based on the total molar number of all structural units, the total molar number of structural units having unsaturated bonds is preferably 10 mol% or less, more preferably 5 mol% or less, and even more preferably 3 mol% or less. Furthermore, it is particularly preferable that the polycarbonate resin does not contain any unsaturated bonds.
[0122] 1-2. End structure of polycarbonate resin
[0123] The end structure of the polycarbonate resin is preferably represented by the following formula (4).
[0124]
[0125] In general formula (4), A is vinyl, isopropenyl, styrene or methine, preferably vinyl.
[0126] In general formula (4), R1 and R2 are each independently selected from alkylene groups with 1 to 20 carbon atoms, either single-bonded or substituted or unsubstituted, preferably from alkylene groups with 1 to 10 carbon atoms, more preferably from alkylene groups with 1 to 5 carbon atoms, and even more preferably from alkylene groups with 1 to 3 carbon atoms.
[0127] In general formula (4), each of R3 is independently selected from hydrogen atom, hydroxyl group, alkyl group with substituted or unsubstituted carbon atoms numbering 1 to 20, alkoxy group with substituted or unsubstituted carbon atoms numbering 1 to 10, aryl group with substituted or unsubstituted carbon atoms numbering 6 to 12, and heteroaryl group with substituted or unsubstituted carbon atoms numbering 5 to 12. R3 is preferably selected from hydrogen atom, hydroxyl group, alkyl group with substituted or unsubstituted carbon atoms numbering 1 to 10, and alkoxy group with substituted or unsubstituted carbon atoms numbering 1 to 6, more preferably selected from hydrogen atom, hydroxyl group, alkyl group with substituted or unsubstituted carbon atoms numbering 1 to 5, and alkoxy group with substituted or unsubstituted carbon atoms numbering 1 to 3, and particularly preferably selected from hydrogen atom, hydroxyl group, alkyl group with substituted or unsubstituted carbon atoms numbering 1 to 3, and alkoxy group with substituted or unsubstituted carbon atoms numbering 1 to 2.
[0128] In general formula (4), Z is independently selected from single bond, ether group (O atom bonded to adjacent carbon atom), carbonyl group and ester group.
[0129] In general formula (4), a is an integer from 0 to 3, preferably an integer from 0 to 2 or 1 to 3, and more preferably an integer from 0 to 1 or 1 to 2. Additionally, 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. Alternatively, b can also be 0.
[0130] In general formula (4), Y is an ether group or an ester group, preferably an ether group.
[0131] The terminal structure of the polycarbonate resin is preferably derived from a compound selected from p-tert-butylphenol (PTBP), 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole (MBZT), 4-hydroxybenzophenone (4-HBP), polyoxyethylene-monoalkyl ether, and p-hydroxyphenylethanol (PHEP).
[0132] The terminal structure of polycarbonate resin has substituents that are independently selected from halogens, hydroxyl groups, cyano groups, alkyl groups with 1 to 20 carbon atoms, alkenyl groups with 1 to 20 carbon atoms, aryl groups with 6 to 12 carbon atoms, etc. When alkyl, alkenyl and aryl groups are included as substituents, the number of carbon atoms in R1 to R3 mentioned above is the total number of carbon atoms including the number of carbon atoms of the substituents.
[0133] 1-3. Manufacturing methods of polycarbonate resin
[0134] Polycarbonate resins can be manufactured using conventional methods, such as those described below.
[0135] The polycarbonate resin used in this invention can be manufactured, for example, by reacting bisphenols, preferably monomers (a) to (c), from which structural units (A) to (C) are derived; monohydric phenols or other compounds with terminal structures, preferably monomers having molecular structures corresponding to the structure of formula (4); and carbonate forming compounds. Known methods can be used, such as the direct reaction of bisphenols with phosgene (phosgene method) or the transesterification reaction of bisphenols with diaryl carbonate (transesterification method).
[0136] In the phosgene process, compounds such as bisphenols (derived structural units (A) to (C)) and monohydric phenols (derived terminal structures) are reacted with phosgene in the presence of an acid binder and a solvent. The acid binder can be, for example, pyridine and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, while the solvent can be, for example, dichloromethane or chloroform. Furthermore, to promote the polycondensation reaction, catalysts such as tertiary amines like triethylamine or quaternary ammonium salts like benzyltriethylammonium chloride are preferred.
[0137] Compounds such as monohydric phenols with derived terminal structures act as polymerization degree regulators. However, in addition, monohydric phenols such as phenol, p-tert-butylphenol, p-cumylphenol, and long-chain alkyl-substituted phenols can be used in combination at a ratio of less than 50% by mass relative to the monohydric phenol with derived terminal structures. Furthermore, small amounts of antioxidants such as sodium sulfite and sodium dithionite, as well as branching agents such as phloroglucinol and indomethacin, can be added as needed. The reaction temperature is typically 0–150°C, preferably 5–40°C. Although the reaction time is affected by the reaction temperature, it is typically 0.5 minutes to 10 hours, preferably 1 minute to 2 hours. Furthermore, during the reaction, it is preferable to maintain the pH of the reaction system above 10.
[0138] On the other hand, in transesterification, for example, compounds such as bisphenols derived from structural units (A) to (C), monohydric phenols derived from terminal structures, and diaryl carbonates are mixed and reacted at high temperature under reduced pressure.
[0139] Examples of diaryl carbonates include diphenyl carbonate, di-p-toluene carbonate, phenyl-p-toluene carbonate, di-p-chlorophenyl carbonate, and dinaphthalene carbonate. Two or more of these compounds can be used together. The reaction is typically carried out at a temperature ranging from 150 to 350°C, preferably from 200 to 300°C, and the final vacuum is preferably set below 1 mmHg to distill off the phenols derived from the diaryl carbonate generated during the transesterification reaction. While the reaction time is affected by factors such as reaction temperature and vacuum, it is typically around 1 to 24 hours. The reaction is preferably carried out in an inert gas environment such as nitrogen or argon. Furthermore, depending on the requirements, a small amount of molecular weight regulators other than monohydric phenols that derive terminal structures can be used in combination, and antioxidants, branching agents, etc., can also be added to the reaction.
[0140] <2. Monomer Mixture for Polymerization>
[0141] The monomer mixture for polymerization comprises monomer (a) of general formula (1) and / or monomer (b) of general formula (2) and monomer (c) of general formula (3). The monomer mixture for polymerization is a monomer mixture for forming structural units of thermoplastic resins and is suitable for manufacturing the above-mentioned polycarbonate resin.
[0142] The monomer mixture for polymerization can be easily manufactured by mixing monomers (a) to (c) using conventional methods.
[0143] In the monomer mixture for polymerization, the proportion of monomers (a) to (c) relative to the total molar number is, for example, 0.5 to 25 mol% of monomers (a) and (b), and 75 to 99.5 mol% of monomer (c). Furthermore, it is preferable that the proportion of monomers (a) to (c) is 1 to 22 mol% or 2 to 24 mol% of monomers (a) to (c), and 78 to 99 mol% or 76 to 98 mol% of monomer (c). More preferably, the proportion of monomers (a) to (b) can also be 3 to 18 mol%, 5 to 15 mol% (greater than 5 mol% or more than 5 mol% but less than 15 mol%), 5 to 20 mol% (greater than 5 mol% or more than 5 mol% but less than 20 mol%), or 5 to 25 mol% (greater than 5 mol% or more than 5 mol% but less than 25 mol%), etc.
[0144] Furthermore, the proportion of monomer (c) in the total molar number of monomers (a) to (c) can be, for example, 82–97 mol%, 85–95 mol% (more than 85 mol% and less than or less than 95 mol%), 80–95 mol% (more than 80 mol% and less than or less than 95 mol%), 75–95 mol% (more than 75 mol% and less than or less than 95 mol%), etc. The proportion of monomer (c) in the total molar number of monomers (a) to (c) can also be 76–96 mol%, 78–98 mol%, 79–97 mol%, etc.
[0145] Furthermore, for example, the total proportion of monomers (a) and (b) is 5 to 20 mol% relative to the total molar number of monomers (a) to (c), and the proportion of monomer (c) is 80 to 95 mol%. The molar ratio of monomers (a) to (c) in the monomer mixture for polymerization is preferably the same as the molar ratio of structural units (A) to (C) in the polycarbonate resin described above.
[0146] It should be noted that the range (mol%) related to the content of the above monomers (a) to (c) includes the range below the upper limit and the range less than the upper limit, and the range above the lower limit and the range greater than the lower limit.
[0147] The monomer mixture for polymerization may also be free of components other than monomers (a) to (c). Preferably, the total number of moles of structural units (a) to (c) in the monomer mixture for polymerization is 50 mol% or more, more preferably 70 mol% or more, further preferably 90 mol% or more, particularly preferably 95 mol% or more or substantially 100 mol%.
[0148] <3. Polycarbonate resin solution>
[0149] The polycarbonate resin solution contains the aforementioned polycarbonate resin and a solvent. There are no particular limitations on the type of solvent, as long as it can dissolve the polycarbonate resin. For example, (meth)acrylate compounds having (meth)acryloyl groups ((meth)acrylate groups) or aromatic compounds having aromatic rings can be used as solvents.
[0150] The (meth)acrylate compound used as a solvent preferably contains at least a (meth)acrylate. There is no particular limitation on the (meth)acrylate, but mono- or di(meth)acrylates with a total carbon number of 4 to 20 are preferred, more preferably mono- or di(meth)acrylates with a total carbon number of 5 to 15, and even more preferably mono- or di(meth)acrylates with a total carbon number of 5 to 10, 5 to 12, 6 to 10, 6 to 12, etc. Preferred examples of (meth)acrylates 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, and 1,6-hexanediol diacrylate. Among them, tetrahydrofurfuryl acrylate (THF-A), tetrahydrofurfuryl methacrylate (THF-M), benzyl acrylate (BZA), phenoxyethyl acrylate, and 1,6-hexanediol diacrylate are more suitable solvents, and THF-M is a particularly preferred example.
[0151] It should be noted that (meth)acrylates include acrylates and methacrylates.
[0152] 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, and toluidine. Among these, styrene, toluene, and xylene are more suitable as solvents.
[0153] Furthermore, in the solvent compound, for example, the refractive index value is 1.40 or more and 1.60 or less, preferably having a refractive index value of 1.42 or more and 1.58 or less, and more preferably having a refractive index value of 1.44 or more and 1.56 or less.
[0154] The aforementioned compounds, using solvents such as (meth)acrylates, exhibit excellent compatibility with polycarbonate resins, resulting in good solubility of the polycarbonate resin in solutions containing (meth)acrylates or similar solvents. Furthermore, the polycarbonate resin solution containing these solvents allows for cross-linking reactions to occur in solution. Moreover, when using such a polycarbonate resin solution, the cured product obtained from the polymerization of the polycarbonate resin exhibits a desirable color. In other words, when polycarbonate resin contained in a polycarbonate resin solution is cured using (meth)acrylates or similar solvents containing THF-M as solvents, cloudiness can be prevented, and a transparent cured product or molded body can be obtained.
[0155] The concentration of polycarbonate resin in the polycarbonate resin solution is not particularly limited, but preferably, based on the total mass of the polycarbonate resin solution, the concentration of polycarbonate resin is 1 to 20% by mass. More preferably, the concentration of polycarbonate resin in the polycarbonate resin solution is 2 to 18% by mass, even more preferably 3 to 16% by mass, and particularly preferably 5 to 15% by mass.
[0156] Polycarbonate resin solutions can be easily manufactured by mixing polycarbonate resin with solvents using conventional methods.
[0157] In polycarbonate resin solutions, for example, when used to form coatings, it is preferable to maintain a balanced and adequate balance of solvent solubility, coatability, adhesion, scratch resistance, and impact resistance. It has been shown that if the intrinsic viscosity of the polycarbonate resin solution is too low, the scratch resistance and impact resistance are insufficient; if the intrinsic viscosity is too high, the solvent solubility decreases and the solution viscosity increases, resulting in reduced coatability of the obtained coating. An ideal intrinsic viscosity range for the polycarbonate resin solution is preferably 0.3 to 2.0 dl / g, more preferably 0.35 to 1.5 dl / g.
[0158] <4. Cross-linked polycarbonate resin>
[0159] Crosslinked polycarbonate resin is obtained by crosslinking the above-mentioned polycarbonate resin. Crosslinked polycarbonate resin can be manufactured, for example, by irradiating the above-mentioned polycarbonate resin solution with energy rays such as ultraviolet light, causing the reactive groups contained in multiple polycarbonate resin molecules in the resin solution to undergo a crosslinking reaction with each other.
[0160] In this way, by polymerizing a self-polymerizing polycarbonate resin in, for example, a solution, a polymer of polycarbonate resin with cross-linking sites (cross-linked polycarbonate resin) can be easily manufactured without the need for secondary components such as polymerization initiators.
[0161] <5. Molded Body>
[0162] The molded articles of the present invention comprise at least a cross-linked polycarbonate resin obtained by causing a cross-linking reaction of a polycarbonate resin. Examples of molded articles include molded articles obtained by cross-linking polycarbonate resin in various coating and adhesive resin applications, such as cast articles. Specific examples of molded articles include films such as substrate films formed on a substrate, coatings (films); adhesive resins such as photosensitive electron lenses and conductive pastes; adhesives, resin modifiers, UV inks, etc. The substrate film is formed on, for example, a PVB (polyvinyl butyral) substrate or a PET (polyethylene terephthalate) substrate. As a cross-linked coating film formed on these substrates, its adhesion to the substrate is particularly excellent. Thus, the coating film obtained by coating a resin solution and curing it by heating is less prone to scratches or peeling during transportation and use due to friction, impact, etc., compared to conventional resin solution coating films.
[0163] The substrate film, which serves as the molded body, can be manufactured, for example, by removing the solvent from a polycarbonate resin solution, irradiating the resin residue with energy rays, or heating it. That is, the coating film is formed through the crosslinking and polymerization reaction of the polycarbonate resin achieved by irradiation with energy rays such as ultraviolet light or heating. The heating temperature during the heating process is preferably 50–150°C, more preferably 70–130°C, and even more preferably 80–120°C.
[0164] The thickness of the substrate film is preferably in the range of 5 to 200 μm, particularly preferably in the range of 10 to 120 μm, and further preferably in the range of 15 to 60 μm. A coating thinner than 5 μm has insufficient strength and can easily damage the substrate, while an excessively thick coating (greater than 200 μm) is prone to peeling due to coating shrinkage. Ultimately, considering the unusable application of peeled and discarded coatings, this is also economically disadvantageous.
[0165] Example
[0166] The present invention will now be described in more detail by way of examples, but the present invention is not limited to these examples.
[0167] (1) Solubility
[0168] Visually inspect the appearance of the resin solution and make a judgment based on the following indicators.
[0169] The resin solution contains no undissolved resin particles and is transparent: "Good".
[0170] The resin solution appears cloudy: "Slightly poor"
[0171] The resin does not dissolve at all: "Poor"
[0172] (2) Crosslinking property (UV curing property)
[0173] The obtained resin solution was poured into a rectangular perforated silicone mold with dimensions of 65×10×3 (mm), and irradiated with UV under the following conditions. The time until curing was determined.
[0174] Equipment used: UV lamp (ultraviolet irradiation device manufactured by Iwasaki Electric Co., Ltd.)
[0175] UV wavelength: 365nm
[0176] UV irradiation intensity: 50mw / cm 2 ×10 minutes
[0177] Curing within 8 minutes: "Good"
[0178] Curing in more than 8 minutes but less than 12 minutes: "Slightly worse"
[0179] Curing in more than 12 minutes but less than 24 minutes: "Acceptable".
[0180] It should be noted that when the sample is in a state where it can be removed from the silicone mold, the sample originating from the resin solution is considered to have cured. That is, the time from the start of UV irradiation until the sample formed from the resin solution can be demolded from the silicone mold is measured and referred to as the "time until curing" mentioned above.
[0181] (3) Appearance of the molded sheet
[0182] The appearance of the resulting molded sheet was visually evaluated.
[0183] The resin composition is free of haze, whitening, and colorlessness, and is visually transparent: "Good".
[0184] Although it may be cloudy or discolored, its transparency is relatively high: "Slightly poor".
[0185] Severe turbidity or cloudiness, lacking transparency (may limit its use in areas requiring transparency, but usable in other areas): "Poor"
[0186] (4) Impact strength
[0187] The impact strength of the resin composition (resin UV-cured sheet) obtained in (2) above was measured using an impact testing machine.
[0188] Impact testing machine: Impact testing machine manufactured by Toyo Seiki Co., Ltd.
[0189] Test conditions: The test piece was fixed on the fixture, and an Izod 2J counterweight was used with a 150-degree drop hammer.
[0190] (5) Drug resistance
[0191] Add 0.5g of the tablet and 4.5g of dichloromethane to a 20ml vial and stir. Visually inspect the resulting solution and judge its appearance according to the following indicators.
[0192] Undissolved matter was produced in the solution: "Good"
[0193] The solution contains no undissolved resin and is transparent: "Poor"
[0194] It should be noted that molded tablets that are not easily dissolved in solvents are considered to have excellent drug resistance.
[0195] (Example 1)
[0196] 96 g (0.36 mol) of bisphenol MIBK (4,4'-(1,3-dimethylbutylidene)bisphenol, hereinafter referred to as "MIBK": manufactured by Honshu Chemical Co., Ltd.), 4.0 g (0.02 mol) of 4,4'-dihydroxybenzophenone (hereinafter referred to as "4,4'-DHBP": manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.5 g of sodium dithionite (antioxidant and color inhibitor) were dissolved in 730 ml of 6.5 w / w% sodium hydroxide aqueous solution.
[0197] Add 300 ml of dichloromethane to the solution, and while stirring and maintaining the temperature at 15–25°C, blow 51.8 g of phosgene into the solution over 40 minutes.
[0198] After the phosgene blowing was completed, 2.20 g of p-tert-butylphenol (hereinafter referred to as "PTBP": manufactured by Dai Nippon Ink Chemical Industry Co., Ltd.) as a molecular weight regulator was added, and the mixture was stirred vigorously to emulsify the reaction solution. After emulsification, 0.5 ml of triethylamine was added, and the mixture was stirred at 20-30°C for about 1 hour to carry out the polymerization reaction.
[0199] After polymerization, the reaction solution was separated into an aqueous phase and an organic phase. The organic phase was neutralized with phosphoric acid, and repeated washing with water was performed until the conductivity of the washing solution (aqueous phase) reached below 100 μS / cm. The resulting polymer solution was transferred to an aluminum dish and placed on a heating plate to evaporate and remove the solvent. The resulting solid was further dried at 120°C for 24 hours to obtain the polymer solid.
[0200] The obtained polymer was analyzed by infrared absorption spectroscopy, and the results confirmed that it was at 1770 cm⁻¹ －1 There is absorption at a nearby carbonyl group, at 1240 cm⁻¹. －1 The presence of ether bonds in the vicinity confirms that the polymer is a polycarbonate resin with carbonate bonds.
[0201] Add 1g of the above polycarbonate resin and 9g of tetrahydrofurfuryl methacrylate (THF-M) to a 20ml vial and stir to obtain a polycarbonate resin solution.
[0202] Next, the above polycarbonate resin solution was poured into a rectangular perforated silicone mold with dimensions of 65×10×3 (mm), and then irradiated with UV light to obtain a UV-cured sheet (molded body). The UV irradiation conditions are as follows.
[0203] Equipment used: UV lamp (ultraviolet irradiation device manufactured by Iwasaki Electric Co., Ltd.)
[0204] UV wavelength: 365nm
[0205] UV irradiation intensity: 50mw / cm 2 ×10 minutes
[0206] The physical properties of the obtained polycarbonate resin, polycarbonate resin solution and molded articles are summarized in Table 1 below.
[0207] (Examples 2-14, Comparative Examples 1-5)
[0208] Except for replacing the raw material monomers (dihydroxy compounds) and chain terminators (hydroxy compounds) with the monomer types and molar ratios (mol%) shown in Table 1, and in some comparative examples, adding 1% by mass of 2-hydroxy-2-methylacetone (hereinafter also referred to as HMP) as a free radical initiator to the resin solution, the same procedure as in Example 1 was followed to obtain polycarbonate resin, polycarbonate resin solution and molded articles.
[0209] The physical properties of the obtained polycarbonate resin, polycarbonate resin solution and molded articles are summarized in the table below.
[0210] [Table 1]
[0211]
[0212] The results of the examples and comparative examples clearly demonstrate that the polycarbonate resins in the embodiments with DHBP structures in the main chain can initiate a curing reaction in a short time without the use of a photopolymerization initiator, and can achieve various physical properties in a balanced and good manner. That is, in each embodiment, curing can be achieved solely by irradiation of polycarbonate resin with energy rays, and molded articles with excellent impact resistance, chemical resistance, and other properties are formed. Furthermore, although the appearance may not show good results in some embodiments such as Example 1, these polycarbonate resins also perform well in terms of impact resistance, etc., and are therefore suitable for applications where color is not important.
[0213] Furthermore, suitable solvents for dissolving polycarbonate resin and forming a polycarbonate resin solution were investigated. Specifically, the following evaluations were conducted on whether resin and solvent in amounts reaching 10% by weight in the mixture could be mixed and miscible, and whether a cured product could be obtained by ultraviolet irradiation. It was confirmed that the polycarbonate resins in each embodiment could form solutions with various solvents, and that crosslinking reactions could be carried out without the use of a polymerization initiator (free radical initiator, HMP). In the evaluation of the progress of the curing reaction, the mixture was irradiated with ultraviolet light under the same conditions as the crosslinking property (UV curability) evaluation item listed in Table 1, and the presence or absence of a cured product was visually confirmed. Furthermore, regarding solubility, the case where a homogeneous solution was formed was evaluated as "good".
[0214] [Table 2]
[0215]
[0216] It should be noted that the molecular structures of the monomers, etc., used in the examples and comparative examples are as follows.
[0217]
[0218] The preferred embodiments of the present invention have been described in detail above with reference to examples, but the present invention is not limited to the embodiments described herein. It is understood that those skilled in the art to which this invention pertains will be able to conceive of various modifications or alterations within the scope of the technical concept described within the claimed protection, and these embodiments are of course also within the technical scope of this invention.
Claims
1. A polycarbonate resin, characterized in that, Include: Structural unit A derived from the monomer shown in general formula (1) below and / or structural unit B derived from the monomer shown in general formula (2) below; and The structural unit C of the monomer is derived from the following general formula (3). Relative to the total molar number of structural units A to C constituting the polycarbonate resin, the total proportion of structural unit A and structural unit B is 0.5 to 25 mol%, and the proportion of structural unit C is 75 to 99.5 mol%. In general formula (1), R 11 ~R 14 and R 15 ~R 18 Each can independently represent hydrogen, fluorine, chlorine, bromine, or iodine, or can be a substituent of 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. In general formula (2), R 21 ~R 25 and R 26 ~R 28 Each can independently represent hydrogen, fluorine, chlorine, bromine, or iodine, or can be a substituent of 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. In general formula (3), R 31 ~R 34 and R 35 ~R 38 Each can independently represent hydrogen, fluorine, chlorine, bromine, or iodine, or can be a substituent of 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. X is or , In the formula, R5 and R6 independently represent hydrogen, fluorine, chlorine, bromine, or iodine, or can be alkyl groups with 1 to 20 carbon atoms, alkoxy groups with 1 to 5 carbon atoms, or aryl groups with 6 to 12 carbon atoms, respectively, or represent groups in which R5 and R6 are bonded to form a carbon ring with 5 to 20 carbon atoms or a heterocycle with 5 to 12 elements. This excludes cases where both R5 and R6 are methyl groups. R7 and R8 can each independently represent hydrogen, fluorine, chlorine, bromine, or iodine, or can be alkyl with 1 to 9 carbon atoms, alkoxy with 1 to 5 carbon atoms, alkenyl with 2 to 12 carbon atoms, or aryl with 6 to 12 carbon atoms, respectively. c represents an integer from 0 to 20.
2. The polycarbonate resin according to claim 1, characterized in that: Relative to the total number of moles of the structural units A to C constituting the polycarbonate resin, the ratio of structural unit A to structural unit B is 5 to 20 mol%, and the ratio of structural unit C is 80 to 95 mol%.
3. The polycarbonate resin according to claim 1, characterized in that: In the general formula (1), R 11 ~R 14 and R 15 ~R 18 Each can independently represent hydrogen or an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, respectively. In general formula (2), R 21 ~R 25 and R 26 ~R 28 Each can independently represent hydrogen or an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, respectively.
4. The polycarbonate resin according to claim 3, characterized in that: The monomer represented by general formula (1) is represented by the following formula (1-1), and the monomer represented by general formula (2) is represented by the following formula (2-1). 。 5. The polycarbonate resin according to claim 1, characterized in that: In the general formula (3), R 31 ~R 34 and R 35 ~R 38 Each can independently represent hydrogen or an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, respectively. The X is or , In the formula, R5 and R6 each independently represent hydrogen or alkyl groups with 1 to 20 carbon atoms or aryl groups with 6 to 12 carbon atoms, which may each have substituents; or they represent groups in which R5 and R6 are bonded to form a carbon ring with 5 to 20 carbon atoms or a heterocycle with 5 to 12 elements. R7 and R8 each independently represent hydrogen or alkyl groups having 1 to 9 carbon atoms or aryl groups having 6 to 12 carbon atoms, respectively.
6. The polycarbonate resin according to claim 5, characterized in that: The monomers represented by the general formula (3) are selected from the following formulas (3-1) to (3-4). 。 7. The polycarbonate resin according to claim 1, characterized in that: The end structure of the polycarbonate resin is represented by the following formula (4). In general formula (4), A is vinyl, isopropenyl, styryl, or methine. R1 and R2 are each independently selected from alkylene groups with 1 to 20 carbon atoms, either single-bonded or substituted or unsubstituted. R3 is independently selected from hydrogen atoms, hydroxyl groups, alkyl groups with or without substituted carbon atoms numbering 1 to 20, alkoxy groups with or without substituted carbon atoms numbering 1 to 10, aryl groups with or without substituted carbon atoms numbering 6 to 12, and heteroaryl groups with or without substituted carbon atoms numbering 5 to 12. Z is independently selected from single bonds, ether groups, carbonyl groups, and ester groups. a is an integer between 0 and 3. b is an integer from 1 to 4. Y is an ether group or an ester group.
8. The polycarbonate resin according to claim 1, characterized in that: The end structure of the polycarbonate resin is derived from compounds selected from p-tert-butylphenol (PTBP), 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole (MBZT), 4-hydroxybenzophenone (4-HBP), polyoxyethylene-monoalkyl ether, and p-hydroxyphenylethanol (PHEP).
9. The polycarbonate resin according to claim 1, characterized in that: The main chain of the polycarbonate resin does not contain unsaturated bonds.
10. A monomer mixture for polymerization, characterized in that: The monomer mixture used for polymerization is used to form the structural units of the thermoplastic resin. The monomer mixture for polymerization comprises: Monomer a represented by general formula (1) and / or monomer b represented by general formula (2) below; and The monomer c shown in the following general formula (3), Relative to the total molar number of monomers a to c, the total proportion of monomer a and monomer b is 0.5 to 25 mol%, and the proportion of monomer c is 75 to 99.5 mol%. In general formula (1), R 11 ~R 14 and R 15 ~R 18 Each can independently represent hydrogen, fluorine, chlorine, bromine, or iodine, or can be a substituent of 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. In general formula (2), R 21 ~R 25 and R 26 ~R 28 Each can independently represent hydrogen, fluorine, chlorine, bromine, or iodine, or can be a substituent of 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. In general formula (3), R 31 ~R 34 and R 35 ~R 38 Each can independently represent hydrogen, fluorine, chlorine, bromine, or iodine, or can be a substituent of 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. X is or , In the formula, R5 and R6 independently represent hydrogen, fluorine, chlorine, bromine, or iodine, or can be alkyl groups with 1 to 20 carbon atoms, alkoxy groups with 1 to 5 carbon atoms, or aryl groups with 6 to 12 carbon atoms, respectively, or represent groups in which R5 and R6 are bonded to form a carbon ring with 5 to 20 carbon atoms or a heterocycle with 5 to 12 elements. This excludes cases where both R5 and R6 are methyl groups. R7 and R8 can each independently represent hydrogen, fluorine, chlorine, bromine, or iodine, or can be alkyl with 1 to 9 carbon atoms, alkoxy with 1 to 5 carbon atoms, alkenyl with 2 to 12 carbon atoms, or aryl with 6 to 12 carbon atoms, respectively. c represents an integer from 0 to 20.
11. A polycarbonate resin solution, characterized in that: It contains the polycarbonate resin and solvent as described in claim 1.
12. The polycarbonate resin solution according to claim 11, characterized in that: The solvent contains at least a (meth)acrylate solvent.
13. The polycarbonate resin solution according to claim 12, characterized in that: The (meth)acrylate is tetrahydrofurfuryl methacrylate (THF-M).
14. The polycarbonate resin solution according to claim 11, characterized in that: Based on the total mass of the polycarbonate resin solution, the concentration of the polycarbonate resin is 1 to 20 by mass.
15. A method for manufacturing a cross-linked polycarbonate resin, characterized in that: Irradiate the polycarbonate resin solution of claim 11 with ultraviolet light.
16. A cross-linked polycarbonate resin, characterized in that: Obtained by the manufacturing method described in claim 15.
17. A molded body, characterized in that: The molded body comprises the crosslinked polycarbonate resin of claim 16.