Polymer and resin composition

Abstract

To provide a polymer excellent in compatibility with a polycarbonate resin including a structural unit derived from isosorbide, and a resin composition comprising the polymer and exhibiting superior mechanical properties.SOLUTION: A polymer comprises a structural unit derived from a dihydroxy compound (A) having a heterocyclic skeleton and / or an alicyclic skeleton, and a structural unit derived from a Michael acceptor (B). The polymer has at least one vinyl group in its molecular structure. The resin composition contains this polymer.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to polymers and resin compositions. [Background technology]

[0002] Polycarbonate resins are generally produced using raw materials derived from petroleum resources. In recent years, concerns about the depletion of petroleum resources have led to a demand for the production of polycarbonate resins using raw materials obtained from biomass resources. Furthermore, concerns about global warming due to increased and accumulated carbon dioxide emissions leading to climate change and other issues have led to a demand for the development of polycarbonates made from plant-derived monomers, which would enable the realization of carbon neutrality.

[0003] Under these circumstances, polycarbonate resins have been proposed that use isosorbide (hereinafter sometimes referred to as "ISB"), a dihydroxy compound (anhydrosugar alcohol) obtained from biomass resources, as a monomer component (e.g., Patent Documents 1 and 2). Furthermore, studies have also been conducted to improve the physical properties of polycarbonate resins containing structural units derived from isosorbide by combining the polycarbonate resin containing structural units derived from isosorbide with other resins. For example, Patent Document 3 describes a polycarbonate resin composition containing a polycarbonate resin containing structural units derived from isosorbide and an acrylic resin in order to improve scratch resistance and optical properties. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2004 / 111106 [Patent Document 2] International Publication No. 2007 / 148604 [Patent Document 3] Patent Publication No. 2021-88651 Summary of the Invention [Problem to be solved by the invention]

[0005] However, polycarbonate resins containing structural units derived from ISB tend to be poorly compatible with other resins due to the characteristic skeleton of ISB, and as described in Patent Document 3, when polycarbonate resins containing structural units derived from ISB are composited with acrylic resins or the like, there is a problem that the mechanical properties of the resin composition are reduced.

[0006] The present invention has been made in view of the above background, and aims to provide a polymer that contains structural units derived from isosorbide and has excellent compatibility with polycarbonate resins, and a resin composition that contains this polymer and has excellent mechanical properties. [Means for solving the problem]

[0007] As a result of intensive research aimed at solving the above problems, the present inventors have discovered that a polymer having structural units derived from a specific compound has excellent compatibility with a polycarbonate resin containing structural units derived from ISB. Furthermore, the present inventors have found that adding a polymer chain containing structural units derived from a vinyl monomer to the polymer can improve compatibility not only with polycarbonate resins containing structural units derived from ISB, but also with other resins.

[0008] That is, one aspect of the present invention is a polymer according to the following items [1] to [5].

[0009] [1] A structural unit derived from a dihydroxy compound (A) having a heterocyclic skeleton and / or an alicyclic skeleton, and structural units derived from a Michael acceptor (B), A polymer that has at least one vinyl group in its molecular structure. [2] The polymer according to [1], wherein the structural unit derived from the dihydroxy compound (A) and the structural unit derived from the Michael acceptor (B) are linked via an ether bond.

[0010] [3] The polymer according to [1] or [2], wherein the vinyl group is contained in one or more polymerizable functional groups selected from the group consisting of a methacryloyl group, an acryloyl group, and a vinyl sulfone group. [4] The polymer according to any one of [1] to [3], wherein the polymer has a relative weight average molecular weight Mw of 100 or more and 200,000 or less. [5] A polymer comprising a first polymer chain comprising the polymer according to any one of [1] to [4], and a second polymer chain comprising a structural unit derived from a vinyl monomer and bonded to the polymerizable functional group of the polymer.

[0011] Another aspect of the present invention is a resin composition according to the following items [6] and [7].

[0012] [6] A resin composition containing the polymer according to any one of [1] to [5]. [7] A polycarbonate resin containing 30% by mass or more and 90% by mass or less of a structural unit represented by the following formula (1): The resin composition according to [6], further comprising an acrylic resin containing 50% by mass or more and 100% by mass or less of a structural unit represented by the following formula (2):

[0013] [ka]

[0014] [ka]

[0015] However, in the formula (2), R 1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent, and R 2 is an alkyl group which may have a substituent. [Effects of the Invention]

[0016] The polymer has structural units derived from a dihydroxy compound (A) having a heterocyclic skeleton and / or an alicyclic skeleton, and therefore has excellent compatibility with polycarbonate resins containing structural units derived from isosorbide (hereinafter sometimes referred to as "ISB structural units").

[0017] The polymer also contains at least one vinyl group. Therefore, by adding a second polymer chain containing a structural unit derived from a vinyl monomer to the vinyl group of a first polymer chain made of the polymer, it is possible to improve not only the compatibility between the polymer and a polycarbonate resin containing ISB structural units, but also the compatibility between the polymer and other resins. Therefore, by adding such a polymer to a resin composition containing a polycarbonate resin containing ISB structural units and other resins, the polymer functions as a compatibilizer, thereby improving the mechanical properties of the resin composition.

[0018] Therefore, according to the above-described embodiment, it is possible to provide a polymer that contains structural units derived from isosorbide and has excellent compatibility with polycarbonate resins, and a resin composition that contains this polymer and has excellent mechanical properties. DETAILED DESCRIPTION OF THE INVENTION

[0019] As used herein, the term "structural unit" refers to a chemical structure formed directly from a raw material compound by a polymerization reaction, and a chemical structure in which a part of the structure of the structural unit of a polymer obtained by a polymerization reaction is converted into another structure by treating the polymer with a chemical reaction. As used herein, the term "alicyclic skeleton" refers to a structure of a molecular skeleton constituting an organic compound that contains a saturated or unsaturated hydrocarbon ring that does not have aromaticity. The alicyclic skeleton may contain one hydrocarbon ring or two or more hydrocarbon rings. As used herein, the term "heterocyclic skeleton" refers to a structure of a molecular skeleton constituting an organic compound that contains a saturated or unsaturated heterocycle. Furthermore, the term "heterocycle" refers to a ring composed of two or more types of atoms. The heterocyclic skeleton may contain one heterocycle or two or more heterocycles.

[0020] In this specification, "(meth)acrylate" is a general term for acrylate and methacrylate. Similarly, "(meth)acrylic acid" is a general term for acrylic acid and methacrylic acid. In this specification, "Michael acceptor" is a general term for compounds having a structure in which an electron-withdrawing group is located adjacent to a vinyl group. Note that the electron-withdrawing group is a general term for a substituent that has a stronger tendency to attract electrons from the atom to which the electron-withdrawing group is bonded to the electron-withdrawing group than a hydrogen atom.

[0021] (polymer) The polymer has structural units derived from a dihydroxy compound (A) having a heterocyclic skeleton and / or an alicyclic skeleton and structural units derived from a Michael acceptor (B), and the polymer has at least one vinyl group in its molecular structure.

[0022] In the polymer, the structural unit derived from the dihydroxy compound (A) and the structural unit derived from the Michael acceptor (B) may be bonded directly or via another structural unit. From the viewpoint of compatibility with a polycarbonate resin having an ISB structural unit, it is preferred that the structural unit derived from the dihydroxy compound (A) and the structural unit derived from the Michael acceptor (B) are bonded via an ether bond. In this case, it is preferred that the oxygen atom of the ether bond is an oxygen atom derived from the dihydroxy compound (A). From the same viewpoint, it is more preferred that the structural unit derived from the dihydroxy compound (A) and the structural unit derived from the Michael acceptor (B) are bonded via a bond represented by the following formula (3):

[0023] [ka]

[0024] In the formula (3), A represents a structure derived from the dihydroxy compound (A), and B represents a structure derived from the Michael acceptor (B). The oxygen atom bonded to A is an oxygen atom derived from the dihydroxy compound (A).

[0025] The polymer has a heterocyclic skeleton and / or an alicyclic skeleton in its molecular structure. The heterocyclic skeleton and the alicyclic skeleton in the polymer are contained in structural units derived from the dihydroxy compound (A). The polymer may also contain a heterocyclic skeleton and / or an alicyclic skeleton derived from the Michael acceptor (B).

[0026] The sum of the content of structural units having a heterocyclic skeleton and the content of structural units having an alicyclic skeleton in the polymer is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 20 mol% or more, based on the total content of all structural units constituting the polymer. In this case, the compatibility of the polymer with a polycarbonate resin containing an ISB structural unit can be further improved. From the same viewpoint, the sum of the content of structural units having a heterocyclic skeleton and the content of structural units having an alicyclic skeleton in the polymer is preferably 100 mol% or less, more preferably 95 mol% or less, and even more preferably 90 mol% or less, based on the total content of all structural units constituting the polymer.

[0027] When constituting a preferred range of the total content of the structural units having a heterocyclic skeleton and the structural units having an alicyclic skeleton, the upper and lower limits of the total content can be combined arbitrarily. For example, the total content of the structural units having a heterocyclic skeleton and the structural units having an alicyclic skeleton may be 5 mol% or more and 100 mol% or less, 10 mol% or more and 95 mol% or less, or 20 mol% or more and 90 mol% or less, based on the total content of all structural units constituting the polymer.

[0028] The total content of the structural unit having a heterocyclic skeleton and the structural unit having an alicyclic skeleton can be calculated based on the molar ratio of the raw material compounds used in the synthesis of the polymer. For example, when the Michael acceptor (B) does not have either a heterocyclic skeleton or an alicyclic skeleton, the molar ratio of the dihydroxy compound (A) used in the synthesis of the polymer can be used as the total content. When the Michael acceptor (B) has a heterocyclic skeleton and / or an alicyclic skeleton, the total content can be used as the molar ratio of the dihydroxy compound (A) used in the synthesis of the polymer and the molar ratio of the Michael acceptor (B).

[0029] The relative weight average molecular weight (Mw) of the polymer is preferably from 100 to 200,000, more preferably from 500 to 100,000, and even more preferably from 1,000 to 50,000. In this case, the compatibility of the polymer with the polycarbonate resin containing the ISB structural unit can be further improved.

[0030] [Dihydroxy compound (A)] The dihydroxy compound (A) used in the synthesis of the polymer has a heterocyclic skeleton and / or an alicyclic skeleton and two hydroxy groups bonded to these structures directly or via a hydrocarbon group or the like. The structural units derived from the dihydroxy compound (A) have the function of increasing the compatibility of the polymer with the ISB structural units in the polycarbonate resin. The polymer may contain structural units derived from one type of dihydroxy compound (A), or may contain structural units derived from two or more types of dihydroxy compounds (A).

[0031] The dihydroxy compound (A) may be, for example, a heterocyclic dihydroxy compound or an alicyclic dihydroxy compound.

[0032] Examples of heterocyclic dihydroxy compounds include the following compounds: 1,4:3,6-dianhydroglucitol (isosorbide), 1,4-anhydroerythritol, 1,4-dithiocyan-2,5-diol, 2,5-furandiethanol, 3,9-bis(2-hydroxyethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane, 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane, 3,9-bis(2-hydroxy-1,1-diethylethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane, and 3,9-bis(2-hydroxy-1,1-dipropylethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane. Among these, as the heterocyclic dihydroxy compound, 1,4:3,6-dianhydroglucitol (isosorbide), 3,9-bis(2-hydroxyethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane, 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane, and 3,9-bis(2-hydroxy-1,1-diethylethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane are preferred, and 1,4:3,6-dianhydroglucitol (isosorbide) is more preferred.

[0033] Examples of alicyclic dihydroxy compounds include the following compounds: dihydroxy compounds which are primary alcohols of alicyclic hydrocarbons, exemplified by 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, pentacyclopentadecanedimethanol, 2,6-decalindimethanol, 1,5-decalindimethanol, 2,3-decalindimethanol, 2,3-norbornane dimethanol, 2,5-norbornane dimethanol, 1,3-adamantanedimethanol, and dihydroxy compounds derived from terpene compounds such as limonene; and dihydroxy compounds which are secondary or tertiary alcohols of alicyclic hydrocarbons, exemplified by 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,3-adamantanediol, hydrogenated bisphenol A, and 2,2,4,4-tetramethyl-1,3-cyclobutanediol. Among these, as the alicyclic dihydroxy compound, it is preferable to use a dihydroxy compound that is a primary alcohol of an alicyclic hydrocarbon, and it is more preferable to use 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, 1,2-cyclohexanedimethanol, or 1,3-cyclohexanedimethanol.

[0034] Dihydroxy oligomers having a heterocyclic skeleton and / or an alicyclic skeleton can also be used as the dihydroxy compound (A). The term "oligomer" used here refers to a general term for dihydroxy compounds terminated at both ends and having a number average molecular weight (Mn) of 10,000 or less, which are obtained by linking dihydroxy compounds via, for example, carbonate bonds or ester bonds.

[0035] The dihydroxy oligomer having a heterocyclic and / or alicyclic skeleton may be, for example, a polycarbonate diol having a heterocyclic and / or alicyclic skeleton, or a polyester diol having a heterocyclic and / or alicyclic skeleton. Examples of the dihydroxy oligomer having a heterocyclic and / or alicyclic skeleton include commercially available polycarbonate diols such as UM90(1 / 3), UM90(1 / 1), and UM(3 / 1) (all manufactured by UBE Corporation), BENEBIOL (registered trademark) HSB830B, BENEBIOL HSB840B, BENEBIOL HSB840H, and BENEBIOL HSB850H (all manufactured by Mitsubishi Chemical Corporation). Among these, it is preferable to use a polycarbonate diol having an isosorbide skeleton as the dihydroxy oligomer, and it is more preferable to use BENEBIOL HSB840B, BENEBIOL HSB840H, or BENEBIOL HSB850H.

[0036] [Michael acceptor (B)] The Michael acceptor (B) used in the synthesis of the polymer has two vinyl groups per molecule and an electron-withdrawing group bonded to the vinyl group. The vinyl groups of the Michael acceptor (B) can bond with the hydroxyl groups of the dihydroxy compound (A). Therefore, by using a Michael acceptor (B) having two vinyl groups per molecule, multiple dihydroxy compounds (A) can be linked via the Michael acceptor (B).

[0037] As the Michael acceptor (B), for example, a bismaleimide compound, a divinyl sulfone compound, a dipropiolic acid ester compound, a di(meth)acrylate compound, etc. Among these, from the viewpoints of cost and variety of structures, it is preferable to use a di(meth)acrylate compound as the Michael acceptor (B).

[0038] Examples of the bismaleimide compound include N,N'-bismaleimide-4,4'-diphenylmethane, 1,1'-(methylenedi-4,1-phenylene)bismaleimide, N,N'-(1,1'-biphenyl-4,4'-diyl)bismaleimide, N,N'-(4-methyl-1,3-phenylene)bismaleimide, 1,1'-(3,3'-dimethyl-1,1'-biphenyl-4,4'-diyl)bismaleimide, N,N'-ethylenedimaleimide, N,N' Examples of the bismaleimide compound include N,N'-(1,2-phenylene)dimaleimide, N,N'-(1,3-phenylene)dimaleimide, N,N'-thiodimaleimide, N,N'-dithiodimaleimide, N,N'-ketone dimaleimide, N,N'-methylene dimaleimide, bis-maleimide methyl ether, 1,2-bis(maleimide)-1,2-ethanediol, N,N'-4,4'-diphenylether-bismaleimide, and 4,4'-bis(maleimide)-diphenyl sulfone. Among these, N,N'-bismaleimide-4,4'-diphenylmethane, 1,1'-(methylenedi-4,1-phenylene)bismaleimide, N,N'-ethylene dimaleimide, and N,N'-(1,2-phenylene)dimaleimide are preferred.

[0039] Examples of the divinyl sulfone compound include divinyl sulfone, bis(vinyl sulfone)tricyclo[5.2.1.0 2,6 ]decane, N,N'-ethylenebis(2-(vinylsulfonyl)acetamide, etc. Among these, it is preferable to use divinyl sulfone as the divinyl sulfone compound.

[0040] Dipropiolic acid ester compounds can be obtained, for example, by reacting a diol with propiolic acid. Examples of dipropiolic acid ester compounds include 1,1'-"1,4-cyclohexanediylbis(methylene)"di-2-propionate, 1,4:3,6-dianhydro-2,5-di-2-propionate, 1,1'-(1,6-hexanediyl)di-2-propionate, and propane-1,3-diyldipropionate. Among these, it is preferable to use 1,1'-"1,4-cyclohexanediylbis(methylene)"di-2-propionate and 1,4:3,6-dianhydro-2,5-di-2-propionate as dipropiolic acid ester compounds.

[0041] Examples of di(meth)acrylate compounds include diesters obtained by reacting a diol with (meth)acrylic acid, and di(meth)acrylates obtained by reacting a compound having two epoxy groups with (meth)acrylic acid.

[0042] Examples of diesters of diols and (meth)acrylic acid include ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate. Acrylate, tetraethylene glycol di(meth)acrylate, 2-hydroxy-1,3-di(meth)acryloyloxypropane, 2,2-bis[4-((meth)acryloyloxyethoxy)phenyl]propane, 2,2-bis[4-((meth)acryloyloxy-polyethoxy)phenyl]propane, bis[4-((meth)acryloyloxy-ethoxy)phenyl]methane, 2-hydroxy-1-(meth)acryloyloxy-3-(meth)acryloyloxypropane, tricyclo(5.2.1.0 2,6Among these, examples of diesters of diols and (meth)acrylic acid include 1,4-cyclohexanedimethanol diacrylate, tricyclo(5.2.1.0), and the like. 2,6 It is preferable to use decanedimethanol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and polyethylene glycol di(meth)acrylate.

[0043] Examples of di(meth)acrylates obtained by reacting an epoxy compound with (meth)acrylic acid include bisphenol A diglycidyl ether (meth)acrylic acid adduct and bisphenol F diglycidyl ether (meth)acrylic acid adduct.

[0044] [Vinyl group] The polymer has one vinyl group in its molecular structure. The vinyl group may be included as part of a polymerizable functional group having a polymerizable unsaturated bond. Examples of such a polymerizable functional group include a methacryloyl group, an acryloyl group, and a vinyl sulfone group. The vinyl group in the polymer is preferably included in one or more polymerizable functional groups selected from the group consisting of a methacryloyl group, an acryloyl group, and a vinyl sulfone group.

[0045] The vinyl group in the polymer can react with a second polymer chain to form a bond when the second polymer chain is added to the polymer. The position of the vinyl group is not particularly limited. For example, the vinyl group may be located at the end of the polymer molecular chain. Alternatively, the vinyl group may be located in the middle of the polymer molecular chain.

[0046] The method for introducing vinyl groups into the polymer can take various forms. For example, by leaving some of the vinyl groups in the Michael acceptor (B) unreacted with the dihydroxy compound (A), the unreacted vinyl groups can be introduced into the polymer.

[0047] When introducing a vinyl group by this method, it is sufficient to adjust the mixing ratio of the dihydroxy compound (A) and the Michael acceptor (B) within an appropriate range during the production of the polymer. More specifically, during the production of the polymer, it is preferable to adjust the mixing ratio of the dihydroxy compound (A) and the Michael acceptor (B) so that the molar ratio of the content of structural units derived from the Michael acceptor (B) to the content of structural units derived from the dihydroxy compound (A) in the polymer is 0.7 or more and 2.0 or less.

[0048] By setting the molar ratio of the content of structural units derived from the dihydroxy compound (A) to the content of structural units derived from the Michael acceptor (B) in the polymer within the specific range, unreacted vinyl groups tend to remain in the polymer. As a result, a polymer having vinyl groups can be easily obtained. From the viewpoint of more easily obtaining a polymer having vinyl groups, the molar ratio of the content of structural units derived from the Michael acceptor (B) to the content of structural units derived from the dihydroxy compound (A) in the polymer is more preferably 0.8 to 1.5, even more preferably 0.9 to 1.4, and most preferably 1.0 to 1.2.

[0049] Furthermore, for example, when producing a polymer, by copolymerizing a compound (C) having a vinyl group in addition to the dihydroxy compound (A) and the Michael acceptor (B), the vinyl group of the compound (C) can be introduced into the polymer. As the compound (C), it is preferable to use a compound having a structure shown in the following formulas (4) to (6).

[0050] [ka]

[0051] [ka]

[0052] [ka]

[0053] However, in the formulas (4) to (6), R 3 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent, and n is an integer of 1 or more and 10 or less.

[0054] The content of the structural units derived from the compound (C) in the polymer is preferably 0.01 to 0.2, more preferably 0.02 to 0.15, and even more preferably 0.05 to 0.12, in terms of molar ratio relative to the content of the structural units derived from the dihydroxy compound (A). In this case, the vinyl group of the compound (C) can be introduced into the polymer more efficiently.

[0055] [Method for producing polymer] The polymer can be obtained, for example, by polymerizing raw material compounds containing a dihydroxy compound (A) and a Michael acceptor (B) under appropriate conditions in the presence of a base catalyst.

[0056] The amount of the base catalyst added is preferably 0.01 or more and 0.5 or less, more preferably 0.02 or more and 0.3 or less, in terms of molar ratio relative to the amount of the dihydroxy compound (A) used.

[0057] The base catalyst can be either a Brønsted base or a Lewis base. Brønsted bases are compounds that can accept hydrogen ions, while Lewis bases are compounds that have an unshared electron pair.

[0058] As the Brønsted base, it is preferable to use a base whose conjugate acid has an acid dissociation constant (hereinafter referred to as "PKa") of 14 or more and 60 or less, more preferably 15 or more and 50 or less, and even more preferably 16 or more and 40 or less. A Brønsted base whose conjugate acid has a PKa within the above-mentioned specific range has a level of basicity that allows it to abstract protons from the hydroxy groups in the dihydroxy compound (A), and can carry out the target reaction without causing unintended side reactions such as anionic polymerization.

[0059] Examples of Bronsted bases include the following bases:

[0060] Alkoxide salts such as t-potassium butoxide, t-sodium butoxide, sodium methoxide, potassium methoxide, sodium ethoxide, and potassium ethoxide; alkali metal hydride compounds such as sodium hydride and potassium hydride; metal amides such as potassium hexamethyldisilamide and lithium isodipropylamide; alkyl metal compounds such as alkyllithium and alkylaluminum; 1-t-butyl-2,2,4,4,4-pentakis(dimethylamino)-2λ 5 ,4λ 5 -Catenadi(phosphazene), 1-ethyl-2,2,4,4,4-pentakis(dimethylamino)-2λ 5 ,4λ 5 -Catenadi(phosphazene), 1-t-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)-phosphoranylideneamino]-2λ 5 ,4λ 5 Phosphorus-based bases, such as phosphazene compounds, such as -catenadi(phosphazene). From the standpoint of reagent safety and cost, it is preferable to use an alkoxide salt as the Bronsted base.

[0061] As the Lewis base, it is preferable to use a tertiary amine compound or a phosphorus compound substituted with an electron-donating group. Examples of the Lewis base include the following bases.

[0062] Tertiary amine compounds such as triethylamine and 1,4-diazabicyclo[2.2.2]octanetriethylenediamine.

[0063] Trimethylphosphine, triethylphosphine, tripropylphosphine, triisopropylphosphine, tri-n-butylphosphine, tri-t-butylphosphine, tri-n-octylphosphine, tricyclohexylphosphine, tribenzylphosphine, triphenylphosphine, diphenylmethylphosphine, dimethylphenylphosphine, diphenylcyclohexylphosphine, dicyclohexylphenylphosphine, diethylphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tri-2,4-xylylphosphine Monophosphine compounds typified by sphines, tri-2,5-xylylphosphine, tri-3,5-xylylphosphine, tris(p-methoxyphenyl)phosphine, tris(pt-butoxyphenyl)phosphine, di-t-butylphenylphosphine(2,4,6)trimethoxytriphenylphosphine, tris(2,4,6-trimethoxyphenyl)phosphine, [4-(N,N-dimethylamino)phenyl]di-t-butylphosphine, di-t-butyl(2-butenyl)phosphine, di-t-butyl(3-methyl-2-butenyl)phosphine, and trimethylphosphine.

[0064] Diphosphine compounds such as 1,2-bis(dimethylphosphino)ethane, bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, 1,2-bis(diphenylphosphino)propane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 2,3-bis(diphenylphosphino)butane, and 1,5-bis(diphenylphosphino)pentane.

[0065] The solvent used in the reaction is not particularly limited, and examples of the solvent that can be used include aromatic hydrocarbon solvents such as toluene, ethylbenzene, and xylene; aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, and cyclohexane; ketone solvents such as acetone, methyl isobutyl ketone, and methyl ethyl ketone; ester solvents such as butyl acetate; ether solvents such as tetrahydrofuran and dioxane; amide solvents such as N,N-dimethylformamide; and sulfoxide solvents such as dimethyl sulfoxide.

[0066] In addition, in the synthesis of the polymer, the reaction may be carried out without using a solvent. In particular, when a diacrylate, which is a Michael acceptor (B) with low reactivity, is used as a reaction substrate, it is preferable to carry out the reaction without using a solvent from the viewpoint of reaction rate.

[0067] The reaction temperature is not particularly limited, but it is preferable to carry out the reaction within a range of, for example, 0°C or higher and 150°C or lower. In particular, when the reaction is carried out without a solvent, it is preferable to carry out the reaction at a temperature equal to or higher than the melting point of the dihydroxy compound (A). By setting the reaction temperature at or higher than the melting point, the dihydroxy compound (A) dissolves and mixes more intimately with the Michael acceptor (B), which is expected to improve the reaction rate.

[0068] The reaction time is not particularly limited, but can generally be set appropriately between 0.5 hours and 48 hours.

[0069] (Polymers having block and / or graft structures) As mentioned above, the polymer has at least one vinyl group, and therefore, by adding another polymer to the vinyl group of the polymer, a block copolymer or a graft copolymer can be obtained.

[0070] For example, by mixing the polymer with a vinyl-based monomer containing a vinyl group and carrying out radical polymerization, a polymer can be obtained that includes a first polymer chain consisting of a polymer containing structural units derived from the dihydroxy compound (A) and structural units derived from the Michael acceptor (B), and a second polymer chain containing structural units derived from the vinyl-based monomer and bonded to the vinyl group of the polymer. The polymer thus obtained has a block structure and / or a graft structure.

[0071] Here, the block structure refers to a structure in which a block consisting of the first polymer chain and a block consisting of the second polymer chain are bonded to each other in series in a polymer chain. A copolymer having a block structure is also called a block copolymer.

[0072] The term "graft structure" refers to a structure comprising a trunk polymer and branch polymers branched from the trunk polymer. A copolymer having a graft structure is sometimes called a "graft copolymer." The trunk polymer in a graft copolymer may be either a first polymer chain or a second polymer chain. However, from the viewpoint of ensuring compatibility with a polycarbonate resin having ISB structural units while improving compatibility with other resins, it is preferable that the trunk polymer in the graft copolymer is a second polymer chain and the branch polymer is a first polymer chain.

[0073] The mass ratio of the second polymer chain in the polymer having a block structure and / or a graft structure is preferably 20 to 90 parts by mass, more preferably 30 to 80 parts by mass, and even more preferably 40 to 70 parts by mass, per 100 parts by mass of the total mass of the polymer. In this case, the compatibility of the polymer with resins other than the polycarbonate resin having an ISB structural unit can be more easily improved.

[0074] The relative weight average molecular weight (Mw) of the polymer having a block structure and / or a graft structure is preferably 1,000 or more and 1,000,000 or less, more preferably 2,000 or more and 500,000 or less, and even more preferably 5,000 or more and 250,000 or less.

[0075] The second polymer chain may be a polymer of one type of vinyl monomer, or may be a polymer of two or more types of vinyl monomers. The vinyl monomer used in the second polymer chain is not particularly limited as long as it has a vinyl group in its molecular structure. Examples of the vinyl monomer used in the second polymer chain include (meth)acrylic acid esters and aromatic vinyl compounds.

[0076] Examples of (meth)acrylic acid esters include linear or branched carbonized (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, i-pentyl (meth)acrylate, n-hexyl (meth)acrylate, heptyl (meth)acrylate, n-octyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. Alkyl (meth)acrylates having a hydrogen skeleton; alkyl (meth)acrylates having an alicyclic skeleton such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dicyclopentadienyl (meth)acrylate, and dicyclopentanyl (meth)acrylate; (meth)acrylates having an aromatic ring introduced into the side chain such as phenyl (meth)acrylate and benzyl (meth)acrylate; polyethylene glycol mono(meth)acrylate, polypropylene (Meth)acrylates having a polyethylene glycol group, such as polyethylene glycol mono(meth)acrylate, methoxypolyethylene glycol mono(meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, diethylene glycol monoethyl ether (meth)acrylate, and polyethylene glycol methyl ether (meth)acrylate; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate hydroxyalkyl (meth)acrylates such as methyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 8-hydroxyoctyl (meth)acrylate; and (meth)acrylates having an oxyethylene group such as methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxymethyl (meth)acrylate, ethoxyethyl (meth)acrylate, propoxymethyl (meth)acrylate, propoxyethyl (meth)acrylate, butoxymethyl (meth)acrylate, and butoxyethyl (meth)acrylate.Among these, as the (meth)acrylic acid ester, it is preferable to use methyl (meth)acrylate, ethyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dicyclopentadienyl (meth)acrylate, dicyclopentanyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, benzyl (meth)acrylate, and methoxyethyl (meth)acrylate. The above-mentioned (meth)acrylic acid esters may be used alone, or two or more kinds of (meth)acrylic acid esters may be used in combination.

[0077] Examples of aromatic vinyl compounds include styrene, α-methylstyrene, divinylbenzene, vinyltoluene, p-styrenesulfonic acid, etc. These aromatic vinyl compounds may be used alone, or two or more aromatic vinyl compounds may be used in combination.

[0078] Vinyl monomers having a polar group can also be used. Examples of vinyl monomers having a polar group include vinyl monomers in which a polar group is directly linked to a vinyl group, such as (meth)acrylic acid, vinyl sulfonic acid, and vinyl phosphonic acid; vinyl monomers in which a polar group is connected to a side chain, such as dimethylaminoethyl (meth)acrylate; and vinyl monomers in which a polar group is introduced into an aromatic ring, such as vinylbenzenesulfonic acid. These vinyl monomers having a polar group may be used alone, or two or more vinyl monomers may be used in combination.

[0079] [Method for producing polymers having block and / or graft structures] The polymer having a block structure and / or a graft structure can be obtained, for example, by radical polymerization of a vinyl monomer in the presence of the polymer having a structural unit derived from a dihydroxy compound (A), a structural unit derived from a Michael acceptor (B), and a vinyl group. Examples of the form of radical polymerization include solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization.

[0080] The polymerization solvent used in the solution polymerization is not particularly limited, and the solution polymerization can be carried out using, for example, aromatic hydrocarbon solvents such as toluene, ethylbenzene, xylene, etc.; aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, cyclohexane, etc.; ketone solvents such as acetone, methyl isobutyl ketone, methyl ethyl ketone, etc.; ester solvents such as butyl acetate, etc.; ether solvents such as tetrahydrofuran, dioxane, etc.; amide solvents such as N,N-dimethylformamide, etc.; or sulfoxide solvents such as dimethyl sulfoxide, etc.

[0081] The amount of the polymerization solvent used is preferably 50 parts by mass or more and 500 parts by mass or less, and more preferably 100 parts by mass or more and 300 parts by mass or less, relative to 100 parts by mass of the total amount of the vinyl-based monomers.

[0082] Examples of radical polymerization initiators used in radical polymerization include peroxides such as dibenzoyl peroxide and tert-butyl permaleate, and azo compounds such as 2,2'-azobisisobutyronitrile and azobisisovaleronitrile. A single radical polymerization initiator may be used, or two or more radical polymerization initiators may be used in combination. The amount of radical polymerization initiator used is preferably 0.0001 to 10 parts by mass, more preferably 0.001 to 1 part by mass, per 100 parts by mass of the total amount of vinyl monomers.

[0083] The polymerization temperature in the radical polymerization may be set appropriately. For example, it is preferable to carry out the radical polymerization at a temperature of −100° C. or higher and 250° C. or lower, as this is a suitable temperature range for using a radical polymerization initiator.

[0084] The polymerization time in the radical polymerization can be appropriately set within the range of, for example, 0.5 hours to 48 hours.

[0085] (Resin composition) A resin composition can be obtained by compounding the polymer with a resin. As described above, the polymer having a block structure and / or a graft structure has excellent compatibility with both a polycarbonate resin having an ISB structural unit and a resin other than the polycarbonate resin. Therefore, the polymer having a block structure and / or a graft structure is suitable as a compatibilizer between a polycarbonate resin having an ISB structural unit and a resin other than the polycarbonate resin.

[0086] The resin composition preferably contains, for example, a polycarbonate resin containing 30% by mass or more and 90% by mass or less of a structural unit represented by the following formula (1), an acrylic resin containing 50% by mass or more and 99% by mass or less of a structural unit represented by the following formula (2), and the polymer.

[0087] [ka]

[0088] [ka]

[0089] However, in the formula (2), R 1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms and optionally having a substituent, and R 2 is an alkyl group which may have a substituent.

[0090] The content of the polycarbonate resin having an ISB structural unit in the resin composition is preferably 10 to 94.9 parts by mass, more preferably 30 to 90 parts by mass, and even more preferably 40 to 85 parts by mass, per 100 parts by mass of the resin composition. The content of the acrylic resin in the resin composition is preferably 5 to 70 parts by mass, more preferably 10 to 60 parts by mass, and even more preferably 20 to 50 parts by mass, per 100 parts by mass of the resin composition. The content of the polymer having a block structure and / or a graft structure is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, and even more preferably 1 to 10 parts by mass, per 100 parts by mass of the resin composition.

[0091] [Polycarbonate resin] The polycarbonate resin blended in the resin composition has at least the structural unit represented by formula (1) (i.e., the structural unit derived from ISB) and a linking group linking adjacent structural units. The polycarbonate resin may further contain a second structural unit having a structure different from that of the structural unit represented by formula (1).

[0092] Examples of compounds that form the second structural unit include aliphatic dihydroxy compounds, alicyclic dihydroxy compounds, ether-containing dihydroxy compounds, acetal-containing dihydroxy compounds, aromatic-containing dihydroxy compounds, and dicarboxylic acids. Note that polycarbonate resins that partially incorporate structural units derived from diester compounds are called polyester carbonate resins. In this specification, the term "polycarbonate resin" encompasses polyester carbonate resins.

[0093] Examples of aliphatic dihydroxy compounds include the following dihydroxy compounds: straight-chain aliphatic dihydroxy compounds such as ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-heptanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol; and branched-chain aliphatic dihydroxy compounds such as 1,3-butanediol, 1,2-butanediol, neopentyl glycol, and hexylene glycol.

[0094] Examples of alicyclic dihydroxy compounds include the following dihydroxy compounds: dihydroxy compounds which are primary alcohols of alicyclic hydrocarbons, exemplified by 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, pentacyclopentadecanedimethanol, 2,6-decalindimethanol, 1,5-decalindimethanol, 2,3-decalindimethanol, 2,3-norbornane dimethanol, 2,5-norbornane dimethanol, 1,3-adamantanedimethanol, and dihydroxy compounds derived from terpene compounds such as limonene; and dihydroxy compounds which are secondary or tertiary alcohols of alicyclic hydrocarbons, exemplified by 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,3-adamantanediol, hydrogenated bisphenol A, and 2,2,4,4-tetramethyl-1,3-cyclobutanediol.

[0095] Examples of the ether-containing dihydroxy compound include oxyalkylene glycols and dihydroxy compounds containing an acetal ring. Examples of the oxyalkylene glycol include diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

[0096] Examples of acetal-containing dihydroxy compounds that can be used include spiroglycol (also known as 3,9-bis(1,1-dimethyl-2-hydroxyethyl-2,4,8,10-tetraoxaspiro[5,5]undecane) and dioxane glycol (also known as 2-(1,1-dimethyl-2-hydroxyethyl)-5-ethyl-5-hydroxymethyl-1,3-dioxane).

[0097] Examples of aromatic-containing dihydroxy compounds that can be used include the following dihydroxy compounds: 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-diethylphenyl)propane, 2,2-bis(4-hydroxy-(3-phenyl)phenyl)propane, 2,2-bis(4-hydroxy-(3,5-diphenyl)phenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, bis(4-hydroxyphenyl)propane, )methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)diphenylmethane, 1,1-bis(4-hydroxyphenyl)-2-ethylhexane, 1,1-bis(4-hydroxyphenyl)decane, bis(4-hydroxy-3-nitrophenyl)methane, 3,3-bis(4-hydroxyphenyl)pentane, 1,3- ...diphenylmethane, 1,1-bis(4-hydroxyphenyl)diphenylmethane, 1,1-bis(4-hydroxyphenyl)diphenylmethane, 1,1-bis(4-hydroxyphenyl)diphenylmethane, 1,1-bis(4- Bis(2-(4-hydroxyphenyl)-2-propyl)benzene, 1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)sulfone, 2,4'-dihydroxydiphenyl sulfone, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxy-3-methylphenyl)sulfide, bis(4-hydroxyphenyl)disulfide, 4, Aromatic bisphenol compounds such as 4'-dihydroxydiphenyl ether and 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether; dihydroxy compounds having an ether group bonded to an aromatic group such as 2,2-bis(4-(2-hydroxyethoxy)phenyl)propane, 2,2-bis(4-(2-hydroxypropoxy)phenyl)propane, 1,3-bis(2-hydroxyethoxy)benzene, 4,4'-bis(2-hydroxyethoxy)biphenyl, and bis(4-(2-hydroxyethoxy)phenyl)sulfone;9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-(2-hydroxypropoxy)phenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)fluorene, 9,9-bis(4-(2-hydroxypropoxy)-3-methylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-isopropylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-isobutylphenyl)fluorene Dihydroxy compounds having a fluorene ring, such as 9,9-bis(4-(2-hydroxyethoxy)-3-tert-butylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-cyclohexylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3,5-dimethylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-tert-butyl-6-methylphenyl)fluorene, and 9,9-bis(4-(3-hydroxy-2,2-dimethylpropoxy)phenyl)fluorene;

[0098] Examples of dicarboxylic acids include the following compounds: aromatic dicarboxylic acids such as terephthalic acid, phthalic acid, isophthalic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-benzophenonedicarboxylic acid, 4,4'-diphenoxyethanedicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid; alicyclic dicarboxylic acids such as 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid; and aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid. These dicarboxylic acids may be used as raw materials for polyester carbonate resins. Depending on the production method, dicarboxylic acid esters such as methyl esters and phenyl esters, or dicarboxylic acid derivatives such as dicarboxylic acid halides, may also be used as raw materials for polycarbonate resins.

[0099] The polycarbonate resin preferably contains, as the second structural unit, a structural unit derived from an aliphatic dihydroxy compound or an alicyclic dihydroxy compound, more preferably a structural unit derived from 1,4-cyclohexanedimethanol or tricyclodecanedimethanol, and even more preferably a structural unit derived from 1,4-cyclohexanedimethanol. A polycarbonate resin containing such a second structural unit can further improve the mechanical properties and heat resistance of the resin composition.

[0100] The content of the second structural unit in the polycarbonate resin is preferably 5% by mass or more, and more preferably 10% by mass or more. Furthermore, the content of the second structural unit is preferably 70% by mass or less, more preferably 60% by mass or less, even more preferably 50% by mass or less, and particularly preferably 45% by mass or less. By setting the content of the second structural unit in the polycarbonate resin within the specific range, it is possible to improve the balance with other physical properties without significantly impairing the excellent properties of the structural unit represented by formula (1). The content of the second structural unit in the polycarbonate resin is preferably 5% by mass or more and 60% by mass or less.

[0101] The use of aromatic-containing dihydroxy compounds such as bisphenol compounds or diester compounds as copolymerization components can sometimes improve the heat resistance of polycarbonate resins. On the other hand, the presence of a large number of aromatic structures in polycarbonate resins tends to reduce weather resistance. Furthermore, because there is a significant difference in the polymerization reactivity between bisphenol compounds or dicarboxylic acids and the dihydroxy compounds that form the structural units represented by formula (1), the presence of bisphenol compounds or dicarboxylic acids in the terminal groups makes it difficult to obtain high-molecular-weight polycarbonate resins, and mechanical properties such as impact resistance tend to be reduced. Increasing the reaction temperature to accelerate the reaction can lead to thermal decomposition of the structural units represented by formula (1), resulting in coloration of the resulting polycarbonate resin. For these reasons, the content of structural units derived from aromatic-containing dihydroxy compounds or dicarboxylic acids is preferably 20% by mass or less, more preferably 10% by mass or less.

[0102] The linking group of the polycarbonate resin is introduced by using a carbonic acid diester or a carbonyl halide in a polycondensation reaction. The linking group introduced into the polycarbonate resin by the carbonic acid diester or the carbonyl halide is a carbonyl group.

[0103] From the viewpoint of being usable in the melt polymerization method described below, it is preferable to use a carbonate diester represented by the following formula (7) in the synthesis of a polycarbonate resin.

[0104] [ka]

[0105] However, in the formula (7), A 1 and A 2 is an aliphatic hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, or an aromatic hydrocarbon group which may have a substituent, and A 1 and A 2 may be the same or different from each other.

[0106] A in the formula (7) 1 and A 2 is preferably a substituted or unsubstituted aromatic hydrocarbon group, more preferably an unsubstituted aromatic hydrocarbon group. Examples of the substituent on the aliphatic hydrocarbon group include an ester group, an ether group, an amide group, and a halogen atom, and examples of the substituent on the aromatic hydrocarbon group include alkyl groups such as a methyl group and an ethyl group.

[0107] Examples of the carbonic acid diester represented by the formula (7) include diphenyl carbonate (hereinafter sometimes abbreviated as DPC), substituted diphenyl carbonates such as ditolyl carbonate, and dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, and di-tert-butyl carbonate. From the viewpoint of reactivity, the carbonic acid diester is preferably diphenyl carbonate or a substituted diphenyl carbonate, and more preferably diphenyl carbonate.

[0108] Carbonate diesters may contain impurities such as chloride ions, which may inhibit the polymerization reaction or deteriorate the color of the resulting resin. Therefore, it is preferable to use carbonate diesters that have been purified, as necessary, by distillation or the like.

[0109] In the polycondensation reaction, the reaction rate and the molecular weight of the resulting resin can be controlled by strictly adjusting the molar ratio of all dihydroxy compounds to all diester compounds used in the reaction. In the case of polycarbonate resins, the molar ratio of carbonate diester to all dihydroxy compounds is preferably adjusted to 0.90 or more and 1.10 or less, more preferably 0.96 or more and 1.05 or less, and particularly preferably 0.98 or more and 1.03 or less. When a diester compound other than the carbonate diester described above is used, the total amount of the carbonate diester and the other diester compound relative to all dihydroxy compounds is adjusted to fall within the above-mentioned molar ratio range. When the molar ratio is within the above-mentioned range, a resin with the desired molecular weight can be produced at a good reaction rate, and the amount of low-molecular-weight compounds remaining in the resin can be reduced, resulting in a resin with excellent color tone, thermal stability, and moldability.

[0110] In the present invention, the method for producing the polycarbonate resin is not particularly limited, and any method may be adopted using the above-mentioned raw materials as appropriate, such as interfacial polymerization, melt transesterification, pyridine method, ring-opening polymerization of a cyclic carbonate compound, or solid-phase transesterification of a prepolymer.

[0111] [Characteristics of polycarbonate resin] ·Molecular weight The molecular weight of polycarbonate resin affects the reduced viscosity and 1 It can be expressed as the number average molecular weight measured by H-NMR, etc. The higher the value obtained by these measurement methods, the higher the molecular weight. 1 The number average molecular weight of the polycarbonate resin measured by H-NMR is preferably 8,000 or more, more preferably 9,000 or more, and even more preferably 10,000 or more. 1 The number average molecular weight of the polycarbonate resin measured by H-NMR is preferably 30,000 or less, more preferably 25,000 or less, and even more preferably 20,000 or less. 1The number average molecular weight of the polycarbonate resin measured by H-NMR is preferably 8,000 or more and 30,000 or less.

[0112] The reduced viscosity of the polycarbonate resin is preferably 0.3 dL / g or more, more preferably 0.35 dL / g or more, and even more preferably 0.4 dL / g or more. The reduced viscosity of the polycarbonate resin is preferably 1.0 dL / g or less, more preferably 0.8 dL / g or less, and even more preferably 0.7 dL / g or less. The reduced viscosity of the polycarbonate resin is preferably 0.3 dL / g or more and 1.0 dL / g or less.

[0113] When the measured molecular weight of the polycarbonate resin is within the above range, sufficient mechanical strength is obtained, and the flowability during melt molding can also be adjusted to a preferred range.

[0114] Glass transition temperature The glass transition temperature of the polycarbonate resin is preferably 80°C or higher, more preferably 85°C or higher, and even more preferably 90°C or higher. The glass transition temperature of the polycarbonate resin is preferably 160°C or lower, more preferably 150°C or lower, and even more preferably 140°C or lower. The glass transition temperature of the polycarbonate resin is preferably 80°C or higher and 160°C or lower. When the glass transition temperature of the polycarbonate resin is within the above range, it has sufficient heat resistance and mechanical properties and is easy to mold.

[0115] [Acrylic resin] The acrylic resin blended in the resin composition is a resin containing structural units derived from alkyl (meth)acrylate. Examples of the alkyl (meth)acrylate used in the acrylic resin include esters of (meth)acrylic acid and alcohols having 1 to 10 carbon atoms. The acrylic resin may be, for example, a homopolymer of methyl methacrylate, or a copolymer of methyl methacrylate and a vinyl monomer other than methyl methacrylate. The proportion of structural units derived from methyl methacrylate in all structural units constituting the acrylic resin is preferably 80% by mass or more, more preferably 85% by mass or more, and even more preferably 90% by mass or more. The upper limit of the proportion of structural units derived from methyl methacrylate in all structural units constituting the acrylic resin is 100% by mass. The proportion of structural units derived from methyl methacrylate in the acrylic resin is preferably 80% by mass or more and 100% by mass or less.

[0116] By adjusting the ratio of the structural unit derived from methyl methacrylate in the acrylic resin to fall within the above-mentioned specific range, the glass transition temperature of the acrylic resin can be suitably increased, and by mixing such an acrylic resin with a polycarbonate resin and the above-mentioned polymer, a resin composition having an excellent balance between heat resistance and fluidity can be easily obtained.

[0117] More specifically, examples of vinyl monomers used in acrylic resins include methyl acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-lauryl (meth)acrylate, n-stearyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, and methoxypolyethylene glycol (meth)acrylate. Examples of suitable vinyl monomers include (meth)acrylates such as acrylate; monofunctional vinyl group-containing monomers such as styrene, α-methylstyrene, vinyltoluene, (meth)acrylonitrile, vinyl chloride, vinyl acetate, and vinyl propionate; and polyfunctional vinyl group-containing monomers such as divinylbenzene, ethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and allyl (meth)acrylate. These vinyl monomers may be used alone, or two or more of them may be used in combination.

[0118] From the viewpoint of improving the thermal decomposition resistance of the acrylic resin, it is preferable that the acrylic resin contains structural units derived from acrylates such as methyl acrylate, ethyl acrylate, n-butyl acrylate, etc. Furthermore, in terms of improving the thermal decomposition resistance and also of preventing the balance of compatibility with the polycarbonate resin and the polymer from being impaired, it is more preferable that the acrylic resin contains structural units derived from methyl acrylate.

[0119] The proportion of monomers other than methyl methacrylate in all monomer units constituting the acrylic resin is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less.

[0120] The molecular weight of the acrylic resin can be measured by GPC, which will be described later. The weight-average molecular weight (Mw) of the acrylic resin is preferably 80,000 or more, more preferably 90,000 or more, and even more preferably 100,000 or more. The weight-average molecular weight (Mw) of the acrylic resin is preferably 200,000 or less, more preferably 180,000 or less, and even more preferably 160,000 or less. The weight-average molecular weight (Mw) of the acrylic resin is preferably 80,000 or more and 200,000 or less. By setting the weight-average molecular weight of the acrylic resin within the above-mentioned specific range, sufficient mechanical strength can be obtained.

[0121] The glass transition temperature of the acrylic resin is preferably 70°C or higher, more preferably 80°C or higher, and even more preferably 90°C or higher. The glass transition temperature of the acrylic resin is preferably 130°C or lower, more preferably 125°C or lower, and even more preferably 120°C or lower. The glass transition temperature of the acrylic resin is preferably 70°C or higher and 130°C or lower. By setting the glass transition temperature of the acrylic resin within the above specific range, a decrease in the mechanical strength of the resin composition can be more easily avoided.

[0122] The method for producing the acrylic resin is not particularly limited, and various methods such as solution polymerization, suspension polymerization, emulsion polymerization, and bulk polymerization can be used. It is preferable to adopt aqueous polymerization such as suspension polymerization or emulsion polymerization as the method for producing the acrylic resin, since it is easy to control the heat generated by polymerization and has excellent productivity. Furthermore, it is more preferable to adopt suspension polymerization as the method for producing the acrylic resin, since the operation for recovering the polymer is simpler.

[0123] (Method of producing resin composition) The resin composition can be obtained, for example, by mechanically melt-kneading the above-mentioned components constituting the resin composition. Examples of melt-kneading machines that can be used include single-screw extruders, twin-screw extruders, Brabender mixers, Banbury mixers, kneader blenders, and roll mills. The melt-kneading may involve kneading all the components at once, or may involve a multi-stage division kneading method in which some of the above-mentioned components are kneaded first, and then the remaining components are added and kneaded.

[0124] Among these methods for producing the resin composition, a method in which each component is continuously introduced into a twin-screw extruder equipped with a vacuum vent and a resin composition is continuously obtained is preferred from the viewpoints of productivity and uniformity of quality. The kneading temperature in melt kneading is preferably 160°C or higher, more preferably 180°C or higher, and even more preferably 200°C or higher. The kneading temperature is preferably 300°C or lower, more preferably 280°C or lower, and even more preferably 260°C or lower. The kneading temperature is preferably 160°C or higher and 300°C or lower. By setting the kneading temperature within the specific range, the components can be mixed to obtain a resin composition while suppressing retention of the components in the kneader and thermal deterioration due to shear heat generation. [Example]

[0125] The structures of the polymer and resin composition according to the present invention will be described in more detail below with reference to examples. Note that the specific embodiments of the polymer and resin composition according to the present invention are not limited to those in the examples, and various modifications are possible without departing from the gist of the present invention.

[0126] (raw materials) The raw materials used in the examples and comparative examples and their abbreviations are shown below.

[0127] [Dihydroxy compound (A)] HSB840B: Polycarbonate diol ("BENEBIOL HSB840B" manufactured by Mitsubishi Chemical Corporation) HSB850H: Polycarbonate diol (Mitsubishi Chemical Corporation "BENEBIOL HSB850H") ISB: Isosorbide (Tokyo Chemical Industry Co., Ltd.) CHDMA: 1,4-cyclohexanedimethanol (Tokyo Chemical Industry Co., Ltd.)

[0128] [Michael acceptor (B)] DVS: Divinyl sulfone (Tokyo Chemical Industry Co., Ltd.) C6DA: 1,6-hexanediol diacrylate (Tokyo Chemical Industry Co., Ltd.) A-DCP: Tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) CHDMA-diyne: Cyclohexanedimethanol dipropiolate

[0129] 〔catalyst〕 P2-t-Bu: 1-tert-butyl-2,2,4,4,4-pentakis(dimethylamino)-2λ 5 ,4λ 5 -Catenadi(phosphazene) (Aldrich, THF solution) TTMPP: Tris(2,4,6-trimethoxyphenyl)phosphine (Aldrich Co., Ltd.) DABCO: 1,4-diazabicyclo[2.2.2]octanetriethylenediamine (Tokyo Chemical Industry Co., Ltd.) t-BuOK: tert-potassium butoxide (Tokyo Chemical Industry Co., Ltd.) PTSA: p-toluenesulfonic acid (Tokyo Chemical Industry Co., Ltd.)

[0130] 〔solvent〕 DMF: Dimethylformamide (Fujifilm Wako Pure Chemical Industries, Ltd.)

[0131] [Radical Polymerization Initiator] AIBN: Azoisobutyronitrile (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0132] [Vinyl Monomer] MMA: Methyl methacrylate ("Acrylate Ester M" manufactured by Mitsubishi Chemical Corporation) MEMA: Methoxyethyl methacrylate (Tokyo Chemical Industry Co., Ltd.) MEA: Methoxyethyl acrylate (Tokyo Chemical Industry Co., Ltd.) MA: Methyl acrylate (Mitsubishi Chemical Corporation) HEMA: Hydroxyethyl methacrylate (Mitsubishi Chemical Corporation)

[0133] [Polycarbonate resin] D7340R: Polycarbonate resin containing structural units derived from ISB ("DURABIO (registered trademark) D7340R" manufactured by Mitsubishi Chemical Corporation)

[0134] [Acrylic resin] VH001: Polymethyl methacrylate ("ACRYPET (registered trademark) VH001" manufactured by Mitsubishi Chemical Corporation)

[0135] (Measurement and evaluation methods) [Relative weight average molecular weight] The relative weight-average molecular weight Mw of the polymer was measured by gel permeation chromatography (GPC). Specifically, approximately 10 mg of polymer was dissolved in 10 mL of tetrahydrofuran to prepare a sample solution with a concentration of approximately 1 mg / mL. The sample solution was filtered using a membrane filter with a pore size of 0.1 μm, and then measurement was performed using a measuring device equipped with a column consisting of a TSK GUARD COLUMN SUPER HH (4.6 × 35 mm, manufactured by Tosoh Corporation) and two TSK-GEL SUPER HM-H (6.0 × 150 mm, manufactured by Tosoh Corporation) connected in series. Detailed measurement conditions are as follows.

[0136] Measuring device: HLC-8220 (Tosoh Corporation) Detector: Refractive index (RI) detector Column and detector temperature: 40°C Eluent: tetrahydrofuran Flow rate: 0.6mL / min Standard material: polymethyl methacrylate (Polymer Laboratories; Mp (peak molecular weight) = 141,500, 55,600, 11,100, 1,590)

[0137] [Glass transition temperature] The glass transition temperatures of the polymer, polycarbonate resin, and resin compositions containing the polymer and polycarbonate resin were measured by differential scanning calorimetry. Specifically, approximately 10 mg of a measurement sample was placed in an aluminum pan and sealed. This aluminum pan was placed in a differential scanning calorimeter (Hitachi High-Tech Science Corporation, "X-DSC7000"). Next, the aluminum pan was heated from 30°C to 180°C at a heating rate of 10°C / min under a nitrogen flow of 20 mL / min. After the temperature of the aluminum pan reached 180°C, this temperature was maintained for 5 minutes. The aluminum pan was then cooled from 180°C to -50°C at a cooling rate of 10°C / min. After the temperature of the aluminum pan reached -50°C, this temperature was maintained for 5 minutes.

[0138] The aluminum pan was then heated from -50°C to 180°C at a heating rate of 10°C / min, and a DSC curve was obtained at each stage. The extrapolated glass transition temperature of the DSC curve obtained during the second heating cycle was determined, and this temperature was used as the glass transition temperature of the sample. The extrapolated glass transition temperature is the temperature corresponding to the intersection of a line extending the low-temperature baseline of the DSC curve toward the high-temperature side and a tangent drawn at the point where the gradient of the curve is maximum in the stepwise change portion of the glass transition.

[0139] [Compatibility between polycarbonate resin and polymer] The compatibility between the polycarbonate resin and the polymer was evaluated using the Fox equation shown below. Fox formula: 1 / Tg (ポリカーボネート.A) =W (ポリカーボネート) / Tg (ポリカーボネート) +W (A) / Tg (A)

[0140] The meanings of the symbols in the Fox formula mentioned above are as follows: Tg (ポリカーボネート.A) : Theoretical glass transition temperature of a composite of polycarbonate resin and polymer (unit: °C) Tg (ポリカーボネート) : Glass transition temperature of polycarbonate resin (unit: °C) Tg (A) : Glass transition temperature of polymer (unit: °C) W (ポリカーボネート) : Mass ratio of polycarbonate resin in the resin composition W (A) : Mass ratio of polymer in resin composition

[0141] The Fox equation is valid when polymer compounds that are completely miscible with each other are compounded in a predetermined ratio. When polycarbonate resin and polymer are completely miscible with each other, the measured glass transition temperature of the resin composition obtained by compounding polycarbonate resin and polymer in a predetermined mass ratio is Tg (ポリカーボネート.A) Therefore, the theoretical glass transition temperature Tg calculated from the Fox equation is (ポリカーボネート.A) It is considered that the smaller the difference between the Tg calculated from the Fox equation and the glass transition temperature of the resin composition, the higher the compatibility between the polycarbonate resin and the polymer. (ポリカーボネート.A) The absolute value of the temperature difference between the glass transition temperature (Tg) and the glass transition temperature (Tc) of the resin composition was used as a measure of the degree of compatibility. Specifically, a Tg of 25 or less was considered to indicate high compatibility between the polycarbonate resin and the polymer.

[0142] [Tensile test] A resin composition containing a polycarbonate resin and a polymer was pressed using a hand press ("Mini Test Press MP-2FH" manufactured by Toyo Seiki Seisakusho, Ltd.) to produce a film of the resin composition. This film was then punched out to produce test specimens having the shape of an L-shaped test specimen as specified in ASTM D-1822.

[0143] The test specimens were then subjected to a tensile test in accordance with JIS K7161:2014 to measure the elongation at break (i.e., the tensile strain at break or the nominal tensile strain at break). A universal testing machine (Shimadzu Corporation, "Autograph (registered trademark) AG-XPLUS10KN") was used for the tensile test. The test speed was 1 mm / min.

[0144] (Polymer synthesis) [Production Example 1] 1.00g of HSB840B and 0.147g of DVS were weighed into a sample bottle, and 1.147g of DMF was added to prepare a solution with a solids content of 50%. Then, 0.0666g of TTMPP was added to the sample bottle, and the raw materials were reacted by stirring at room temperature (25°C) for 1 hour. This resulted in a solution containing the polymer of Production Example 1. The molar ratio of the raw materials used in this example was HSB840B / DVS / TTMPP = 1 / 1 / 0.1.

[0145] [Production Example 2] These raw materials were reacted in the same manner as in Production Example 1, except that 1.00 g of HSB850H, 0.147 g of DVS, and 0.0666 g of TTMPP were weighed into a sample bottle. This resulted in a solution containing the polymer of Production Example 2. The molar ratio of the raw materials used in this example was HSB840B / DVS / TTMPP=1 / 1 / 0.1.

[0146] [Production Example 3] These raw materials were reacted in the same manner as in Production Example 1, except that 1.00 g of ISB, 0.808 g of DVS, and 0.364 g of TTTPP were weighed into a sample bottle. As a result, a solution containing the polymer of Production Example 3 was obtained. The molar ratio of the raw materials used in this example was ISB / DVS / TTMPP=1 / 1 / 0.1.

[0147] [Production Example 4] 1.00 g of ISB and 1.55 g of C6DA were weighed into a sample bottle, which was then heated to 80°C. Then, 0.68 mL of a 1 M THF solution of P2-t-Bu was added to the sample bottle using a syringe, and the mixture was stirred for 1 hour while maintaining the temperature at 80°C, allowing these raw materials to react. This resulted in a solution containing the polymer of Production Example 4. The molar ratio of the raw materials used in this example was ISB / C6DA / P2-t-Bu = 1 / 1 / 0.1.

[0148] [Production Example 5] 1.00 g of CHDMA and 0.0779 g of t-BuOK were weighed into a sample bottle. The sample bottle was then heated to 80°C and stirred for 15 minutes. Next, 1.55 g of C6DA was added to the sample bottle, and the mixture was stirred for 1 hour while maintaining the temperature at 80°C, allowing these raw materials to react. This resulted in a solution containing the polymer of Production Example 5. The molar ratio of the raw materials used in this example was CHDMA / C6DA / t-BuOK = 1 / 1 / 0.1.

[0149] [Production Example 6] These raw materials were reacted in the same manner as in Production Example 5, except that 1.00 g of CHDMA, 0.0779 g of t-BuOK, and 2.11 g of A-DCP were weighed into a sample bottle. This resulted in a solution containing the polymer of Production Example 6. The molar ratio of the raw materials used in this example was CHDMA / A-DCP / t-BuOK = 1 / 1 / 0.1.

[0150] [Production Example 7] 20.0 g of CHDMA, 19.4 g of propiolic acid, 4.56 g of PTSA, and 154.2 g of toluene were weighed into a three-neck flask equipped with a Dean-Stark tube. The molar ratio of these compounds was CHDMA / propiolic acid / PTSA = 1.0 / 2.0 / 0.13. The flask was then heated to 120 °C and refluxed for 6 hours. During the reaction, the by-product water was removed using a Dean-Stark tube. After the reaction was complete, the solvent was removed using a rotary evaporator to synthesize solid CHDMA-diyne.

[0151] Next, 1.00 g of ISB, 2.04 g of CHDMA-diyne obtained by the method described above, and 0.00976 g of HEMA were weighed into a sample bottle, and 7.33 g of DMF was added to dissolve them. Then, 0.076 g of DABCO was added to the sample bottle and stirred for 1 hour to react these raw materials. This resulted in a solution containing the polymer of Production Example 7. The molar ratio of the raw materials used in the synthesis of this polymer was ISB / CHDMA-diyne / HEMA / DABCO = 1 / 1.2 / 0.1 / 0.1.

[0152] [Production Example 8] 95 parts by weight of MEMA, 5 parts by weight of MA, 0.03 parts by weight of AIBN, and 100 parts by weight of toluene were weighed into a Schlenk tube, and nitrogen bubbling was performed for 15 minutes at a flow rate of 200 mL / min. The flow was then switched to nitrogen, the Schlenk tube was heated to 80 °C, and the raw materials were reacted for 5 hours. This resulted in a solution containing the polymer of Production Example 8. Note that the polymer of this example does not have a structural unit derived from the dihydroxy compound (A).

[0153] [Production Example 9] The raw materials were reacted in the same manner as in Production Example 8, except that MEA was used instead of MEMA. As a result, a solution containing the polymer of Production Example 9 was obtained. A polymer was obtained. Note that the polymer of this example does not have a structural unit derived from the dihydroxy compound (A).

[0154] [Production Example 10] 40 parts by weight of the polymer synthesized in Production Example 7, 60 parts by weight of MMA as a vinyl monomer, and 100 parts by weight of DMF were mixed. Then, 0.03 parts by weight of AIBN as a radical polymerization initiator was added to the mixed solution and thoroughly mixed. This mixed solution was placed in a Schlenk flask, and nitrogen bubbling was performed for 15 minutes at a flow rate of 200 mL / min. After completion of bubbling, the nitrogen flow rate was maintained and changed to nitrogen flow, and the Schlenk flask was heated to 80 °C and the reaction was carried out for 5 hours. The reaction solution was reprecipitated with MeOH to obtain a solid graft copolymer.

[0155] (Preparation and Evaluation of Resin Compositions) Examples 1 to 7 The polymers were purified by reprecipitation from the solutions containing the polymers obtained in Production Examples 1 to 7. The polymers were dried overnight at 80°C under reduced pressure using a vacuum heat dryer. Then, D7340R and the dried polymer were weighed into sample bottles so that the mass ratio of D7340R / polymer was 90 / 10 or 70 / 30, and methylene chloride was added to prepare a homogeneous solution. The solution was placed in an aluminum cup and dried at room temperature for 24 hours to remove the methylene chloride, yielding a resin composition containing the polymer and polycarbonate resin.

[0156] The measured glass transition temperatures of the resin compositions thus obtained are shown in the "Measured Tg" column of Table 1. The "Theoretical Tg" column of the same table also shows the Tg calculated based on the Fox formula. (ポリカーボネート.A) The value of |ΔTg| is shown, and the absolute value of the difference between the theoretical Tg and the measured Tg is shown in the "|ΔTg|" column. Furthermore, when the value of |ΔTg| is 25°C or less in the resin composition composited at any mass ratio, the polymer is judged to have excellent compatibility with the polycarbonate resin having ISB structural units, and the symbol "Good" is entered in the "Compatibility Evaluation" column. Furthermore, when the value of |ΔTg| is greater than 25°C in the resin composition composited at any mass ratio, the polymer is judged to have poor compatibility with the polycarbonate resin having ISB structural units, and the symbol "Poor" is entered in the "Compatibility Evaluation" column.

[0157] Comparative Examples 1 and 2 Using the polymers obtained in Production Examples 8 and 9, resin compositions containing polymers and polycarbonate resin were obtained in the same manner as in Examples 1 to 7, except that the mass ratio of D7340R to the dried polymer was changed to D7340R / polymer = 80 / 20. The "Measured Tg" column in Table 1 shows the glass transition temperatures of the resin compositions measured by the above-mentioned method. The Tg calculated based on the Fox formula was also (ポリカーボネート.A)The values ​​are shown in the "Theoretical Tg" column of the table. Furthermore, the "|ΔTg|" column of the table shows the absolute value of the difference between the theoretical Tg and the actually measured Tg, and the "Compatibility Evaluation" column shows the evaluation results based on the |ΔTg| value.

[0158] [Table 1]

[0159] As shown in Table 1, the polymers of Production Examples 1 to 7 have structural units derived from a dihydroxy compound (A) having a heterocyclic skeleton and / or an alicyclic skeleton and structural units derived from a Michael acceptor (B). Therefore, as shown in Examples 1 to 7, these polymers have excellent compatibility with polycarbonate resins containing ISB structural units.

[0160] In contrast, the polymers of Production Examples 8 and 9 did not have either a structural unit derived from the dihydroxy compound (A) or a structural unit derived from the Michael acceptor (B), and therefore, as shown in Comparative Examples 1 and 2, these polymers were inferior to the polymers of Production Examples 1 to 7 in compatibility with polycarbonate resins containing ISB structural units.

[0161] From these results, it is believed that the polymers of the present invention have improved compatibility with polycarbonate resins containing ISB structural units because a heterocyclic or alicyclic skeleton similar to the ISB structural unit in polycarbonate resins is introduced into the main chain. In contrast, the acrylic resins of Production Examples 8 and 9 do not have a heterocyclic or alicyclic skeleton introduced into the main chain, which is thought to result in reduced compatibility with polycarbonate resins containing ISB structural units. Furthermore, when a heterocyclic or alicyclic skeleton is introduced into the side chain of an acrylic resin or the like, there is a limit to how much of these structures can be increased. Therefore, it can be inferred that polymers having a heterocyclic or alicyclic skeleton introduced into the side chain have lower compatibility with polycarbonate resins containing ISB structural units compared to the polymers of the present invention having a heterocyclic or alicyclic skeleton introduced into the main chain.

[0162] Example 8 D7340, VH001, and the graft copolymer obtained in Production Example 10 were weighed out in the mass ratios shown in Table 2 and kneaded using a kneading / extrusion tester ("Labo Plastomill (registered trademark) 4C150" manufactured by Toyo Seiki Seisaku-sho, Ltd.) to prepare a resin composition. The kneading temperature was 230°C, the kneading speed was 30 rpm, and the kneading time was 5 minutes. The resin composition thus obtained was subjected to a tensile test using the method described above. The "Elongation" column in Table 2 shows the tensile strain at break or nominal tensile strain at break obtained from the tensile test.

[0163] Comparative Example 3 Except for not blending the graft copolymer, a resin composition was prepared in the same manner as in Example 8. The "Tensile elongation" column in Table 2 shows the tensile elongation of the resin composition obtained by the tensile test.

[0164] [Table 2]

[0165] The polymer of Production Example 10 is a block copolymer having a first polymer chain containing structural units derived from the dihydroxy compound (A) and structural units derived from the Michael acceptor (B), and a second polymer chain containing structural units derived from a vinyl monomer and bonded to the vinyl group of the first polymer chain. By compounding such a block copolymer with a polycarbonate resin and an acrylic resin containing ISB structural units, the mechanical properties of the resin composition can be improved, as shown in Table 2.

[0166] As described above, the present invention can provide a polymer that has excellent compatibility with polycarbonate resins containing ISB structural units. Furthermore, polymers having block and / or graft structures synthesized from the polymers of the present invention act as compatibilizers in the composite formation of polycarbonate resins containing ISB structural units with other resins. The resin compositions of the present invention have excellent mechanical properties when molded, and are therefore suitable for use in automotive interior and exterior components, outdoor building materials (such as lighting covers, carports, and highway soundproofing walls), display front panels, and housings for electrical and electronic devices.

Claims

1. a structural unit derived from a dihydroxy compound (A) having a heterocyclic skeleton and / or an alicyclic skeleton; and structural units derived from a Michael acceptor (B), A polymer having at least one vinyl group in its molecular structure.

2. 2. The polymer according to claim 1, wherein the structural unit derived from the dihydroxy compound (A) and the structural unit derived from the Michael acceptor (B) are linked via an ether bond.

3. 2. The polymer according to claim 1, wherein the vinyl group is contained in one or more polymerizable functional groups selected from the group consisting of a methacryloyl group, an acryloyl group, and a vinyl sulfone group.

4. The polymer according to claim 1, wherein the relative weight average molecular weight of the polymer is 100 or more and 200,000 or less.

5. A polymer comprising: a first polymer chain comprising the polymer of claim 1; and a second polymer chain comprising a structural unit derived from a vinyl-based monomer and bonded to the vinyl group of the polymer.

6. A resin composition comprising the polymer according to any one of claims 1 to 5.

7. a polycarbonate resin containing 30% by mass or more and 90% by mass or less of a structural unit represented by the following formula (1); The resin composition according to claim 6, further comprising an acrylic resin containing 50% by mass or more and 100% by mass or less of a structural unit represented by the following formula (2): 【Chemical 1】 【Chemistry 2】 (However, in the formula (2), R 1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent, and R 2 represents an alkyl group which may have a substituent.

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