Polymer compound, method for producing polymer compound, composition, method for producing composition, and resin composition

Abstract

To provide a polymer compound which has a large content of a branched polymer, and has a high degree of branch of the branched polymer, and a method for producing the same.SOLUTION: There is provided a polymer compound in which a plurality of polymer chains are connected to each other by a di- or higher connection group, wherein the plurality of polymer chains either or both of a dithioester group and a vinylidene group at a terminal of the polymer chains, the di- or higher connection group has either or both of a thioether group and a thioether structure, a ratio (absolute Mw / relative Mw) of an absolute weight average molecular weight (absolute Mw) to a relative weight average molecular weight (relative Mw) is 1.25 or more, when the di- or higher connection group has two or more thioether structures, a smallest distance between sulfur atoms of the two or more thioether structures is 200 or more in terms of molecular weight.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polymer compound, a method for producing a polymer compound, a composition, a method for producing a composition, and a resin composition. [Background technology]

[0002] Polymer compounds with multiple polymer chains bonded to thiol groups within the molecule are used in paints, adhesives, pressure-sensitive adhesives, compatibilizers, dispersants, etc. In recent years, environmental concerns have led to a demand for reducing the amount of volatile organic compounds (VOCs) used when using these compounds for the above-mentioned purposes. Because VOCs are used as solvents for applying resins, if the solution viscosity can be reduced from the perspective of ease of handling, it will be possible to reduce VOCs. As a method for reducing the solution viscosity of a polymer compound, a method of introducing branches into the polymer compound is known.

[0003] Patent Document 1 discloses a polymer compound obtained by radically polymerizing a vinyl monomer using, as a chain transfer agent, an organic sulfide compound obtained by Michael addition of a polyvalent mercaptan and a vinyl compound.

[0004] Patent Document 2 discloses a polymer compound obtained by reacting a polyfunctional thiol compound with a compound having a reactive group that reacts with a thiol group in a predetermined ratio range to obtain a chain transfer agent having a thiol group, and then radically polymerizing a vinyl compound in the presence of the chain transfer agent. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2001-064252 [Patent Document 2] International Publication No. 2020 / 203837 Summary of the Invention [Problem to be solved by the invention]

[0006] It is generally known that there is a correlation between the molecular weight of a polymer compound and its solution viscosity. The higher the molecular weight, the higher the solution viscosity. In some cases, achieving the minimum molecular weight necessary to satisfy the required physical properties does not result in sufficient viscosity reduction. Patent Documents 1 and 2 disclose methods for reducing viscosity by introducing branches into polymer compounds, but the resulting product is a mixture of linear polymers and branched polymers, and there is room for improvement in reducing viscosity by increasing the content of branched polymers and the degree of branching.

[0007] An object of the present invention is to provide a polymer compound having a high content of branched polymer and a high degree of branching of the branched polymer, and a method for producing the same. [Means for solving the problem]

[0008] [1] A polymer compound in which multiple polymer chains are linked by divalent or higher linking groups, the plurality of polymer chains have either or both of a dithioester group and a vinylidene group at the ends of the polymer chains; the divalent or higher valent linking group has either or both of a thiol group and a thioether structure, Relative weight average molecular weight (relative M w ) to the absolute weight average molecular weight (absolute M w ) ratio (absolute M w / Relative M w ) is 1.25 or more, when the divalent or higher valent linking group has two or more thioether structures, the shortest distance between sulfur atoms of the two or more thioether structures is 200 or more in terms of molecular weight; High molecular compound. [2] The polymer compound according to [1], wherein the polymer compound has a structure represented by formula (1A) or a structure represented by formula (1B). [ka] In formula (1A), P m is the polymer chain and Z1 is any one selected from the group consisting of a sulfur atom, a carbon atom, a nitrogen atom, and an oxygen atom, and the substituent on each atom is not particularly limited. In formula (1B), P m is the polymer chain and Z 2 is an electron-withdrawing substituent. [3] The polymer compound according to [1], wherein the divalent or higher valent linking group includes a structure represented by formula (2): [ka] In formula (2), R 1 and R 2 are each independently any one selected from the group consisting of a hydrogen atom, a monovalent hydrocarbon group, a hydroxyl group, and a monovalent electron-withdrawing group, and R 3 is any one selected from the group consisting of an oxygen atom, a divalent hydrocarbon group, and a divalent electron-withdrawing group, and -* is a bond. [4] The polymer compound according to [1] or [2], wherein when the divalent or more linking group has a thiol group, the divalent or more linking group has 1 to 300 thiol groups per molecule of the polymer compound. [5] The absolute M w / Relative M w The polymer compound according to any one of [1] to [4], wherein the value of [6] A step of reacting a polyfunctional thiol compound (A) with a compound (B) having a reactive group that reacts with a thiol group to obtain a polymerizing chain transfer agent (F) having a thiol group; a step of polymerizing a vinyl compound in the presence of the thiol group-containing polymerizing chain transfer agent (F), a high chain transfer constant chain transfer agent (G) that easily causes chain transfer, and a radical polymerization initiator (H) to obtain a polymer compound; A method for producing a polymer compound, comprising: [7] The high chain transfer constant chain transfer agent (G) is at least one organic compound selected from the group consisting of addition-fragmentation chain transfer agents (G1) and thiol-based chain transfer agents (G2), The addition-fragmentation chain transfer agent (G1) has a chain transfer constant C tr The value of is 1 or greater, The thiol chain transfer agent (G2) has a chain transfer constant C tr The value of is 2 or more, [6] A method for producing a polymer compound according to [6]. [8] The method for producing a polymer compound according to [6], wherein the high chain transfer constant chain transfer agent (G) contains a structure represented by formula (3A) or a structure represented by formula (3B). [ka] In formula (3A), R 1 represents a monovalent to trivalent hydrocarbon group which may have a substituent, and Z3 represents an electron-withdrawing substituent. In formula (3B), X is a substituent that is eliminated as a radical when the polymer-growing radical is added to the chain transfer agent, and Z 4 is an electron-withdrawing substituent. [9] The method for producing a polymer compound according to [6], wherein the reactive group reactive with a thiol group of the compound (B) having a reactive group reactive with a thiol group is at least one selected from the group consisting of an acrylate group and a glycidyl group.

[10] A composition comprising, as a main component, a compound (E) having a moiety derived from a polyfunctional thiol compound (A) and a moiety derived from a compound (B) having a reactive group that reacts with a thiol group, A composition satisfying formula (11) and formula (12). r×(f A -1)×(f B -1)<1.2 (11) r=(f B ×y) / (f A ×x) ···(12) In formula (11) and formula (12), f A is the average number of thiol groups per molecule of the polyfunctional thiol compound (A), and f Bf is the average number of reactive groups reactive with the thiol group per molecule of the compound (B) having the reactive group reactive with the thiol group. A is greater than or equal to 2, and f B is 1.2 or more, except for the case where there is only compound (A) having two thiol groups and only compound (B) having two reactive groups. In formula (12), x and y are x and y, respectively, when the molar ratio of the portion derived from the polyfunctional thiol compound (A) to the portion derived from the compound (B) having a reactive group that reacts with a thiol group is defined as x:y.

[11] The composition according to

[10] , wherein the compound (E) is a compound having at least one thiol group per molecule.

[12] f A +f B The composition according to

[10] or

[11] , wherein the value is >4.

[13] The composition according to any one of

[10] to

[12] , wherein the reactive group that reacts with a thiol group is at least one selected from the group consisting of acrylate groups and has a formula weight of 200 or more.

[14] The composition according to any one of

[10] to

[13] , which is a chain transfer agent in a radical polymerization reaction system.

[15] A method for producing a composition, comprising reacting a polyfunctional thiol compound (A) with a compound (B) having a reactive group that reacts with a thiol group under conditions that satisfy formulas (13) and (14). r'×(f A -1)×(f B -1)<1.2 (13) r'=(f B ×y') / (f A ×x') ···(14) In formula (13) and formula (14), f A is the average number of thiol groups per molecule of the polyfunctional thiol compound (A), and f B is the average number of the reactive groups per molecule of the compound (B). A is greater than or equal to 2, and f Bis 1.2 or more, except for the case where there is only the compound (A) having two thiol groups and only the compound (B) having two reactive groups. In the formula (14), x' and y' respectively represent x' and y' when the molar ratio of the polyfunctional thiol compound (A) to the compound (B) is x':y'.

[16] f A +f B The method for producing the composition according to

[15] , wherein the value of the formula (I) is 4 or more.

[17] A method for producing the composition according to

[15] or

[16] , comprising reacting the polyfunctional thiol compound (A) with a compound (B) having a reactive group that reacts with the thiol group in the presence of a catalyst (C).

[18] The amount of the solvent at the start of the reaction between the polyfunctional thiol compound (A) and the compound (B) having a reactive group reactive with a thiol group is 50 mass% or less of the total mass of the polyfunctional thiol compound (A) and the compound (B) having a reactive group reactive with a thiol group, The method for producing a composition according to any one of

[15] to

[17] , wherein the external temperature during the reaction between the polyfunctional thiol compound (A) and the compound (B) having a reactive group that reacts with the thiol group is 10 to 50°C.

[19] A resin composition comprising the polymer compound according to any one of [1] to [5] or the composition according to any one of

[10] to

[14] , and a thermoplastic resin. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a polymer compound having a high content of branched polymer and a high degree of branching of the branched polymer, and a method for producing the same. DETAILED DESCRIPTION OF THE INVENTION

[0010] The following describes in detail the forms for implementing the present invention, but the present invention is not limited to the embodiments described below, and various modifications are possible without departing from the gist of the present invention.

[0011] In this specification and claims, a numerical range expressed by "to" means a numerical range that includes the numerical values ​​before and after "to" as the lower and upper limits. In this specification and claims, "(meth)acrylic" means acrylic and methacrylic. Similarly, "(meth)acrylate" means acrylate and methacrylate, and "(meth)acryloyloxy" means acryloyloxy and methacryloyloxy.

[0012] [Polymer Compound and Method for Producing Polymer Compound] The polymer compound of the present invention is a polymer compound in which a plurality of polymer chains are linked by a linking group having a valence of two or more.

[0013] The relative weight average molecular weight (hereinafter simply referred to as "relative M w ") relative to the absolute weight average molecular weight (hereinafter simply referred to as "absolute M w ") ratio (absolute M w / Relative M w The lower limit of the ratio (absolute M w / Relative M w ) is equal to or greater than the lower limit, the solution containing the polymer compound of the present invention can be prevented from becoming highly viscous. The ratio (absolute M w / Relative M w The upper limit of the ratio (absolute M) is usually 3, preferably 2.1, more preferably 2, even more preferably 1.95, and even more preferably 1.90. w / Relative M w ) is not more than the lower limit, the resin composition to which the polymer compound of the present invention is added has excellent heat resistance. The ratio (absolute M w / Relative M w) is preferably in the range of 1.25 to 3, more preferably 1.25 to 2.1, even more preferably 1.25 to 2, still more preferably 1.27 to 1.95, and even more preferably 1.29 to 1.9.

[0014] The relative M of the polymer compound of the present invention w The lower limit is preferably 1,000, more preferably 1,500, even more preferably 5,000, still more preferably 10,000, even more preferably 20,000, and particularly preferably 40,000. The relative M of the polymer compound of the present invention w The upper limit is preferably 200,000, more preferably 1,800,000, even more preferably 1,500,000, still more preferably 1,200,000, even more preferably 800,000, and particularly preferably 500,000. The relative M of the polymer compound of the present invention w The range is preferably 1,000 to 2,000,000, more preferably 1,500 to 1,800,000, even more preferably 5,000 to 1,500,000, still more preferably 10,000 to 1,200,000, even more preferably 20,000 to 800,000, and particularly preferably 40,000 to 500,000.

[0015] The relative M w is a polymethyl methacrylate equivalent value measured using gel permeation chromatography (GPC). w is the molecular weight calculated by the method described in the Examples below.

[0016] The absolute M of the polymer compound of the present invention w The lower limit is preferably 1,250, more preferably 1,500, even more preferably 5,000, still more preferably 10,000, even more preferably 20,000, and particularly preferably 40,000. The absolute M of the polymer compound of the present invention wThe upper limit is preferably 2,000,000, more preferably 1,800,000, even more preferably 1,500,000, still more preferably 1,200,000, even more preferably 800,000, and particularly preferably 500,000. The absolute M of the polymer compound of the present invention w The range is preferably 1,250 to 2,000,000, more preferably 1,500 to 1,800,000, even more preferably 5,000 to 1,500,000, still more preferably 10,000 to 1,200,000, even more preferably 20,000 to 800,000, and particularly preferably 40,000 to 500,000.

[0017] The absolute Mw of the polymer compound is the molecular weight measured using gel permeation chromatography (GPC) and a light scattering detector. w Specifically, is the molecular weight calculated by the method described in the Examples below.

[0018] The solution viscosity of the polymer compound of the present invention is determined by dissolving the polymer compound of the present invention in butyl acetate to prepare a solution having a solid content (polymer compound) concentration of 40 mass %, and measuring the viscosity of the prepared polymer compound solution at room temperature (25°C) using an E-type viscometer. The solution viscosity thus determined depends on the molecular weight of the polymer compound, but is preferably 5 Pa·s or less, more preferably 2 Pa·s or less.

[0019] The divalent or higher valent linking group has either or both of a thiol group (-SH) and a thioether structure (-S-). The divalent or higher valent linking group may have both a thiol group and a thioether structure, or may have only one of them.

[0020] When the divalent or higher valent linking group has a thiol group, the number of thiol groups per one divalent or higher valent linking group may be one or two or more. When the divalent or higher valent linking group has a thioether structure, the number of thioether structures per one divalent or higher valent linking group may be one or two or more.

[0021] In the present invention, the "divalent or higher valent linking group" refers to a moiety that links multiple polymer chains within a polymer compound. The multiple polymer chains may be the same or different. The polymer chain is usually composed of repeating units described below. The polymer chain may be a homopolymer or a copolymer.

[0022] When the divalent or more linking group has a thiol group, the divalent or more linking group preferably has 1 to 300 thiol groups, and more preferably 5 to 100 thiol groups, per molecule of the polymer compound.

[0023] The divalent or higher valent linking group preferably has a thioether structure, from the viewpoints of excellent long-term thermal stability and ease of production to obtain a variety of compounds. When the divalent or higher valent linking group has a thioether structure, the polymer compound of the present invention tends to have excellent long-term thermal stability because the thioether structure has peroxide decomposition ability in the system. When the divalent or higher valent linking group has a thioether structure, it preferably has a structure represented by formula (2) from the viewpoint of improving heat resistance.

[0024] [ka]

[0025] In formula (2), R 1 and R 2 are each independently any one selected from the group consisting of a hydrogen atom, a monovalent hydrocarbon group, a hydroxyl group, and a monovalent electron-withdrawing group.

[0026] The monovalent hydrocarbon group is not particularly limited, but is preferably an alkyl group, more preferably an alkyl group having 6 or less carbon atoms, even more preferably a methyl group or an ethyl group, and even more preferably a methyl group.

[0027] The monovalent electron-withdrawing group is not particularly limited, but is preferably a halogen atom such as a fluorine atom or a chlorine atom, a phenyl group (-CH), a halogenated hydrocarbon group such as a trifluoromethyl group, a carboxyl group (-COOH), an alkoxycarbonyl group (-COOR) such as a methoxycarbonyl group, an aryloxycarbonyl group (-COOR) such as a phenoxycarbonyl group, an acyl group (-COR) such as an acetyl group, a cyano group (-CN), an aryl group or a substituted aryl group, a nitro group (-NO), a sulfo group (-SOH), an alkoxysulfonyl group (-SOR), an alkanesulfonyl group (-SOR), an alkanesulfinyl group (-SOR), a carbamoyl group (-CONH), or an alkylcarbamoyl group (-CONHR).

[0028] R 1 is preferably a hydrogen atom. 2 is preferably a hydrogen atom, a methyl group or a hydroxyl group.

[0029] In formula (2), R 3 is any one selected from the group consisting of an oxygen atom, a divalent hydrocarbon group, and a divalent electron-withdrawing group.

[0030] The divalent hydrocarbon group is not particularly limited, but is preferably an alkylene group, more preferably an alkylene group having 6 or less carbon atoms, even more preferably a methylene group or ethylene group, and even more preferably a methylene group.

[0031] The divalent electron-withdrawing group is not particularly limited, but is preferably a carbonyl group (-CO-), an ester group (-COO-), a sulfo group (-SO3-), a sulfonyl group (-SO2-), a sulfinyl group (-SO-), an amide group (-CONH-), an aryl group, or a substituted aryl group.

[0032] R 3is preferably a methylene group or an ester group.

[0033] In formula (2), -* is a bond.

[0034] In equation (2), R 1 is a hydrogen atom, and R 2 is a hydrogen atom, a methyl group, or a hydroxyl group, and R 3 is a methylene group or an ester group, and R 1 is a hydrogen atom, and R 2 is a hydroxyl group, and R 3 is a methylene group, or R 1 is a hydrogen atom, and R 2 is a hydrogen atom or a methyl group, and R 3 is an ester group is more preferred.

[0035] The structure represented by formula (2) can be formed, for example, by reacting the thiol group of the polyfunctional thiol compound (A) with the (meth)acrylate group of a mono(meth)acrylate compound or a poly(meth)acrylate compound.

[0036] The divalent or higher linking group is preferably a divalent or higher group derived from a polymerizing chain transfer agent (F) described below.

[0037] The polymer compound preferably has a structure represented by formula (1A) or a structure represented by formula (1B).

[0038] [ka] In formula (1A), P m is the polymer chain and Z 1 is any one selected from the group consisting of a sulfur atom, a carbon atom, a nitrogen atom, and an oxygen atom, and the substituent on each atom is not particularly limited. In formula (1B), P m is the polymer chain and Z 2 is an electron-withdrawing substituent.

[0039] <Oligomerization chain transfer agent (F)> The polymerizing chain transfer agent (F) has a portion derived from the polyfunctional thiol compound (A) and a portion derived from a compound (B) (hereinafter also simply referred to as "compound (B)") having a reactive group that reacts with a thiol group. The polymerizing chain transfer agent (F) is a compound having a thioether structure formed by the reaction of a thiol group of the polyfunctional thiol compound (A) with a reactive group reactive with the thiol group of the compound (B), and having multiple thiol groups. The polymerizing chain transfer agent (F) may also be a mixture of multiple different compounds.

[0040] The polymerizing chain transfer agent (F) can be obtained, for example, by subjecting a polyfunctional thiol compound (A) and a compound (B) to an addition polymerization reaction. In the addition polymerization reaction between the polyfunctional thiol compound (A) and the compound (B), a solvent may or may not be used. When a solvent is used in the addition polymerization reaction, the solvent is not particularly limited, and for example, methyl ethyl ketone, tetrahydrofuran (THF), or toluene may be used. However, when a solvent is used in the addition polymerization reaction, in order to improve the reaction efficiency, the amount of solvent at the start of the addition reaction is preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably 10% by mass or less, based on the total mass of the polyfunctional thiol compound (A) and the compound (B). It is even more preferable that no solvent is used.

[0041] The molar ratio (reactive groups / thiol groups) of the total amount of thiol groups in the multifunctional thiol compound (A) used in the addition polymerization reaction of the multifunctional thiol compound (A) and the compound (B) to the total amount of reactive groups in the compound (B) is not particularly limited in its lower limit, but is preferably 1 / 8 or more. On the other hand, the upper limit of the molar ratio (reactive group / thiol group) is not particularly limited, but is preferably 1 / 1.2 or less, more preferably 1 / 1.5 or less, and even more preferably 1 / 3 or less. When the molar ratio (reactive group / thiol group) is equal to or greater than the lower limit and equal to or less than the upper limit, a chain transfer agent (F) having a plurality of thiol groups is easily obtained.

[0042] The external temperature during the addition polymerization reaction of the polyfunctional thiol compound (A) and the compound (B) is not particularly limited, but is preferably 10 to 80° C., more preferably 10 to 50° C., and even more preferably 25 to 50° C. The external temperature during the reaction refers to, for example, the set temperature of a water bath or oil bath that heats the reaction vessel.

[0043] The reaction time for the addition polymerization reaction between the polyfunctional thiol compound (A) and the compound (B) is preferably 0.05 to 10 hours, more preferably 2 to 5 hours. When the reaction time is 0.05 hours or more, it is easy to prevent the reaction raw materials from remaining unreacted.

[0044] The polyfunctional thiol compound (A) is a compound having at least two thiol groups in the molecule. The polyfunctional thiol compound (A) may be an aliphatic polythiol compound or an aromatic polythiol compound.

[0045] Examples of the fatty acid polythiol compound include an aliphatic polythiol compound that does not have sulfur atoms other than the thiol group, and an aliphatic polythiol compound that has sulfur atoms other than the thiol group.

[0046] Examples of the aliphatic polythiol compound having no sulfur atoms other than the thiol group include methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,6-hexanedithiol, 1,2,3-propanetrithiol, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethylpropane-1,3-dithiol, and the like. Toxicbutane-1,2-dithiol, 2-methylcyclohexane-2,3-dithiol, 1,1-bis(mercaptomethyl)cyclohexane, thiomalic acid bis(2-mercaptoethyl ester), 2,3-dimercapto-1-propanol(2-mercaptoacetate), 2,3-dimercapto-1-propanol(3-mercaptopropionate), 2,3-dimercapto-1-propanol(3-mercaptobutyrate), diethylene glycol bis(2- mercaptoacetate), diethylene glycol bis(3-mercaptopropionate), diethylene glycol bis(3-mercaptobutyrate), 1,2-dimercaptopropyl methyl ether, 2,3-dimercaptopropyl methyl ether, 2,2-bis(mercaptomethyl)-1,3-propanedithiol, bis(2-mercaptoethyl) ether, ethylene glycol bis(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropionate) propionate), ethylene glycol bis(3-mercaptobutyrate), tetraethylene glycol bis(3-mercaptopropionate), trimethylolpropane bis(2-mercaptoacetate), trimethylolpropane bis(3-mercaptopropionate), trimethylolpropane bis(3-mercaptobutyrate), pentaerythritol tetrakis(2-mercaptoacetate) (also known as pentaerythritol tetrakisthioglycolate).), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), tetrakis(mercaptomethyl)methane, dipentaerythritol hexakis(2-mercaptoacetate), dipentaerythritol hexakis(3-mercaptopropionate), and dipentaerythritol hexakis(3-mercaptobutyrate).

[0047] Examples of the aliphatic polythiol compound having a sulfur atom in addition to the thiol group include bis(mercaptomethyl) sulfide, bis(mercaptomethyl) disulfide, bis(mercaptoethyl) sulfide, bis(mercaptoethyl) disulfide, bis(mercaptopropyl) sulfide, bis(mercaptomethylthio)methane, bis(2-mercaptoethylthio)methane, bis(3-mercaptopropylthio)methane, 1,2-bis(mercaptomethylthio)ethane, 1,2-bis(2 -mercaptoethylthio)ethane, 1,2-bis(3-mercaptopropyl)ethane, 1,3-bis(mercaptomethylthio)propane, 1,3-bis(2-mercaptoethylthio)propane, 1,3-bis(3-mercaptopropylthio)propane, 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(2-mercaptoethylthio)propane, 1,2,3-tris(3-mercaptopropylthio)propane, 1,2-bis[(2-mercaptoethyl)thio] -3-Mercaptopropane, 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol, 4,8-dimercaptomethyl-1,11-mercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-mercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-mercapto-3,6,9-trithiaundecane, tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane Examples of such mercaptomethyldisulfide include tetrakis(3-mercaptopropylthiomethyl)methane, bis(2,3-dimercaptopropyl)sulfide, bis(1,3-dimercaptopropyl)sulfide, 2,5-dimercapto-1,4-dithiane, 2,5-dimercaptomethyl-1,4-dithiane, 2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiane, bis(mercaptomethyl)disulfide, bis(mercaptoethyl)disulfide, and bis(mercaptopropyl)disulfide.

[0048] Furthermore, examples of the aliphatic polythiol compound having a sulfur atom in addition to the thiol group include hydroxymethyl sulfide bis(2-mercaptoacetate), hydroxymethyl sulfide bis(3-mercaptopropionate), hydroxymethyl sulfide bis(3-mercaptobutyrate), hydroxyethyl sulfide bis(2-mercaptoacetate), hydroxyethyl sulfide bis(3-mercaptopropionate), hydroxyethyl sulfide bis(3-mercaptobutyrate), Hydroxypropyl sulfide bis(2-mercaptoacetate), hydroxypropyl sulfide bis(3-mercaptopropionate), hydroxypropyl sulfide bis(3-mercaptobutyrate), hydroxymethyl disulfide bis(2-mercaptoacetate), hydroxymethyl disulfide bis(3-mercaptopropionate), hydroxymethyl disulfide bis(3-mercaptobutyrate), hydroxyethyl disulfide bis(2-mercaptoacetate), Hydroxyethyl disulfide bis(3-mercaptopropionate), hydroxyethyl disulfide bis(3-mercaptobutyrate), hydroxypropyl disulfide bis(2-mercaptoacetate), hydroxypropyl disulfide bis(3-mercaptopropionate), hydroxypropyl disulfide bis(3-mercaptobutyrate), 2-mercaptoethyl ether bis(2-mercaptoacetate), 2-mercaptoethyl ether bis(3-mercaptopropionate) thiamin-2,5-diol bis(3-mercaptobutyrate), 2-mercaptoethyl ether bis(3-mercaptobutyrate), 1,4-dithiane-2,5-diol bis(2-mercaptoacetate), 1,4-dithiane-2,5-diol bis(3-mercaptopropionate), 1,4-dithiane-2,5-diol bis(3-mercaptobutyrate), thiodiglycolic acid bis(2-mercaptoethyl ester), thiodipropionic acid bis(2-mercaptoethyl ester), thiodibutanoic acid bis(2-mercaptoethyl ester), 4,Other examples include 4-thiodibutyric acid bis(2-mercaptoethyl ester), dithiodiglycolic acid bis(2-mercaptoethyl ester), dithiodipropionic acid bis(2-mercaptoethyl ester), dithiodibutanoic acid bis(2-mercaptoethyl ester), 4,4-dithiodibutyric acid bis(2-mercaptoethyl ester), thiodiglycolic acid bis(2,3-dimercaptopropyl ester), thiodipropionic acid bis(2,3-dimercaptopropyl ester), thiodibutanoic acid bis(2,3-dimercaptopropyl ester), dithioglycolic acid bis(2,3-dimercaptopropyl ester), dithiodipropionic acid bis(2,3-dimercaptopropyl ester), and dithiodibutanoic acid bis(2,3-dimercaptopropyl ester).

[0049] Examples of the aromatic polythiol compound include aromatic polythiol compounds that do not have sulfur atoms other than thiol groups, and aromatic polythiol compounds that have sulfur atoms other than thiol groups.

[0050] Examples of the aromatic polythiol compound having no sulfur atoms other than the thiol group include 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis(mercaptomethyl)benzene, 1,3-bis(mercaptomethyl)benzene, 1,4-bis(mercaptomethyl)benzene, 1,2-bis(mercaptoethyl)benzene, 1,3-bis(mercaptoethyl)benzene, 1,4-bis(mercaptoethyl)benzene, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, and 1,2,3-trimercaptobenzene. Examples include 1,2,4-tris(mercaptomethyl)benzene, 1,3,5-tris(mercaptomethyl)benzene, 1,2,3-tris(mercaptoethyl)benzene, 1,2,4-tris(mercaptoethyl)benzene, 1,3,5-tris(mercaptoethyl)benzene, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,3-di(p-methoxyphenyl)propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, and 2,4-di(p-mercaptophenyl)pentane.

[0051] Examples of aromatic polythiol compounds having a sulfur atom in addition to the thiol group include 1,2-bis(mercaptoethylthio)benzene, 1,3-bis(mercaptoethylthio)benzene, 1,4-bis(mercaptoethylthio)benzene, 1,2,3-tris(mercaptomethylthio)benzene, 1,2,4-tris(mercaptomethylthio)benzene, 1,3,5-tris(mercaptomethylthio)benzene, 1,2,3-tris(mercaptoethylthio)benzene, 1,2,4-tris(mercaptoethylthio)benzene, and 1,3,5-tris(mercaptoethylthio)benzene.

[0052] The polyfunctional thiol compound (A) is preferably a fatty acid polythiol compound, and from the viewpoint of suppressing decomposition of the linking group due to chain transfer, an aliphatic polythiol compound having no disulfide bond is more preferable, and an aliphatic polythiol compound having no sulfur atoms other than the thiol group is even more preferable.

[0053] The average number of thiol groups per molecule of the polyfunctional thiol compound (A) is preferably more than 1.5, more preferably 2 or more, and even more preferably 2.5 or more. The average number of thiol groups per molecule of the polyfunctional thiol compound (A) is preferably 8 or less, more preferably 6 or less, and even more preferably 5 or less. The average number of thiol groups per molecule of the polyfunctional thiol compound (A) is preferably more than 1.5 and 8 or less, more preferably 2 to 6, and even more preferably 2.5 to 5.

[0054] The polyfunctional thiol compound (A) is preferably a polyfunctional thiol compound having an ester bond in the molecule. The polyfunctional thiol compound having an ester bond in the molecule is preferably a fatty acid polythiol compound having an ester bond in the molecule, more preferably an aliphatic polythiol compound having an ester bond in the molecule but not a disulfide bond, still more preferably an aliphatic polythiol compound having an ester bond in the molecule but not having a sulfur atom other than the thiol group, and even more preferably an aliphatic polythiol compound having an ester bond in the molecule and in which the thiol group is located at the β-position of the ester bond.

[0055] Examples of the polyfunctional thiol compound (A) include pentaerythritol tetrakis(3-mercaptopropionate) (PEMP), pentaerythritol tetrakis(2-mercaptoacetate) (PEMA), dipentaerythritol hexakis(3-mercaptopropionate) (DPMP), tetraethylene glycol bis(3-mercaptopropionate) (EGMP), and pentaerythritol tetrakis(3-mercaptobutyrate). The polyfunctional thiol compound (A) may be used alone or in combination of two or more kinds.

[0056] The lower limit of the molecular weight of the polyfunctional thiol compound (A) is preferably 80, more preferably 300. When the molecular weight of the polyfunctional thiol compound (A) is equal to or greater than the lower limit, handling difficulties due to odor are more likely to be resolved. The upper limit of the molecular weight of the polyfunctional thiol compound (A) is preferably 2,000, more preferably 800. When the molecular weight of the polyfunctional thiol compound (A) is equal to or less than the upper limit, handling difficulties due to increased viscosity are more likely to be resolved. The molecular weight of the polyfunctional thiol compound (A) is preferably in the range of 80 to 2,000, more preferably 300 to 800. The molecular weight of the polyfunctional thiol compound (A) is a molecular weight theoretically calculated based on the chemical structure.

[0057] Compound (B) is a compound having at least one reactive group (hereinafter also simply referred to as "reactive group") that reacts with a thiol group in the molecule.

[0058] The reactive group is, for example, a functional group that can react with a thiol group to form an SC bond. Examples of the reactive group include a (meth)acrylate group, a glycidyl group, and a vinyl group (excluding the vinyl group contained in the (meth)acrylate group). The reactive group is preferably at least one selected from the group consisting of a (meth)acrylate group and a glycidyl group, more preferably a (meth)acrylate group, and even more preferably an acrylate group, because of its high addition reactivity with a thiol group. The reactive group is preferably at least one selected from the group consisting of acrylate groups and has a formula weight of 200 or more.

[0059] The thiol group of the polyfunctional thiol compound (A) reacts with the (meth)acrylate group, glycidyl group, or vinyl group of the compound (B) to form a thioether structure (RS-R'), where R and R' each represent any organic group.

[0060] Examples of the compound (B) include (meth)acrylic acid, mono(meth)acrylate compounds, poly(meth)acrylate compounds, monovinyl compounds, polyvinyl compounds, monoepoxy compounds, and polyepoxy compounds.

[0061] Examples of the mono(meth)acrylate compound include alkyl(meth)acrylates having a linear or branched alkyl group having 1 to 30 carbon atoms, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, glycidyl(meth)acrylate, methoxyethyl(meth)acrylate, ethoxyethyl(meth)acrylate, and ethoxyethoxyethyl(meth)acrylate.

[0062] Examples of the poly(meth)acrylate compound include a diester compound obtained by reacting a diol with (meth)acrylic acid, a polyester compound obtained by reacting a compound having three or more hydroxyl groups per molecule with (meth)acrylic acid, and a compound obtained by reacting a compound having two or more epoxy groups with (meth)acrylic acid.

[0063] Examples of the diester compounds obtained by reacting the diol with 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, neopentyl ... Examples include 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, and 2-hydroxy-1-(meth)acryloyloxy-3-(meth)acryloyloxypropane.

[0064] Examples of polyester compounds obtained by reacting the compound having three or more hydroxyl groups per molecule with (meth)acrylic acid include trimethylolpropane tri(meth)acrylate, tetramethylol tri(meth)acrylate, pentaerythritol tetrakis(meth)acrylate (tetramethylolmethane tetra(meth)acrylate), and dipentaerythritol hexakis(meth)acrylate.

[0065] Examples of the compound obtained by reacting the compound having two or more epoxy groups with (meth)acrylic acid include a bisphenol A diglycidyl ether (meth)acrylic acid adduct and a bisphenol F diglycidyl ether (meth)acrylic acid adduct.

[0066] Examples of the monovinyl compound include styrene compounds, vinyl ether compounds, fumaric acid, monoalkyl esters of fumaric acid, dialkyl esters of fumaric acid, maleic acid, monoalkyl esters of maleic acid, dialkyl esters of maleic acid, itaconic acid, monoalkyl esters of itaconic acid, dialkyl esters of itaconic acid, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl ketone, vinylpyridine, and vinylcarbazole. Examples of the styrene-based compound include α-methylstyrene, vinyltoluene, and styrene. Examples of the vinyl ether compounds include methyl vinyl ether, ethyl vinyl ether, and isobutyl vinyl ether.

[0067] Examples of the polyvinyl compound include butadiene, isoprene, and allyl acrylate, as well as compounds having a plurality of structures equivalent to the above-mentioned monovinyl compounds in one molecule. An example of a compound having a plurality of structures equivalent to the monovinyl compound in one molecule is divinylbenzene.

[0068] Examples of the monoepoxy compound include phenyl glycidyl ether, cresyl glycidyl ether, pt-butylphenyl glycidyl ether, butyl glycidyl ether, alcohol glycidyl ethers having 12 to 14 carbon atoms, butane diglycidyl ether, hexane diglycidyl ether, cyclohexane dimethyl diglycidyl ether, and glycidyl ethers based on polyethylene glycol or polypropylene glycol.

[0069] Examples of the polyepoxy compound include neopentyl glycol diglycidyl ether, bisphenol-type epoxy resins, novolac-type epoxy resins, and compounds having a plurality of glycidyl groups. Examples of the bisphenol type epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol A / bisphenol F copolymer type epoxy resin. Examples of the novolac type epoxy resin include cresol novolac type epoxy resin and phenol novolac type epoxy resin. Examples of the compound having a plurality of glycidyl groups include triglycidyl aminophenol, biphenyl diglycidyl ether, triglycidyl isocyanurate, polyglycidyl (meth)acrylate, and copolymers of glycidyl (meth)acrylate and a vinyl monomer copolymerizable therewith.

[0070] The compound (B) is preferably at least one selected from the group consisting of 1,6-hexanediol diacrylate, ethylhexyl acrylate, trimethylolpropane triacrylate, and tetraethylene glycol diacrylate. The compound (B) may be used alone or in combination of two or more kinds.

[0071] The lower limit of the number of reactive groups per molecule of compound (B) is preferably 1. When only one type of compound (B) is used, the lower limit of the number of reactive groups per molecule of compound (B) is preferably 2. The upper limit of the number of the reactive groups per molecule of the compound (B) is preferably 8, more preferably 6. The number of reactive groups per molecule of compound (B) is preferably in the range of 1 to 8, more preferably 1 to 6. When only one compound (B) is used, the number of reactive groups per molecule of compound (B) is preferably in the range of 2 to 8, more preferably 2 to 6.

[0072] The lower limit of the average number of reactive groups per molecule of the compound (B) is preferably 1.2, more preferably 1.3, and even more preferably 1.5. The upper limit of the average number of reactive groups per molecule of the compound (B) is preferably 8, more preferably 6, and even more preferably 3. The average number of reactive groups per molecule of compound (B) is preferably in the range of 1.2 to 8, more preferably 1.3 to 6, and even more preferably 1.5 to 3, since the polymer compound of the present invention can be easily obtained.

[0073] The upper limit of the molecular weight of the compound (B) is preferably 2,000, more preferably 1,000. When the molecular weight of the compound (B) is equal to or less than the upper limit, handling difficulties due to increased viscosity can be more easily resolved. The molecular weight of the compound (B) is preferably in the range of 300 to 2,000, more preferably 300 to 1,000. The molecular weight of the compound (B) is a molecular weight theoretically calculated based on the chemical structure.

[0074] The addition polymerization reaction between the polyfunctional thiol compound (A) and the compound (B) is preferably carried out in the presence of a catalyst (C). There are no particular limitations on the catalyst (C), but a phosphine compound is preferred. The phosphine compound nucleophilically attacks the reactive group of the compound (B) to produce a phosphine enolate, a zwitterionic intermediate. Because the phosphine enolate is highly basic, it abstracts a proton from the thiol group, forming a phosphonium and simultaneously generating a thiolate anion. The thiolate anion then nucleophilically adds to the reactive group, abstracting a proton from another thiol group or a phosphonium, thereby bonding the thiol group and the reactive group.

[0075] Examples of the phosphine compound include phosphines and diphosphines. Examples of the phosphines include 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 Examples include m-tolylphosphine, tri-p-tolylphosphine, tri-2,4-xylylphosphine, tri-2,5-xylylphosphine, tri-3,5-xylylphosphine, tris(p-methoxyphenyl)phosphine, tris(pt-butoxyphenyl)phosphine, di-t-butylphenylphosphine, [4-(N,N-dimethylamino)phenyl]di-t-butylphosphine, di-t-butyl(2-butenyl)phosphine, di-t-butyl(3-methyl-2-butenyl)phosphine, and trimethylphosphine.

[0076] Examples of the diphosphines include 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.

[0077] The catalyst (C) may be used alone or in combination of two or more kinds. The amount of catalyst (C) used is preferably 0.001 to 10% by mass, more preferably 0.002 to 5% by mass, and even more preferably 0.004 to 3% by mass, per gram of polyfunctional thiol compound (A). When the amount of catalyst (C) used is at least the lower limit of the above range, the reaction proceeds easily, and when it is at most the upper limit of the above range, there is no effect of the remaining catalyst.

[0078] <High C trChain transfer agent (G) high C tr The chain transfer agent (G) is preferably at least one organic compound selected from the group consisting of addition-fragmentation chain transfer agents (hereinafter also referred to as "addition-fragmentation chain transfer agents (G1)") and thiol-based chain transfer agents (hereinafter also referred to as "thiol-based chain transfer agents (G2)").

[0079] high C tr The chain transfer agent (G) preferably contains, in its molecular structure, a structure represented by formula (3A) (dithioester group) or a structure represented by formula (3B) (vinylidene group).

[0080] [ka]

[0081] In formula (3A), R 1 R is a monovalent to trivalent hydrocarbon group which may have a substituent. 1 It is preferable that an electron-withdrawing group is present on the carbon adjacent to S. Examples of the electron-withdrawing group include a cyano group (-CN), an ester group (-COOR), a carboxylic acid group (-COOH), a phenyl group (-CH), or a phenyl group where a substituent is substituted with an electron-withdrawing group (-CHR).

[0082] In formula (3A), Z 3 is an electron-withdrawing substituent. Z 3is not particularly limited as long as it is an electron-withdrawing group, but the optimal conditions vary depending on the monomer to be reacted from the viewpoint of the stability of the radicals generated. For example, electron-withdrawing groups are preferred for conjugated monomers, such as a phenyl group (-CH), or a phenyl group in which a substituent is substituted with an electron-withdrawing group (-CHR), or an alkyl sulfide group (-SR), a benzyl sulfide group (-S-CH-Ph), or a benzyl sulfide group in which an electron-withdrawing substituent is introduced on the benzyl group (-S-CH-CHR). On the other hand, when an electron-rich monomer is used, an electron-donating substituent is desirable, and substitution with, for example, a nitrogen atom or an oxygen atom is even more preferred. Examples of nitrogen atom substitution include pyrazole group (-N2C3H4), pyrazole with a substituent (-N2C3H3R) or (-N2C3H2R2), N-methyl N-phenyl group (-NCH3C6H6), N-methyl N-pyrrole group (-NCH3NCH4), N-alkyl N-alkyl group (-NR1R2), pyrrole group (NC4H4), and amide group (-NCOR). Examples of oxygen atom substitution include alkyl ether group (-OR), phenyl ether group (-OC6H6), or phenyl group with a substituent (-C6R6···*). *···R includes a hydrogen atom.

[0083] In formula (3B), X is a substituent that leaves as a radical when the polymer-growing radical is added to the chain transfer agent. X is not particularly limited as long as it is a monovalent leaving group, but is preferably a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, a sulfide group (-SR), a halogenated hydrocarbon group such as a trifluoromethyl group, an ether group (-O-), a silyl group (-SiR1R2R3) such as a trimethylsilyl group, a phosphate ester group (-PO(OR)2), an alkyl metal (-MR1R2R3) typified by tributyltin, or a nitro group (-NO2).

[0084] In formula (3B), Z 4 is an electron-withdrawing substituent. Z 4is not particularly limited as long as it is a monovalent electron-withdrawing group, but is preferably a halogen atom such as a fluorine atom or a chlorine atom, a phenyl group (-CH), a halogenated hydrocarbon group such as a trifluoromethyl group, a carboxyl group (-COOH), an alkoxycarbonyl group (-COOR) such as a methoxycarbonyl group, an aryloxycarbonyl group (-COOR) such as a phenoxycarbonyl group, an acyl group (-COR) such as an acetyl group, a cyano group (-CN), an aryl group or a substituted aryl group, a nitro group (-NO), a sulfo group (-SOH), an alkoxysulfonyl group (-SOR), an alkanesulfonyl group (-SOR), an alkanesulfinyl group (-SOR), a carbamoyl group (-CONH), or an alkylcarbamoyl group (-CONHR).

[0085] high C tr High C when an organic compound having a structure represented by formula (3A) is used as a chain transfer agent (G) tr The amount of the chain transfer agent (G) added is not particularly limited, but is preferably 0.1 to 25 mol %, more preferably 0.1 to 10 mol %, and even more preferably 0.1 to 1 mol %, relative to the number of moles of thiol groups in the polymerizing chain transfer agent (F).

[0086] high C tr If the amount of the chain transfer agent (G) added exceeds 25 mol% relative to the amount of the polymerizing chain transfer agent (F), the polymerization reaction often occurs via the high Ctr chain transfer agent (G), and the chain transfer agent (F) is not used, which tends to make it difficult to produce a branched polymer. tr When the amount of chain transfer agent (G) added is within the range of 0.1 to 25 mol % relative to the amount of polymerizing chain transfer agent (F), polymerization can be carried out while maintaining a short arm molecular weight of the resulting star polymer. This reduces the influence of steric hindrance on the polymer chain, making the unreacted thiol of chain transfer agent (F) more reactive, thereby increasing the degree of branching of the polymer.

[0087] high C tr High C when an organic compound having a structure represented by formula (3B) is used as a chain transfer agent (G) trThe amount of the chain transfer agent (G) added is not particularly limited, but is preferably 1 to 35 mol %, more preferably 5 to 35 mol %, and even more preferably 20 to 35 mol %, relative to the number of moles of thiol groups in the polymerizing chain transfer agent (F).

[0088] high C tr When the amount of the chain transfer agent (G) added is less than 1 mol % relative to the amount of the polymerizing chain transfer agent (F), high C tr Chain transfer agents (G) are rarely used and tend to be ineffective. tr When the amount of the chain transfer agent (G) added is within a range of 1 to 35 mol % relative to the amount of the polymerizing chain transfer agent (F), the arm molecular weight of the produced polymer can be reduced, thereby achieving the above-mentioned effects.

[0089] high C tr High C when an organic compound having a structure represented by formula (3A) is used as a chain transfer agent (G) tr Chain transfer constant C of chain transfer agent (G) to MMA at 60°C tr The value of is preferably 1 to 5, more preferably 2 to 5, even more preferably 3 to 5, and even more preferably 3.5 to 5. tr When the value of C is within the range of 1 to 5, the effect of lowering the arm molecular weight of the polymerizing chain transfer agent (F) is sufficiently exhibited, and a large amount of low molecular weight components that lead to a deterioration in physical properties are not generated. tr When the value is within the range of 3 to 5, the arm molecular weight of the produced star polymer can be further reduced, thereby achieving the above-mentioned effects.

[0090] high C tr When an organic compound having a structure represented by formula (3A) is used as the chain transfer agent (G), high C tr The amount of the chain transfer agent (G) added is preferably 1 to 25 mol %, more preferably 5 to 25 mol %, and even more preferably 20 to 25 mol %, based on the number of moles of thiol groups in the polymerizing chain transfer agent (F).

[0091] <Radical polymerizable monomer (D)> The polymer chain in the polymer compound of the present invention has a structural unit derived from the radical polymerizable monomer (D). Examples of the radical polymerizable monomer (D) include acrylic acid, methacrylic acid, mono(meth)acrylate compounds, poly(meth)acrylate compounds, monovinyl compounds, and polyvinyl compounds, which are exemplified for the compound (B). The constitutional units derived from the radical polymerizable monomer (D) that form the polymer chain may be of one type or of two or more types.

[0092] <Method of manufacturing polymer compounds> The polymer compound of the present invention can be prepared, for example, by reacting a polyfunctional thiol compound (A) with a compound (B) to synthesize a polymerizable chain transfer agent (F) having multiple thiol groups, and then synthesizing the polymerizable chain transfer agent (F) and a high chain transfer constant chain transfer agent (G) (hereinafter referred to as "high C") that is likely to cause chain transfer. tr The copolymer can be obtained by polymerizing a vinyl compound in the presence of a chain transfer agent (G) and a radical polymerization initiator (H). That is, the polymer compound of the present invention can be produced by radically polymerizing a vinyl compound using a polymerizing chain transfer agent (F), whereby some of the multiple thiol groups possessed by the polymerizing chain transfer agent (F) serve as starting points for polymer chain growth, and the thiol groups bond to the polymer chain, while the remaining thiol groups remain unreacted.

[0093] The polymer compound of the present invention also contains a polymerizing chain transfer agent (F) and a high C tr It is obtained by radically polymerizing a radically polymerizable monomer (D) using a chain transfer agent (G). The amount of the polymerizing chain transfer agent (F) used in the radical polymerization of the radical polymerizable monomer (D) is not particularly limited, but is preferably 0.2 to 20 parts by mass, more preferably 0.6 to 15 parts by mass, per 100 parts by mass of the total amount of the radical polymerizable monomer (D). tr The amount of the chain transfer agent (G) used is not particularly limited, but is preferably 0.001 to 5 parts by mass, more preferably 0.002 to 4 parts by mass, per 100 parts by mass of the total amount of the radical polymerizable monomers (D).

[0094] Examples of the radical polymerization include solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization.

[0095] Examples of polymerization solvents used in the radical polymerization include aromatic hydrocarbon solvents (toluene, ethylbenzene, xylene, etc.), aliphatic hydrocarbon solvents (pentane, hexane, heptane, octane, cyclohexane, etc.), ketone solvents (acetone, methyl isobutyl ketone, methyl ethyl ketone, etc.), ester solvents (butyl acetate, etc.), and alcohol solvents (methanol, ethanol, etc.). The polymerization solvent may be one type or two or more types. The amount of the polymerization solvent used is preferably 50 to 500 parts by mass, more preferably 100 to 300 parts by mass, per 100 parts by mass of the total amount of the radical polymerizable monomers (D).

[0096] Examples of the radical polymerization initiator (H) used in the radical polymerization include peroxides such as dibenzoyl peroxide and tert-butyl permaleate, and azo compounds such as 2,2'-azobisisobutyronitrile and azobisisovaleronitrile. The radical polymerization initiator (H) may be one type or two or more types. The amount of radical polymerization initiator (H) 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 radical polymerizable monomers (D).

[0097] The polymerization temperature of the radical polymerization can be set as appropriate, and is preferably, for example, from −100 to 250° C., which is a suitable temperature range for using the radical polymerization initiator (H).

[0098] The polymerization time for the radical polymerization can be appropriately set, for example, from 0.5 to 48 hours.

[0099] As described above, the polymer compound of the present invention has a structure in which a plurality of polymer chains are linked by the divalent or higher linking group, the divalent or higher linking group having either or both of a thiol group and a thioether structure, and further has either or both of a dithioester group and a vinylidene group substituted with an electron-withdrawing group at the polymer terminal, and the ratio (absolute M w / Relative M w ) is controlled within a specific range. This has the effect of preventing the viscosity of a solution containing the polymer compound of the present invention from increasing.

[0100] [Composition and method for producing the composition] The composition of the present invention is a composition containing, as a main component, a compound (E) having a portion derived from a polyfunctional thiol compound (A) and a portion derived from a compound (B) having a reactive group that reacts with a thiol group, and is a composition that satisfies formulas (11) and (12). r×(f A -1)×(f B -1)<1.2 (11) r=(f B ×y) / (f A ×x) ···(12) In formula (11) and formula (12), f A is the average number of thiol groups per molecule of the polyfunctional thiol compound (A), and f B is the average number of the reactive groups per molecule of the compound (B). A is greater than or equal to 2, and f B is 1.2 or more, except for the case where there is only the compound (A) having two thiol groups and only the compound (B) having two reactive groups. In formula (12), x and y are x and y, respectively, when the molar ratio of the portion derived from the polyfunctional thiol compound (A) to the portion derived from the compound (B) is x:y.

[0101] The composition of the present invention has excellent solubility in polymerization solvents and monomers, and can be suitably used as a chain transfer agent in the production of the polymer compound. In addition, the composition of the present invention has the effect of suppressing the increase in viscosity of a solution to which it is added.

[0102] The compound (E) may be a single compound that satisfies the formulas (11) and (12), or may be a group of multiple compounds that satisfy the formulas (11) and (12). The composition of the present invention contains the compound (E) as a main component. That is, it is sufficient that the composition contains the compound (E) in the largest amount by mass ratio, and the composition may contain, in addition to the compound (E), for example, unreacted polyfunctional thiol compound (A) or compound (B), etc. The composition of the present invention preferably contains 50% by mass or more of compound (E) relative to the total mass of the composition, more preferably 70% by mass or more, even more preferably 80% by mass or more, and even more preferably 90% by mass or more.

[0103] The compound (E) has a portion derived from the polyfunctional thiol compound (A) and a portion derived from the compound (B) having a reactive group that reacts with a thiol group. In compound (E), the portion derived from the polyfunctional thiol compound (A) means the portion formed based on the polyfunctional thiol compound (A) in the structure formed when the polyfunctional thiol compound (A) reacts with a compound (B) having a reactive group that reacts with a thiol group. Similarly, in compound (E), the portion derived from compound (B) having a reactive group that reacts with a thiol group means the portion formed based on compound (B) in the structure formed when polyfunctional thiol compound (A) reacts with compound (B) having a reactive group that reacts with a thiol group. In the present invention, the portion derived from the polyfunctional thiol compound (A) may be referred to as a structural unit consisting of the polyfunctional thiol compound (A). In the present invention, the portion derived from the compound (B) having a reactive group that reacts with a thiol group may be referred to as a structural unit consisting of the compound (B) having a reactive group that reacts with a thiol group.

[0104] The thioether structure may be a moiety having a structure shown in formula (2) from the viewpoint of improving heat resistance.

[0105] [ka]

[0106] In formula (2), R 1 and R 2 are each independently any one selected from the group consisting of a hydrogen atom, a monovalent hydrocarbon group, a hydroxyl group, and a monovalent electron-withdrawing group, and R 3 is any one selected from the group consisting of an oxygen atom, a divalent hydrocarbon group, and a divalent electron-withdrawing group, and -* is a bond.

[0107] Compound (E) preferably has a thioether structure, and more preferably has a structure represented by formula (1), in that it is easy to produce and a variety of compounds can be easily obtained. When the compound (E) has a thioether structure, the polymer compound obtained by polymerization using the compound (E) as a chain transfer agent tends to have excellent long-term thermal stability. Furthermore, when the compound (E) has a thioether structure, the polymer compound obtained by polymerization using the compound (E) as a chain transfer agent tends to have excellent mechanical properties.

[0108] The compound (E) preferably has at least one thiol group per molecule. The average number of thiol groups per molecule of the compound (E) is not particularly limited to a lower limit, but is preferably 3 or more, more preferably 4 or more. On the other hand, the upper limit of the average number of thiol groups per molecule of the compound (E) is not particularly limited, but is preferably 50 or less, more preferably 30 or less. When the average number of thiol groups per molecule of the compound (E) is equal to or greater than the above lower limit, the number of branches of the polymer obtained when the composition of the present invention is used as a chain transfer agent is likely to be sufficient, and the heat resistance of the polymer is also increased. When the average number of thiol groups per molecule of the compound (E) is equal to or less than the upper limit, the solution viscosity of the polymer obtained when the composition of the present invention is used as a chain transfer agent can be reduced.

[0109] The above description can be applied as it is to the polyfunctional thiol compound (A) and the compound (B) having a reactive group that reacts with a thiol group.

[0110] The composition of the present invention satisfies formulas (11) and (12). r×(f A -1)×(f B -1)<1.2 (11) r=(f B ×y) / (f A ×x) ···(12) In formula (11) and formula (12), f A is the average number of thiol groups per molecule of the polyfunctional thiol compound (A), and f B is the average number of the reactive groups per molecule of the compound (B). A is greater than or equal to 2, and f B is 1.2 or more, except for the case where there is only the compound (A) having two thiol groups and only the compound (B) having two reactive groups. In formula (12), x and y are x and y, respectively, when the molar ratio of the portion derived from the polyfunctional thiol compound (A) to the portion derived from the compound (B) is x:y.

[0111] The composition of the present invention has excellent solubility in polymerization solvents and monomers by satisfying the formulas (11) and (12). The reason for this is presumed to be as follows: A -1) and (f B -1) When the values ​​of these are small, there are fewer reaction sites during the production of the composition, so the molecular weight of the composition does not become too large, and it has excellent solubility. When the value of r is small, the number of thiol groups in the product increases, the number of branches in the composition increases, and the solubility improves. In addition, r, (f A -1), (f B If we try to reduce all the values ​​of r × (f −1), it will impose significant restrictions on the raw materials used for manufacturing. A -1)×(f BThe raw materials for producing the composition may be adjusted so that the product of (a) and (b) is less than 1.2, and it is not necessary to reduce all of the values. From this perspective, the present invention also has the advantage of allowing greater freedom in the selection of raw materials for producing the composition.

[0112] The value of formula (11) is 1.2 or less. The present inventors have found that in a composition containing compound (E), when formula (11) is 1.2 or less, the composition has excellent solubility in polymerization solvents and monomers and is also suitable as a chain transfer agent. When the value of formula (11) exceeds 1.2, the composition is prone to gelation or hardening, is insoluble in solvents, and is incompatible with other resins, etc. The upper limit of the value of formula (11) is 1.2 or less, preferably 1.15 or less, and more preferably 1.1 or less. On the other hand, the lower limit of the value of formula (11) is not particularly limited, but is preferably 0.1 or more, more preferably 0.3 or more. When the value of formula (11) is equal to or less than the upper limit of the above range, the solubility in the polymerization solvent and monomer is better. When the value of formula (11) is equal to or greater than the lower limit of the above range, the number of unreacted functional groups per molecule of the obtained compound (E) increases, making it easier to use as a chain transfer agent. For example, when the composition of the present invention containing compound (E) is used as a chain transfer agent, the solution viscosity of the obtained polymer can be reduced, improving handleability.

[0113] Average number of thiol groups per molecule of polyfunctional thiol compound (A) f A The lower limit of f is 2 or more, preferably 2.5 or more, and more preferably 3 or more. On the other hand, the average number f of thiol groups per molecule of the polyfunctional thiol compound (A) A Although the upper limit is not particularly limited, it is preferably 9 or less, more preferably 6 or less, from the viewpoint of preventing insolubilization of the multi-branched thiol compound (A).

[0114] Average number of reactive groups per molecule of compound (B) f B The lower limit of f is 1.2 or more, preferably 1.3 or more, and more preferably 1.5 or more. On the other hand, the average number f of reactive groups per molecule of compound (B) BAlthough there are no particular limitations on the upper limit, from the viewpoint of reducing unreacted thiol groups remaining in the product, it is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less.

[0115] However, this does not include the case where only the compound (A) having two thiol groups and only the compound (B) having two reactive groups are used. That is, when a multi-branched thiol compound (A) having two thiol groups is reacted with only the compound (B) having two reactive groups that react with thiol groups, the resulting compound (E) is almost linear. Therefore, when the compound (E) is used as a chain transfer agent, the number of branches of the resulting polymer is insufficient.

[0116] f A +f B is preferably greater than 4, more preferably 4.5 or greater, and even more preferably 5 or greater. A +f B When it is more than 4, the resulting compound (E) has more branches, and the solubility of the composition is increased. Also, f A +f B is preferably 12 or less, more preferably 10 or less. Furthermore, f A +f B is preferably more than 4 and 12 or less, and more preferably 4.5 to 10.

[0117] The ratio (x / y) of the number of moles x of the portion derived from the polyfunctional thiol compound (A) to the number of moles y of the portion derived from the compound (B) is not particularly limited to a lower limit, but is preferably 0.5 or more, more preferably 0.8 or more, and even more preferably 1 or more. On the other hand, the ratio (x / y) has no particularly limited upper limit, but is preferably 8 or less, more preferably 6 or less, and even more preferably 4 or less. It is preferable to set the ratio (x / y) to the above lower limit or more and the above upper limit or less from the viewpoint of the number of branches and solubility of the compound (E).In addition, the compound (E) is likely to have a thiol group, and is therefore easily usable as a chain transfer agent.

[0118] Relative M of the composition of the present invention wIn terms of solubility and the like, the molecular weight is preferably 1,000 or more, more preferably 1,000 to 50,000, and even more preferably 2,000 to 20,000. In addition, the relative M w is a polymethyl methacrylate-equivalent value measured using gel permeation chromatography (GPC). In the differential molecular weight distribution obtained by GPC measurement of the composition of the present invention, typically, multiple molecular weight peaks are observed in the molecular weight region of 1,000 or more. In this case, it is preferable that all of these multiple molecular weight peaks are within the above-mentioned range.

[0119] As a method for producing the composition of the present invention, it is preferable to react a polyfunctional thiol compound (A) with a compound (B) having a reactive group that reacts with a thiol group under conditions that satisfy formulas (13) and (14). r'×(f A -1)×(f B -1)<1.2 (13) r'=(f B ×y') / (f A ×x') ···(14) In formula (13) and formula (14), f A is the average number of thiol groups per molecule of the polyfunctional thiol compound (A), and f B is the average number of the reactive groups per molecule of the compound (B). A is greater than or equal to 2, and f B is 1.2 or more, except for the case where there is only the compound (A) having two thiol groups and only the compound (B) having two reactive groups. In the formula (14), x' and y' respectively represent x' and y' when the molar ratio of the polyfunctional thiol compound (A) to the compound (B) is x':y'.

[0120] x', y' and r' are values ​​at the time of charging for the reaction, but when the composition after the reaction is used as it is as a "composition containing compound (E)", they are equal to x, y and r, respectively.

[0121] f in equation (13) A and f BThe preferred range of f in formula (11) is A and f B is the same as r'×(f A -1)×(f B The preferred range of r × (f −1) is also A -1)×(f B -1). Furthermore, the preferred ratios of x' and y' are the same as the preferred ratios of x and y in formula (11), and the preferred value of r' is the same as the preferred value of r in formula (11).

[0122] Examples of the polyfunctional thiol compound (A) and the compound (B) include the above-mentioned polyfunctional thiol compound (A) and compound (B), respectively.

[0123] The resulting composition preferably contains the compound (E) as the main component, and may contain unreacted polyfunctional thiol compound (A) and compound (B).

[0124] The conditions for this reaction can be the same as those for obtaining the chain transfer agent (F) by the addition polymerization reaction of the polyfunctional thiol compound (A) and the compound (B). Although there are no particular limitations on this reaction, it is preferable to carry out the reaction in the presence of a catalyst (C). As for the catalyst (C), the above description can be applied as is.

[0125] Furthermore, the composition may be used in combination with additives such as pigments, ultraviolet absorbers, adhesion promoters, release agents, stabilizers, antioxidants, antifoaming agents, plasticizers, and viscosity modifiers, if necessary. The amount of the additive used is preferably less than 5% by mass, more preferably less than 3% by mass, and even more preferably less than 1% by mass, based on the total mass of the composition.

[0126] As described above, in the present invention, when the composition containing the compound (E) satisfies the above conditions, the composition has a large number of branches, does not form a crosslinked polymer network, and has excellent solubility in polymerization solvents and monomers.

[0127] The composition of the present invention can be suitably used as a chain transfer agent in a radical polymerization reaction system. Branched polymers produced using the composition of the present invention as a chain transfer agent have a large number of branches, so even if they have a high molecular weight, the viscosity of the solution to which they are added can be maintained low. Therefore, for example, a paint containing the branched polymer can achieve both improved coating film properties and excellent paintability. Furthermore, this branched polymer also has the effect of excellent heat resistance. Furthermore, when the composition containing the compound (E) of the present invention is added to a thermoplastic resin, it improves the heat resistance of the thermoplastic resin and has the effect of suppressing the viscosity of the solution to which it is added. Therefore, the composition may be used as an additive to paints, etc.

[0128] [Resin composition] The resin composition of the present invention includes the above-described polymer compound or composition and a thermoplastic resin, such as polyamide, polyester, polycarbonate, polyethersulfone, polyphenylene ether, polyphenylene sulfide, polyetheretherketone, polyetherketone, polyimide, polytetrafluoroethylene, polyether, polyolefin, liquid crystal polymer, polyarylate, polysulfone, polyacrylonitrilestyrene, polystyrene, polyacrylonitrile, polymethyl methacrylate (PMMA), polyglycidyl methacrylate (PGMA), and acrylonitrile-butadiene-styrene copolymer (ABS). The thermoplastic resin is preferably an addition polymerization polymer such as polysulfone, polyacrylonitrile styrene, polystyrene, polyacrylonitrile, polymethyl methacrylate (PMMA), polyglycidyl methacrylate (PGMA), or acrylonitrile-butadiene-styrene copolymer (ABS). The thermoplastic resins may be used alone or in combination of two or more. [Example]

[0129] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to the examples described below, and various modifications are possible without departing from the gist of the present invention.

[0130] [Raw materials] The raw materials used in the examples and comparative examples and their abbreviations are shown below.

[0131] <Multifunctional thiol compound (A)> PEMP: Pentaerythritol tetrakis(3-mercaptopropionate) (SC Organic Chemicals) PEMA: Pentaerythritol tetrakis(2-mercaptoacetate) (Tokyo Chemical Industry Co., Ltd.)

[0132] <Compound (B)> C6DA: 1,6-hexanediol diacrylate (Mitsubishi Chemical Corporation) M260: Polyethylene glycol diacrylate (Aronix (registered trademark) M260, manufactured by Toagosei Co., Ltd.) EHA: 2-ethylhexyl acrylate

[0133] <Catalyst (C)> TPP: Triphenylphosphine (Tokyo Chemical Industry Co., Ltd.)

[0134] <Radical polymerizable monomer (D)> MMA: Methyl methacrylate (acrylic ester M, manufactured by Mitsubishi Chemical Corporation) MA: methyl acrylate EHA: 2-ethylhexyl acrylate MAA: methacrylic acid

[0135] <High C tr Chain transfer agent (G) CPDB: 2-cyano-2-propyldithiobenzoate (Aldrich) PhSH: Thiophenol (Tokyo Chemical Industry Co., Ltd.) EBMA: Ethyl-α-bromomethyl acrylate CDTP: 4-cyano-4-dodecylthiocarbonylthiopentanoic acid (Aldrich) OcSH: 1-octanethiol (Fujifilm Wako Pure Chemical Industries, Ltd.) However, OcSH is not a "high C" material as defined in the present invention. tr It is not a chain transfer agent (G).

[0136] <Radical polymerization initiator (H)> AIBN: 2,2'-azobisbutyronitrile

[0137] <Solvent> DMF: Dimethylformamide (Fujifilm Wako Pure Chemical Industries, Ltd.) Diglyme: Diethylene glycol dimethyl ether (Tokyo Chemical Industry Co., Ltd.)

[0138] [Measurement and evaluation methods] <Relative M w , Absolute M w , Absolute M w / Relative M w 〉 (Relative M w ) Relative M of polymer compounds w was measured by gel permeation chromatography (GPC) under the following conditions: Device: HLC-8220 (Tosoh Corporation) Column: TSK GUARD COLUMN SUPER HH (4.6 x 35 mm, manufactured by Tosoh Corporation) and two TSK-GEL SUPER HM-H (6.0 x 150 mm, manufactured by Tosoh Corporation) connected in series Detector: Refractive index (RI) detector Column and detector temperature: 40°C Eluent: tetrahydrofuran Flow rate: 0.6mL / min Sample concentration: 2 mg / mL (tetrahydrofuran solution) Standard material: polymethyl methacrylate (Polymer Laboratories; Mp (peak molecular weight) = 141,500, 55,600, 11,100, 1,590)

[0139] (Absolutely M w ) The absolute Mw of the polymer compound was measured by gel permeation chromatography (GPC) under the following conditions: Apparatus: General-purpose HPLC Prominence (Shimadzu Corporation) Column: One guard column (Showa Denko) and two analytical columns (Showa Denko) connected in series Detector: Multi-angle light scattering detector (((MA)LS) DAWN HELEOS II (Wyatt) Column and detector temperature: 35°C Eluent: tetrahydrofuran Flow rate: 1.0mL / min Sample concentration: 2 mg / mL (tetrahydrofuran solution) Analysis software: OmniSEC (Malvern Panalytical, included with the instrument)

[0140] (Absolutely M w / Relative M w ) Measured absolute M w The relative M w Divide by M w / Relative M w was calculated.

[0141] <Distance between thioether structures> The distance between thioether structures in the linking group of the polymer compound was defined as the molecular weight obtained by adding 2 (the molecular weight of two hydrogen atoms) to the molecular weight value of the compound (B) used.

[0142] <Solution viscosity> The solution viscosity of the polymer compound was measured by the following method. (1) The polymer compounds of the examples and comparative examples were dissolved in butyl acetate to prepare solutions with a solid content (polymer compound) concentration of 40 mass %. (2) The viscosity of the prepared polymer compound solution was measured at room temperature (25°C) using an E-type viscometer.

[0143] <Proportion of branched polymers in polymer compounds> The proportion of branched polymer in the polymer compound was calculated by the following method. The reprecipitated polymer compound was subjected to GPC light scattering measurement to determine the intrinsic viscosity η, calculated from the absolute molecular weight Mw and the radius of gyration Rg. An MH-Plot was then created, with the horizontal axis representing the logarithm of the absolute molecular weight Mw and the vertical axis representing the logarithm of the intrinsic viscosity η. The MH-Plot of the polymer compound obtained in the present invention exhibits a steep slope on the low molecular weight side and a shallow slope on the high molecular weight side. This indicates that the low molecular weight component is dominated by linear polymers, while the high molecular weight component is dominated by branched polymers. Therefore, the polymers present on the high molecular weight side were defined as branched polymers from the point where the slope of the MH-Plot on the low molecular weight side intersects with the slope of the MH-Plot on the high molecular weight side, and the proportion of branched polymers relative to the total amount was calculated [%].

[0144] <Degree of branching> The branching degree of the polymer compound was calculated by the following method. The star polymer compound can be decomposed by applying a known transesterification method, for example, a method of adding a Lewis acid such as a metal alkoxide and an alcohol to the reprecipitated polymer compound. The branching degree was calculated using the Mp (peak top molecular weight) of the polymer compound before the transesterification reaction and the Mp of the polymer compound after the transesterification reaction according to the following formula: Degree of branching = (peak top molecular weight before reaction) / (peak top molecular weight after reaction)

[0145] [Manufacturing Example 1] 10 g of PEMA was used as the polyfunctional thiol compound (A), and 0.1 g of finely crushed TPP was added as the catalyst (C), mixed, and heated to 80°C with stirring until homogeneous and completely dissolved. 3.49 g of C6DA was added as the compound (B) to the resulting mixture, and the molar ratio of PEMA to C6DA was adjusted to PEMA:C6DA = 1.5:1.0. The mixture was stirred at room temperature (25°C) to obtain the polymerized chain transfer agent (F-1).

[0146] [Manufacturing Example 2] A polymerizing chain transfer agent (F-2) was produced in the same manner as in Production Example 1, except that 11.3 g of PEMP was used as the polyfunctional thiol compound (A) instead of 10 g of PEMA, and 10.8 g of M260 was used as the compound (B) instead of 3.49 g of C6DA.

[0147] [Manufacturing Example 3] A polymerizing chain transfer agent (F-3) was produced in the same manner as in Production Example 1, except that C6DA and EHA were used as compound (B) instead of C6DA, and the molar ratio of PEMA to C6DA to EHA was PEMA:C6DA:EHA = 1.5:1.0:1.0.

[0148] [Example 1] In a 50 mL Schlenk flask equipped with a stirrer and a nitrogen inlet tube, 100 parts by mass of MMA (radical polymerizable monomer (D-1)) as the radical polymerizable monomer (D), 3.40 parts by mass of the polymerizable chain transfer agent (F-1) obtained in Production Example 1 as the chain transfer agent (F) relative to 100 parts by mass of the radical polymerizable monomer (D), and high C tr CPDB (high C) as a chain transfer agent (G) tr A chain transfer agent (G-1) was added in an amount of 0.0316 parts by mass relative to 100 parts by mass of the radical polymerizable monomer (D), and AIBN (radical polymerization initiator (H-1)) was added as a radical polymerization initiator (H) in an amount of 0.3 mol% relative to the radical polymerizable monomer (D), and DMF was further added as a solvent. tr The chain transfer agent (G), the radical polymerization initiator (H), and the solvent were mixed in the Schlenk flask to obtain a solids solution (radical polymerizable monomer (D), chain transfer agent (F), high C tr A mixed solution containing a chain transfer agent (G) and a radical polymerization initiator (H) at a concentration of 0.5% by mass was prepared. The mixed solution was heated to 80°C while stirring under a nitrogen atmosphere. After heating and stirring for 5 hours, the mixed solution was reprecipitated using methanol as a poor solvent to obtain a polymer compound. The relative M of the obtained polymer compound w , Absolute M w, absolute Mw / relative Mw, solution viscosity, high C in the number of moles of thiol groups of the polymerizing chain transfer agent (F) tr The molar ratio of the chain transfer agent, the distance between thioether structures, and the degree of branching were measured or calculated. The results of the measurements or calculations are shown in the corresponding columns in Table 1.

[0149] [Examples 2 and 3] The amount of the polymerizing chain transfer agent (F) was changed to 5.51 parts by mass (Example 2) or 6.97 parts by mass (Example 3) per 100 parts by mass of the radical polymerizable monomer (D), and tr A polymer compound was obtained in the same manner as in Example 1, except that the amount of chain transfer agent (G) was changed to 0.0520 parts by mass (Example 2) or 0.0639 parts by mass (Example 3) per 100 parts by mass of radical polymerizable monomer (D). The relative M of the obtained polymer compound w , Absolute M w , absolute Mw / relative Mw, solution viscosity, high C in the number of moles of thiol groups of the polymerizing chain transfer agent (F) tr The molar ratio of the chain transfer agent, the distance between thioether structures, and the degree of branching were measured or calculated. The results of the measurements or calculations are shown in the corresponding columns in Table 1.

[0150] [Examples 4 to 6] As the polymerizing chain transfer agent (F), instead of the polymerizing chain transfer agent (F-1), the polymerizing chain transfer agent (F-2) obtained in Production Example 2 was used, and the amount of the polymerizing chain transfer agent (F) was changed to 4.81 parts by mass (Example 4), 7.82 parts by mass (Example 5), or 9.89 parts by mass (Example 6) per 100 parts by mass of the radical polymerizable monomer (D). tr A polymer compound was obtained in the same manner as in Example 1, except that the amount of chain transfer agent (G) was changed to 0.0447 parts by mass (Example 4), 0.0738 parts by mass (Example 5), or 0.0907 parts by mass (Example 6) per 100 parts by mass of radical polymerizable monomer (D). The relative M of the obtained polymer compound w , solution viscosity, high C in the number of moles of thiol groups of the polymerizing chain transfer agent (F) trThe molar ratio of the chain transfer agent, the distance between thioether structures, and the degree of branching were measured or calculated. The results of the measurements or calculations are shown in the corresponding columns in Table 1.

[0151] [Examples 7 to 9] The amount of the polymerizing chain transfer agent (F) was changed to 2.58 parts by mass (Example 7), 4.17 parts by mass (Example 8), or 5.28 parts by mass (Example 9) per 100 parts by mass of the radical polymerizable monomer (D), and tr As a chain transfer agent (G), CPDB (high C tr Instead of the chain transfer agent (G-1), PhSH (high C tr Chain transfer agent (G-2) was used to produce high C tr A polymer compound was obtained in the same manner as in Example 1, except that the amount of chain transfer agent (G) was changed to 0.402 parts by mass (Example 7), 0.646 parts by mass (Example 8), or 0.816 parts by mass (Example 9) per 100 parts by mass of radical polymerizable monomer (D). The relative M of the obtained polymer compound w , solution viscosity, high C in the number of moles of thiol groups of the polymerizing chain transfer agent (F) tr The molar ratio of the chain transfer agent, the distance between thioether structures, and the degree of branching were measured or calculated. The results of the measurements or calculations are shown in the corresponding columns in Table 1.

[0152] [Examples 10 to 12] As the polymerizing chain transfer agent (F), instead of the polymerizing chain transfer agent (F-1), the polymerizing chain transfer agent (F-2) obtained in Production Example 2 was used, and the amount of the polymerizing chain transfer agent (F) was changed to 3.65 parts by mass (Example 10), 5.93 parts by mass (Example 11), or 7.50 parts by mass (Example 12) per 100 parts by mass of the radical polymerizable monomer (D); and tr As a chain transfer agent (G), CPDB (high C tr Instead of the chain transfer agent (G-1), PhSH (high C tr Chain transfer agent (G-2) was used to produce high C trA polymer compound was obtained in the same manner as in Example 1, except that the amount of chain transfer agent (G) was changed to 0.402 parts by mass (Example 10), 0.646 parts by mass (Example 11), or 0.816 parts by mass (Example 12) per 100 parts by mass of radical polymerizable monomer (D). The relative M of the obtained polymer compound w , solution viscosity, high C in the number of moles of thiol groups of the polymerizing chain transfer agent (F) tr The molar ratio of the chain transfer agent, the distance between thioether structures, and the degree of branching were measured or calculated. The results of the measurements or calculations are shown in the corresponding columns in Table 1.

[0153] [Table 1]

[0154] [Examples 13 to 15] The amount of the polymerizing chain transfer agent (F) was changed to 2.58 parts by mass (Example 13), 4.17 parts by mass (Example 14), or 5.27 parts by mass (Example 15) per 100 parts by mass of the radical polymerizable monomer (D), and tr As a chain transfer agent (G), CPDB (high C tr Chain transfer agent (G-1)) was replaced with EBMA (high C tr Chain transfer agent (G-3) is used to produce high C tr A polymer compound was obtained in the same manner as in Example 1, except that the amount of chain transfer agent (G) was changed to 0.705 parts by mass (Example 13), 1.13 parts by mass (Example 14), or 1.43 parts by mass (Example 15) per 100 parts by mass of radical polymerizable monomer (D). The relative M of the obtained polymer compound w , solution viscosity, high C in the number of moles of thiol groups of the polymerizing chain transfer agent (F) tr The molar ratio of the chain transfer agent, the distance between thioether structures, and the degree of branching were measured or calculated. The results of the measurements or calculations are shown in the corresponding columns in Table 2.

[0155] [Examples 16 to 18] As the polymerizing chain transfer agent (F), instead of the polymerizing chain transfer agent (F-1), the polymerizing chain transfer agent (F-2) obtained in Production Example 2 was used, and the amount of the polymerizing chain transfer agent (F) was changed to 3.65 parts by mass (Example 16), 5.93 parts by mass (Example 17), or 7.50 parts by mass (Example 18) per 100 parts by mass of the radical polymerizable monomer (D). tr As a chain transfer agent (G), CPDB (high C tr Chain transfer agent (G-1)) was replaced with EBMA (high C tr Chain transfer agent (G-3) is used to produce high C tr A polymer compound was obtained in the same manner as in Example 1, except that the amount of chain transfer agent (G) was changed to 0.705 parts by mass (Example 16), 1.13 parts by mass (Example 17), or 1.43 parts by mass (Example 18) per 100 parts by mass of radical polymerizable monomer (D). The relative M of the obtained polymer compound w , solution viscosity, high C in the number of moles of thiol groups of the polymerizing chain transfer agent (F) tr The molar ratio of the chain transfer agent and the distance between thioether structures were measured or calculated. The measurement or calculation results are shown in the corresponding columns in Table 2.

[0156] [Example 19] As the radical polymerizable monomer (D), instead of 100 parts by mass of MMA (radical polymerizable monomer (D-1)), 70 parts by mass of MMA (radical polymerizable monomer (D-1)) and 30 parts by mass of MA (radical polymerizable monomer (D-2)) were used, the amount of the polymerizable chain transfer agent (F) was changed to 3.44 parts by mass per 100 parts by mass of the radical polymerizable monomer (D), and high C tr As a chain transfer agent (G), CPDB (high C tr Instead of chain transfer agent (G-1), CDTP (high C tr Chain transfer agent (G-4) is used to produce high C tr A polymer compound was obtained in the same manner as in Example 1, except that the amount of the chain transfer agent (G) was changed to 0.0067 parts by mass per 100 parts by mass of the radical polymerizable monomer (D). The relative M of the obtained polymer compound w, solution viscosity, high C in the number of moles of thiol groups of the polymerizing chain transfer agent (F) tr The molar ratio of the chain transfer agent and the distance between thioether structures were measured or calculated. The measurement or calculation results are shown in the corresponding columns in Table 2.

[0157] [Examples 20 and 21] As the radical polymerizable monomer (D), instead of 100 parts by mass of MMA (radical polymerizable monomer (D-1)), 72 parts by mass of MMA (radical polymerizable monomer (D-1)), 15 parts by mass of EHA (radical polymerizable monomer (D-3)), and 13 parts by mass of MAA (radical polymerizable monomer (D-4)) were used; the amount of the polymerizable chain transfer agent (F) was changed to 2.00 parts by mass (Example 20) or 4.72 parts by mass (Example 21) relative to 100 parts by mass of the radical polymerizable monomer (D); tr As a chain transfer agent (G), CPDB (high C tr Instead of chain transfer agent (G-1), CDTP (high C tr Chain transfer agent (G-4) is used to produce high C tr A polymer compound was obtained in the same manner as in Example 1, except that the amount of chain transfer agent (G) was changed to 0.034 parts by mass (Example 20) or 0.080 parts by mass (Example 21) per 100 parts by mass of radical polymerizable monomer (D). The relative M of the obtained polymer compound w , solution viscosity, high C in the number of moles of thiol groups of the polymerizing chain transfer agent (F) tr The molar ratio of the chain transfer agent and the distance between thioether structures were measured or calculated. The measurement or calculation results are shown in the corresponding columns in Table 2.

[0158] [Table 2]

[0159] [Comparative Examples 1 to 3] The amount of the polymerizing chain transfer agent (F) was changed to 3.44 parts by mass (Comparative Example 1), 5.57 parts by mass (Comparative Example 2), or 7.04 parts by mass (Comparative Example 3) relative to 100 parts by mass of the radical polymerizable monomer (D), and trA polymer compound was obtained in the same manner as in Example 1, except that the chain transfer agent (G) was not used. The relative Mw, absolute Mw, absolute Mw / relative Mw, solution viscosity, distance between thioether structures, and degree of branching of the obtained polymer compound were measured or calculated. The measurement or calculation results are shown in the corresponding columns in Table 3.

[0160] [Comparative Examples 4 to 6] The amount of the polymerizing chain transfer agent (F) was changed to 2.58 parts by mass (Comparative Example 4), 4.17 parts by mass (Comparative Example 5), or 5.28 parts by mass (Comparative Example 6) relative to 100 parts by mass of the radical polymerizable monomer (D), and tr Chain transfer agent (G) CPDB (high C tr Chain transfer agent (G-1) was replaced with OcSH (high C tr Chain transfer agent (G-5) is used to produce high C tr Polymer compounds were obtained in the same manner as in Example 1, except that the amount of chain transfer agent (G) was changed to 0.523 parts by weight (Comparative Example 4), 0.848 parts by weight (Comparative Example 5), or 1.07 parts by weight (Comparative Example 6) relative to 100 parts by weight of radical polymerizable monomer (D). The relative M of the obtained polymer compound w , solution viscosity, high C in the number of moles of thiol groups of the polymerizing chain transfer agent (F) tr The molar ratio of the chain transfer agent, the distance between thioether structures, and the degree of branching were measured or calculated. The results of the measurements or calculations are shown in the corresponding columns in Table 3. However, the degree of branching in Comparative Example 6 was not calculated.

[0161] [Comparative Examples 7 to 9] As the polymerizing chain transfer agent (F), instead of the polymerizing chain transfer agent (F-1), the polymerizing chain transfer agent (F-2) obtained in Production Example 2 was used, and the amount of the polymerizing chain transfer agent (F) was changed to 4.89 parts by mass (Comparative Example 7), 8.21 parts by mass (Comparative Example 8), or 10.0 parts by mass (Comparative Example 9) per 100 parts by mass of the radical polymerizable monomer (D). tr A polymer compound was obtained in the same manner as in Example 1, except that the chain transfer agent (G) was not used. The relative Mw, absolute Mw, absolute Mw / relative Mw, solution viscosity, distance between thioether structures, and degree of branching of the obtained polymer compound were measured or calculated. The results of the measurement or calculation are shown in the corresponding columns in Table 3. However, measurement of absolute Mw and calculation of absolute Mw / relative Mw were not performed for Comparative Example 8.

[0162] [Comparative Example 10] As the radical polymerizable monomer (D), 70 parts by mass of MMA (radical polymerizable monomer (D-1)) and 30 parts by mass of MA (radical polymerizable monomer (D-2)) were used instead of 100 parts by mass of MMA (radical polymerizable monomer (D-1)), the amount of the polymerizable chain transfer agent (F) was changed to 3.44 parts by mass (Comparative Example 10) relative to 100 parts by mass of the radical polymerizable monomer (D), and tr A polymer compound was obtained in the same manner as in Example 1, except that the chain transfer agent (G) was not used. The relative Mw, solution viscosity, and distance between thioether structures of the obtained polymer compound were measured. The measurement results are shown in the corresponding columns in Table 3.

[0163] [Comparative Examples 11 to 12] As the radical polymerizable monomer (D), 72 parts by mass of MMA (radical polymerizable monomer (D-1)), 15 parts by mass of EHA (radical polymerizable monomer (D-3)), and 13 parts by mass of MAA (radical polymerizable monomer (D-4)) were used instead of 100 parts by mass of MMA (radical polymerizable monomer (D-1)). The amount of the polymerizable chain transfer agent (F) was changed to 2.00 parts by mass (Example 20) or 4.72 parts by mass (Example 21) relative to 100 parts by mass of the radical polymerizable monomer (D). tr A polymer compound was obtained in the same manner as in Example 1, except that the chain transfer agent (G) was not used. The relative Mw, solution viscosity, and distance between thioether structures of the obtained polymer compound were measured. The measurement results are shown in the corresponding columns in Table 3.

[0164] [Table 3]

Claims

1. A polymer compound in which a plurality of polymer chains are linked by a divalent or higher linking group, the plurality of polymer chains have either or both of a dithioester group and a vinylidene group at the ends of the polymer chains; the divalent or higher valent linking group has a thioether structure formed by a reaction between a polyfunctional thiol compound (A) and a compound (B) having a reactive group reactive with a thiol group, and is a group derived from a polymerizing chain transfer agent (F) having a plurality of thiol groups; the ratio of absolute weight average molecular weight (absolute Mw) to relative weight average molecular weight (relative Mw) (absolute Mw / relative Mw) is 1.25 or more; when the divalent or higher valent linking group has two or more thioether structures, the shortest distance between sulfur atoms of the two or more thioether structures is 200 or more in terms of molecular weight; High molecular compound.

2. The polymer compound according to claim 1 , wherein the polymer compound has a structure represented by formula (1A) or a structure represented by formula (1B): 【Chemistry 1】 In formula (1A), Pm is a polymer chain, Z １ is any one selected from the group consisting of a sulfur atom, a carbon atom, a nitrogen atom, and an oxygen atom, and the substituent on each atom is not particularly limited. In formula (1B), Pm is a polymer chain, Z ２ is an electron-withdrawing substituent.

3. The polymer compound according to claim 1 , wherein the divalent or higher valent linking group includes a structure represented by formula (2): 【Chemistry 2】 In formula (2), R １ and R ２ are each independently any one selected from the group consisting of a hydrogen atom, a monovalent hydrocarbon group, a hydroxyl group, and a monovalent electron-withdrawing group, and R ３ represents any one selected from the group consisting of an oxygen atom, a divalent hydrocarbon group, and a divalent electron-withdrawing group, and -* represents a bond.

4. 3. The polymer compound according to claim 1, wherein when the divalent or higher valent linking group has a thiol group, the divalent or higher valent linking group has 1 to 300 thiol groups per molecule of the polymer compound.

5. The polymer compound according to any one of claims 1 to 4, wherein the absolute Mw / relative Mw is 3 or less.

6. a step of reacting a polyfunctional thiol compound (A) with a compound (B) having a reactive group that reacts with a thiol group to obtain a polymerizing chain transfer agent (F) having a thiol group; a step of polymerizing a vinyl compound in the presence of the thiol group-containing polymerizing chain transfer agent (F), a high chain transfer constant chain transfer agent (G) that easily causes chain transfer, and a radical polymerization initiator (H) to obtain a polymer compound; A method for producing a polymer compound, comprising:

7. the high chain transfer constant chain transfer agent (G) is at least one organic compound selected from the group consisting of addition-fragmentation chain transfer agents (G1) and thiol-based chain transfer agents (G2); the addition-fragmentation chain transfer agent (G1) has a chain transfer constant Ctr to methyl methacrylate at 60°C of 1 or more; The thiol chain transfer agent (G2) has a chain transfer constant Ctr to methyl methacrylate at 60°C of 2 or more. A method for producing the polymer compound according to claim 6.

8. The method for producing a polymer compound according to claim 6 , wherein the high chain transfer constant chain transfer agent (G) comprises a structure represented by formula (3A) or a structure represented by formula (3B). 【Transformation 3】 In formula (3A), R １ represents a monovalent to trivalent hydrocarbon group which may have a substituent, and Z ３ is an electron-withdrawing substituent. In formula (3B), X is a substituent that is eliminated as a radical when the polymer-growing radical is added to the chain transfer agent, and Z ４ is an electron-withdrawing substituent.

9. 7. The method for producing a polymer compound according to claim 6, wherein the reactive group reactive with a thiol group in the compound (B) having a reactive group reactive with a thiol group is at least one selected from the group consisting of an acrylate group and a glycidyl group.

10. A resin composition comprising the polymer compound according to any one of claims 1 to 5 and a thermoplastic resin.

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