Polymerization initiator or photosensitizer, polymerization initiation composition, and method for producing resin

Abstract

Provided are a polymerization initiator or photosensitizer, a polymerization initiation composition, and a method for producing a resin, said polymerization initiator or photosensitizer being capable of efficiently performing photopolymerization using light having a wavelength of 365 nm and having excellent heat resistance. A polymerization initiator or photosensitizer according to the present invention is composed of the following component (A). Component (A): a benzophenone derivative having two or more thioether groups to which an aromatic hydrocarbon group having or not having a substituent is bonded.

Description

Technical Field

[0001] This invention relates to a polymerization initiator or photosensitizer, a polymerization initiation composition, and a method for manufacturing a resin. Background Technology

[0002] Resins, especially thermoplastic resins, are manufactured by polymerizing monomers using polymerization initiators. Among polymerization initiators, photopolymerization initiators that initiate polymerization reactions by irradiation with ultraviolet-visible light are known, and various compounds such as benzophenone-based and acylphosphine oxide-based initiators are used.

[0003] In recent years, due to the energy-saving nature of photopolymerization light sources, the use of light-emitting diodes (LEDs) in light sources has been increasing, creating a demand for compounds that can effectively initiate photopolymerization reactions by absorbing ultraviolet light suitable for LEDs (e.g., light with a wavelength of 365 nm). As examples of such compounds, benzophenone-based polymerization initiators having thioether groups or polymerization initiation compositions comprising benzophenone-based polymerization initiators and amine compounds have been proposed (Patent Documents 1-3).

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2022-145340.

[0007] Patent Document 2: Japanese Patent Application Publication No. 52-104592.

[0008] Patent document 3: Japanese Patent Application Publication No. 2021-024974. Summary of the Invention

[0009] The problem that the invention aims to solve

[0010] However, as mentioned above, conventional benzophenone-based polymerization initiators and polymerization initiation compositions using these initiators suffer from insufficient reactivity, leaving room for further improvement. For example, while benzophenone-based polymerization initiators with one thioether group in their structure exhibit absorption at long wavelengths, this absorption is insufficient, requiring the use of anthracene-based sensitizers or acylphosphine oxide-based polymerization initiators. Benzophenone-based polymerization initiators with two methylthio groups in their structure, while having longer wavelengths than those with one substituted group, still suffer from low curing properties (i.e., low reactivity) and low heat resistance.

[0011] The present invention was made in view of the above circumstances, and its object is to provide a polymerization initiator or photosensitizer, polymerization initiation composition and resin manufacturing method that can efficiently perform photopolymerization using light containing a wavelength of 365nm and has excellent heat resistance.

[0012] Methods for solving problems

[0013] The inventors, through repeated and in-depth research to solve the above-mentioned problems, discovered that a polymerization initiation composition containing benzophenone, which incorporates two or more thioethers as thioether groups bonded to an aromatic hydrocarbon skeleton, and various amine compounds, exhibits strong sensitivity to ultraviolet light containing a wavelength of 365 nm, and superior photopolymerization performance under this wavelength condition, compared to conventional benzophenone initiators. This led to the completion of the present invention.

[0014] That is, the polymerization initiator or photosensitizer of the present invention is characterized by being composed of the following component (A).

[0015] Component (A): Benzophenone derivative having two or more thioether groups bonded with or without substituents of aromatic hydrocarbon groups.

[0016] The polymerization initiation composition of the present invention is characterized by comprising the following components (A) and (B).

[0017] Component (A): Benzophenone derivative having two or more thioether groups bonded with or without substituents of aromatic hydrocarbon groups.

[0018] Component (B): An amine compound in which the carbon atom adjacent to the nitrogen atom has one or more hydrogen atoms.

[0019] The polymerization initiation composition of the present invention is characterized by comprising the following components (A) and (C).

[0020] Component (A): Benzophenone derivative having two or more thioether groups bonded with or without substituents of aromatic hydrocarbon groups.

[0021] Component (C): Polymerization initiator, which is selected from intramolecular cleavage free radical polymerization initiators, cationic polymerization initiators and anionic polymerization initiators.

[0022] The method for manufacturing the resin of the present invention is characterized in that the polymerization initiator or photosensitizer is added to the resin raw material containing monomers, and light containing a wavelength of 365nm is irradiated to polymerize the monomers through photopolymerization.

[0023] The effects of the invention

[0024] If the polymerization initiator or photosensitizer, polymerization initiation composition and resin manufacturing method according to the present invention are used, photopolymerization can be carried out efficiently with a small amount of light containing a wavelength of 365 nm, and the heat resistance is also excellent. Detailed Implementation

[0025] The following is a detailed description of how to implement the present invention.

[0026] In this specification, the number of carbon atoms is represented as an integer.

[0027] (Polymerization initiator or photosensitizer)

[0028] The polymerization initiator or photosensitizer of the present invention is composed of the following component (A).

[0029] Component (A): A benzophenone derivative having two or more thioether groups bonded to aromatic hydrocarbon groups with or without substituents.

[0030] When the polymerization initiator or photosensitizer of the present invention is a polymerization initiator, it is excited by irradiating it with light containing a wavelength of 365 nm, and reacts with other compounds to generate free radical species, which have the function of initiating polymerization.

[0031] When the polymerization initiator or photosensitizer of the present invention is a photosensitizer, by irradiating it with light containing a wavelength of 365 nm, it is excited and has the function of transferring the excitation energy to other photopolymerization initiators, thereby enabling a polymerization reaction to occur. This is useful because it allows the use of a light source near 365 nm even when using a photopolymerization initiator with low sensitivity to 365 nm light.

[0032] The benzophenone derivative of component (A) has two or more thioether groups bonded to aromatic hydrocarbon groups, with or without substituents. The number of thioether groups is not particularly limited, but preferably 2 to 4, more preferably 2. The bonding position of the thioether groups in the benzophenone derivative is not particularly limited, but preferably at position 2 or 4, more preferably at position 4. Preferably, 2,2' substitution, 2,4' substitution, or 4,4' substitution are preferred, more preferably 4,4' substitution.

[0033] A thioether group bonded with an aromatic hydrocarbon group, with or without substituents, is a group represented by the following formula.

[0034] [Chemical Formula 1]

[0035] In the formula, R represents an aromatic hydrocarbon group with or without substituents. The number of carbon atoms in the aromatic hydrocarbon group is not particularly limited, but is preferably 18 or less, more preferably 10 or less, and even more preferably 6 or less. Specific examples of aromatic hydrocarbon groups include phenyl, naphthyl, and anthracenyl groups. Phenyl is preferred.

[0036] When the aromatic hydrocarbon group has a substituent, the substituent is not particularly limited, and examples include hydrocarbon groups, oxygen-containing groups, nitrogen-containing groups, sulfur-containing groups, phosphorus-containing groups, halogens, etc. Among these, hydrocarbon groups, oxygen-containing groups, nitrogen-containing groups, and sulfur-containing groups are preferred, and hydrocarbon groups are more preferred.

[0037] The hydrocarbon group is not particularly limited, and examples include saturated or unsaturated aliphatic hydrocarbon groups, saturated or unsaturated alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and hydrocarbon groups combining these. The number of carbon atoms in the hydrocarbon group is preferably 1 to 22. Saturated aliphatic hydrocarbon groups are preferred. Saturated aliphatic hydrocarbon groups can be linear or branched.

[0038] From the viewpoint of enabling efficient photopolymerization, when component (A) acts as a polymerization initiator, the carbon number of the linear or branched saturated aliphatic hydrocarbon group that serves as the substituent for R is preferably 1 to 18, more preferably 1 to 12, further preferably 1 to 8, particularly preferably 1 to 4, especially preferably 2 to 4, and most preferably 3 or 4. Among the linear or branched saturated aliphatic hydrocarbon groups, branched saturated aliphatic hydrocarbon groups are preferred. For example, 1-methylethane-1-yl, 1-methylpropane-1-yl, 2-methylpropane-1-yl, and 2-methylpropane-2-yl are preferred.

[0039] In addition, the number of substituents in R can be 1 to 5, preferably 1 to 3, more preferably 1 or 2.

[0040] When component (A) functions as a photosensitizer, the number of carbon atoms in the linear or branched saturated aliphatic hydrocarbon group that is a substituent of said R is preferably 1 to 18, more preferably 1 to 12, further preferably 1 to 8, and particularly preferably 1 to 4. Among the linear or branched saturated aliphatic hydrocarbon groups, branched saturated aliphatic hydrocarbon groups are preferred.

[0041] In addition, the number of substituents in R can be 1 to 5, preferably 1 to 3, more preferably 1 or 2.

[0042] The benzophenone derivative of component (A) has or does not have substituents at positions other than the thioether group, which is bonded to an aromatic hydrocarbon group with or without a substituent, located at positions 2-6 and 2'-6' of the benzophenone skeleton. The number of such substituents is preferably 4 or less, more preferably 2 or less, and even more preferably none. The substituents are not particularly limited, and examples include, for instance, hydrocarbon groups, oxygen-containing groups, nitrogen-containing groups, sulfur-containing groups, phosphorus-containing groups, halogens, etc. Specific examples include those describing substituents for aromatic hydrocarbon groups in R, and refer to their descriptions.

[0043] In a preferred example, the benzophenone derivative of component (A) is represented by the following formula (1).

[0044] [Chemical Formula 2]

[0045] In the formula, R 1 and R 2 Each can be used independently to represent an aromatic hydrocarbon group that has or does not have a saturated aliphatic hydrocarbon group.

[0046] As a specific example of an aromatic hydrocarbon group in an aromatic hydrocarbon group having or not having a saturated aliphatic hydrocarbon group, examples of aromatic hydrocarbon groups in R can be given, and refer to their description.

[0047] Considering the reactivity of photopolymerization, absorption of long-wavelength ultraviolet light (molar absorptivity at 365 nm), heat resistance, and compatibility with monomers or solvents, R 1 and R 2 The preferred embodiment is an aromatic hydrocarbon group having a saturated aliphatic hydrocarbon group, each independently. As a saturated aliphatic hydrocarbon group, it is preferably a straight-chain or branched saturated aliphatic hydrocarbon group with 1 to 18 carbon atoms, more preferably with 1 to 12 carbon atoms, further preferably with 1 to 8 carbon atoms, particularly preferably with 1 to 4 carbon atoms, especially preferably with 2 to 4 carbon atoms, and most preferably with 3 or 4 carbon atoms. Among the straight-chain or branched saturated aliphatic hydrocarbon groups, branched saturated aliphatic hydrocarbon groups are preferred. As R 1 and R 2 Examples of preferred embodiments include aromatic hydrocarbon groups having two saturated aliphatic hydrocarbon groups, more preferably having 1 to 8 carbon atoms in the two saturated aliphatic hydrocarbon groups, and even more preferably having one or more butyl groups in the two aromatic hydrocarbon groups. As R 1 and R 2 Another example of a preferred embodiment is an aromatic hydrocarbon group having one saturated aliphatic hydrocarbon group, more preferably a saturated aliphatic hydrocarbon group having 3 or 4 carbon atoms.

[0048] If component (A) of the present invention has the structure described above, that is, if it has two or more thioether groups bonded with aromatic hydrocarbon groups with or without substituents, it has a high molar absorptivity compared to conventional structures with one thioether group bonded with an aromatic hydrocarbon group or structures with two thioether groups bonded with saturated aliphatic hydrocarbon groups. In particular, it has a high molar absorptivity at light containing 365 nm. Therefore, it can efficiently carry out photopolymerization and is useful as an initiator and / or photosensitizer for photopolymerization.

[0049] The polymerization initiator or photosensitizer of the present invention preferably has a molar absorptivity of 30,000 L / (mol·cm) or more at the maximum absorption wavelength of component (A). A high molar absorptivity for longer wavelengths of ultraviolet light is useful; for example, a molar absorptivity of 3,000 L / (mol·cm) or more at 365 nm is preferred, more preferably 4,000 L / (mol·cm) or more, and even more preferably 5,000 L / (mol·cm) or more.

[0050] In the photopolymerization reaction, component (A) of the present invention may also be present in the resin after the reaction. In this case, from the viewpoint that if the heat resistance is low (low thermal decomposition temperature), component (A) in the resin composition containing component (A) will thermally decompose under high temperature conditions, resulting in the leakage of decomposition products and problems such as resin discoloration / coloring, it is preferable to have a component with high heat resistance (high thermal decomposition temperature). From the viewpoint of heat resistance, R in the stated formula (1) 1 and R 2 The preferred component is a saturated aliphatic hydrocarbon group with 2 to 6 carbon atoms in the branched chain. The thermal decomposition temperature can be indicated by the 5% weight loss temperature. At the following resin molding temperatures, the 5% weight loss temperature of component (A) is preferably 300°C or higher, more preferably 320°C or higher, and even more preferably 335°C or higher.

[0051] The molding temperature of the resin is known, for example, as follows. It is not particularly limited and can be applied to, for example, styrene-based resins (polystyrene: PS, molding temperature 100°C), cycloolefin-based resins (molding temperature 100°C), (meth)acrylic resins (polymethyl methacrylate, molding temperature 160°C), acrylonitrile-butadiene-styrene copolymers (acrylonitrile-butadiene-styrene copolymer: ABS, molding temperature 220°C), etc.

[0052] The above disclosure also applies to methods of using component (A) to initiate the polymerization reaction of monomers and to photosensitization methods of using component (A) to move excitation energy to other photopolymerization initiators to initiate the polymerization reaction of monomers.

[0053] (Polymerization initiation composition)

[0054] The polymerization initiation composition of the present invention includes the following components (A) and (B).

[0055] Component (A): Benzophenone derivative having two or more thioether groups bonded with or without substituents of aromatic hydrocarbon groups.

[0056] Component (B): An amine compound having one or more hydrogen atoms on the carbon atom adjacent to the nitrogen atom. The polymerization initiation composition of the present invention comprises the following component (A) and the following component (C).

[0057] Component (A): A benzophenone derivative having two or more thioether groups bonded with or without substituents of aromatic hydrocarbon groups. Component (C): Polymerization initiator, selected from intramolecular cleavage free radical polymerization initiators, cationic polymerization initiators and anionic polymerization initiators.

[0058] In this invention, component (A) is the component described above as a polymerization initiator or photosensitizer. Specific details regarding the method of using the polymerization initiation composition of this invention can be found in the described portion. In the polymerization initiation composition of this invention comprising components (A) and (B), component (A) primarily functions as a polymerization initiator. In the polymerization initiation composition of this invention comprising components (A) and (C), component (A) primarily functions as a photosensitizer.

[0059] The polymerization initiation composition of the present invention, comprising component (A) and component (B), generates radical species through a reaction between two molecules of component (A) and component (B). Specifically, the benzophenone derivative of component (A) is excited by light irradiation, and this excited state interacts with an amine compound of component (B) as a hydrogen donor, thereby abstracting hydrogen from the amine compound and generating an active radical in the amine compound. Polymerization is then typically initiated by the radical generated from the amine compound.

[0060] The amine compound of component (B) has one or more hydrogen atoms on the carbon atom adjacent to the nitrogen atom.

[0061] It should be noted that the phrase "a carbon atom adjacent to a nitrogen atom has one or more hydrogen atoms" means that at least one carbon atom adjacent to a nitrogen atom has one or more hydrogen atoms. Therefore, the presence of carbon atoms without hydrogen atoms as adjacent to a nitrogen atom, in addition to this at least one carbon atom, does not preclude the presence of carbon atoms without hydrogen atoms. Furthermore, the atoms bonded to a nitrogen atom are not limited to carbon atoms; other atoms such as hydrogen atoms can also be bonded.

[0062] Examples of such amine compounds are not particularly limited, but include, for example, aminobenzoic acid compounds, amine compounds in which aliphatic hydrocarbon groups and / or saturated aliphatic hydrocarbon groups containing hydroxyl groups are bonded to nitrogen atoms, amine compounds in which aliphatic hydrocarbon groups and aromatic groups are bonded to nitrogen atoms, amine compounds in which aliphatic hydrocarbon groups and aliphatic hydrocarbon groups containing unsaturated groups are bonded to nitrogen atoms, amine compounds having two or more nitrogen atoms, and heterocyclic compounds having nitrogen atoms. These amine compounds may also contain two or more nitrogen atoms in one molecule. The amino group contained in the amine compound may be any one of primary, secondary, or tertiary amino groups, and is preferably an amine compound having a tertiary amino group. The carbon atom adjacent to the nitrogen atom of the amine compound may be bonded to other atoms through double or triple bonds, but is preferably at least one of them bonded to other carbon atoms through a single bond. For example, in the case of a tertiary amine compound, two or fewer of the three carbon atoms adjacent to the nitrogen atom may or may not have unsaturated bonds, and preferably one or more may not have unsaturated bonds.

[0063] Preferably, the compounds are aminobenzoic acid compounds; amine compounds in which an aliphatic hydrocarbon group or a saturated aliphatic hydrocarbon group containing a hydroxyl group is bonded to a nitrogen atom; amine compounds in which a saturated aliphatic hydrocarbon group containing a hydroxyl group is bonded to a nitrogen atom; amine compounds in which an aliphatic hydrocarbon group or an aliphatic hydrocarbon group having a carbon-carbon double bond is bonded to a nitrogen atom; amine compounds in which an aliphatic hydrocarbon group or an aromatic group is bonded to a nitrogen atom; amine compounds in which an aliphatic hydrocarbon group or an aromatic group is bonded to a nitrogen atom, and there are two or more nitrogen atoms; amine compounds containing a heterocyclic ring having a six-membered ring with a nitrogen atom, more preferably aminobenzoic acid compounds; aliphatic hydrocarbon groups or compounds containing a hydroxyl group... Amine compounds in which a saturated aliphatic hydrocarbon group is bonded to a nitrogen atom; amine compounds in which a saturated aliphatic hydrocarbon group containing a hydroxyl group is bonded to a nitrogen atom; amine compounds in which an aliphatic hydrocarbon group or a group having a carbon-carbon double bond is bonded to a nitrogen atom; amine compounds in which an aliphatic hydrocarbon group or an aromatic group is bonded to a nitrogen atom, more preferably aminobenzoic acid compounds; amine compounds in which an aliphatic hydrocarbon group or an aliphatic hydrocarbon group having a carbon-carbon double bond is bonded to a nitrogen atom; amine compounds in which an aliphatic hydrocarbon group is bonded to a nitrogen atom, having two or more nitrogen atoms, particularly preferably aminobenzoic acid compounds.

[0064] In the foregoing, amine compounds containing aliphatic hydrocarbon groups and / or saturated aliphatic hydrocarbon groups containing hydroxyl groups bonded to nitrogen atoms, amine compounds containing saturated aliphatic hydrocarbon groups containing hydroxyl groups bonded to nitrogen atoms; amine compounds containing aliphatic hydrocarbon groups bonded to nitrogen atoms, although preferred examples include amine compounds containing only the groups shown herein bonded to nitrogen atoms, do not necessarily preclude the bonding of hydrogen atoms to nitrogen atoms. The groups shown herein are primarily monovalent groups. However, this does not necessarily preclude them from being divalent groups such as aromatic groups bonded to terminal divalent aliphatic hydrocarbon groups.

[0065] Amine compounds in which aliphatic hydrocarbon groups and aromatic groups are bonded to nitrogen atoms, while preferred examples include amine compounds in which only the groups shown herein are bonded to nitrogen atoms, do not necessarily preclude the bonding of hydrogen atoms to nitrogen atoms. Here, the aromatic group may be a heterocyclic aromatic group containing heteroatoms such as nitrogen atoms, in addition to aromatic groups composed solely of hydrocarbons. The groups shown herein are primarily monovalent groups. However, this does not necessarily preclude divalent groups such as divalent aliphatic hydrocarbon groups or others bonded to the terminal.

[0066] Amine compounds in which aliphatic hydrocarbon groups and groups containing unsaturated groups are bonded to nitrogen atoms, and amine compounds in which aliphatic hydrocarbon groups and groups containing carbon-carbon double bonds are bonded to nitrogen atoms, although preferred examples include amine compounds in which only the groups shown herein are bonded to nitrogen atoms, this does not necessarily preclude the bonding of hydrogen atoms to nitrogen atoms. The groups shown herein are primarily monovalent groups, but this does not necessarily preclude them from being divalent groups such as divalent aliphatic hydrocarbon groups, etc., bonded to the ends of other groups.

[0067] Amine compounds in which an aliphatic hydrocarbon group is bonded to a nitrogen atom and there are two or more nitrogen atoms, although preferred examples include amine compounds containing nitrogen atoms bonded only to an aliphatic hydrocarbon group, do not necessarily preclude the bonding of a hydrogen atom to at least one nitrogen atom. The aliphatic hydrocarbon group is a monovalent or divalent group. As a divalent group, it includes aliphatic hydrocarbon groups bonded to nitrogen atoms at both ends.

[0068] As a component (B), preferably, examples include aminobenzoic acid compounds represented by the following formula (2), or amine compounds represented by the following formula (3) in which an aliphatic hydrocarbon group or a saturated aliphatic hydrocarbon group containing a hydroxyl group is bonded to a nitrogen atom.

[0069] [Chemical Formula 3]

[0070] In the formula, R 3 and R 4 Represented as a saturated aliphatic hydrocarbon group, R 5 It is represented as a hydrocarbon group.

[0071] [Chemical Formula 4]

[0072] In the formula, R 6 When n is 2 or more, R represents either an aliphatic hydrocarbon group or a saturated aliphatic hydrocarbon group containing a hydroxyl group independently. 7 It is represented as an aromatic group. n is an integer from 1 to 3. Aliphatic hydrocarbon groups may or may not have a phenyl group as a substituent.

[0073] In equation (2), R 3 and R 4 The saturated aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 1 to 8, further preferably 1 to 4, and particularly preferably 1 to 2. Specifically, examples include methyl, ethane-1-yl, propane-1-yl, 1-methylethane-1-yl, butane-1-yl, 1-methylpropane-1-yl, 2-methylpropane-1-yl, 2-methylpropane-2-yl, pentane-1-yl, pentane-2-yl, hexane-1-yl, heptane-1-yl, octane-1-yl, nonane-1-yl, decane-1-yl, undecane-1-yl, dodecane-1-yl, etc.

[0074] R 5 The hydrocarbon group is not particularly limited if it is a group composed of carbon and hydrogen, but is preferably a saturated or unsaturated aliphatic hydrocarbon group, more preferably a saturated aliphatic hydrocarbon group, preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 4 carbon atoms. Examples of saturated aliphatic hydrocarbon groups include those described above as R 3 and R 4 The examples are shown.

[0075] In a particularly preferred example, R 3 R 4 R 5 Each is an independent saturated aliphatic hydrocarbon group with 1 to 4 carbon atoms.

[0076] As specific examples of aminobenzoic acid compounds represented by the formula (2), without particular limitation, examples include, for example, ethyl dimethylaminobenzoate, ethyl methylaminobenzoate, ethyl diethylaminobenzoate, etc.

[0077] In the above equation (3), R 6 The aliphatic hydrocarbon group is a saturated or unsaturated aliphatic hydrocarbon group, preferably a saturated aliphatic hydrocarbon group. R 6 The aliphatic hydrocarbon group preferably has 1 to 8 carbon atoms, more preferably 1 to 4, and even more preferably 1. 6 Aliphatic hydrocarbon groups can also have phenyl groups as substituents. In R 6Among aliphatic hydrocarbon groups, examples of saturated aliphatic hydrocarbon groups, such as those mentioned above as R, can be cited. 3 and R 4 The example given. R 6 The saturated aliphatic hydrocarbon group containing hydroxyl groups preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 2 carbon atoms. The number of hydroxyl groups is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1. Specifically, examples include hydroxymethyl, hydroxyethane-1-yl, hydroxypropane-1-yl, hydroxybutane-1-yl, hydroxypentane-1-yl, hydroxyhexane-1-yl, hydroxyheptane-1-yl, and hydroxyoctane-1-yl; preferably hydroxymethyl, hydroxyethane-1-yl, hydroxypropane-1-yl, and hydroxybutane-1-yl; more preferably hydroxyethane-1-yl.

[0078] R 7 The aromatic group preferably has 4 to 10 carbon atoms. Furthermore, the aromatic group may also contain nitrogen or sulfur atoms, and preferably also contains nitrogen atoms. Examples of aromatic groups include phenyl, naphthyl, pyrrole, pyridyl, and azepinyl, with phenyl and pyridyl being preferred. 7 Amine compounds with aromatic groups are not specifically limited to these compounds; examples include dimethylaminopyridine, dimethylaniline, and N,N-dimethylbenzylamine.

[0079] In equation (3), n is preferably 3, and n R 6 Preferably, at least one of the amine groups is a saturated aliphatic hydrocarbon group containing a hydroxyl group, and the others are aliphatic hydrocarbon groups. Specific examples of such amine compounds are not particularly limited, and examples include, for instance, dimethylethanolamine, methyldiethanolamine, triethanolamine, triethylamine, triisopropylamine, dimethylaminopyridine, dimethylaniline, etc., with dimethylethanolamine, methyldiethanolamine, and triethanolamine being preferred.

[0080] Among the amine compounds exemplified above as component (B), there is no particular limitation on amine compounds in which an aliphatic hydrocarbon group or a group containing an unsaturated group is bonded to a nitrogen atom. Examples include amine compounds containing 1 to 4 nitrogen atoms and having 18 or fewer carbon atoms in the group containing the unsaturated group. Preferably, the amine compound is one in which the unsaturated group is bonded to one end of the divalent aliphatic hydrocarbon group and to a nitrogen atom at the other end of the divalent aliphatic hydrocarbon group. There is no particular limitation on the unsaturated group. Examples include groups containing double or triple bonds between carbon atoms or between carbon atoms and heteroatoms, with groups containing carbon-carbon double bonds being more preferred. There is no particular limitation on the carbon-carbon double bond group. Examples include groups containing vinyl, allyl, (meth)acryloyl, (meth)acryloyloxy, acrylamide, etc. Specific examples of such amine compounds, without particular limitation, include, for example, 2-dimethylaminoethyl acrylate.

[0081] Among the amine compounds exemplified above as component (B), amine compounds having two or more nitrogen atoms are not particularly limited, and examples include, for example, amine compounds containing 2 to 5 nitrogen atoms, amine compounds in which nitrogen atoms are linked by divalent saturated aliphatic hydrocarbons, or polyalkylene imides. Specific examples of such amine compounds are not particularly limited, and examples include, for example, ethylenediamine, dimethylethylenediamine, tetramethylethylenediamine, diethylenetriamine, pentamethyldiethylenetriamine, triethyltetramine, hexamethyltriethylenetetramine, tetraethylpentamine, piperazine, dimethylpiperazine, and polyethyleneimine with a molecular weight of 200 to 100,000. Polyethyleneimine can be any of linear, branched, or cyclic structures, or a mixture thereof. The nitrogen atoms contained in polyethyleneimine can be any of primary, secondary, or tertiary amines, or a mixture thereof. An amine compound in which an aliphatic hydrocarbon group is bonded to a nitrogen atom and there are two or more nitrogen atoms, preferably a straight-chain and / or branched-chain compound, more preferably a branched-chain compound.

[0082] Among the amine compounds exemplified above as component (B), heterocyclic compounds having nitrogen atoms are not particularly limited. Preferably, compounds having a saturated or unsaturated heterocycle containing 1 to 4 nitrogen atoms and 2 to 12 carbon atoms are examples. More preferably, heterocyclic compounds containing a 6-membered ring having nitrogen atoms are examples, and even more preferably, heterocyclic compounds containing 2 nitrogen atoms and 4 to 10 carbon atoms are examples. Specific examples of heterocyclic compounds having nitrogen atoms are not particularly limited, and examples include, for instance, diazabicyclooctane, diazabicycloundecene, diazabicyclononene, pyrrolizidine, quinuclidine, hexamethylenetetramine, indolizidine, etc.

[0083] In the polymerization initiation composition of the present invention, the ratio of component (A) to component (B) can be set as a molar ratio of 10:1 to 1:10, preferably 5:1 to 1:5, more preferably 3:1 to 1:3, and even more preferably 1:1 to 1:3.

[0084] The polymerization initiation composition of the present invention is not particularly limited in terms of the amount of monomers involved, but from the viewpoint of efficient reaction, it is preferable that components (A) and (B) are each involved in amounts of 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.2% by mass or more.

[0085] The polymerization initiation composition of the present invention is not particularly limited in terms of the amount of monomers involved, but from the viewpoint of efficient reaction, it is preferable that components (A) and (B) are each involved in amounts of 0.001 mol% or more, more preferably 0.01 mol% or more, and even more preferably 0.1 mol% or more.

[0086] In the polymerization initiation composition of the present invention, other components besides components (A) and (B) may be incorporated without impairing the effects of the present invention. These other components are not particularly limited and examples include, for instance, solvents, sensitizers, silane coupling agents, resin additives, antistatic agents, ultraviolet absorbers, antioxidants, etc.

[0087] The polymerization initiation composition of the present invention, comprising component (A) and component (C), generates radical, cationic, or anionic species through a reaction between two molecules of component (A) and component (C). Specifically, upon light irradiation, the benzophenone derivative of component (A) becomes excited, and component (C) receives this excitation energy, generating a radical, cationic, or anionic species. Polymerization is then typically initiated by the radical, cationic, or anionic species generated by component (C).

[0088] The polymerization initiator of component (C) is selected from intramolecular cleavage type free radical polymerization initiators, as well as cationic polymerization initiators and anionic polymerization initiators.

[0089] As an intramolecular cleavage-type free radical polymerization initiator, there are no particular limitations. Examples include, for instance, benzil ketal compounds, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine oxides.

[0090] As a benzoylazone compound, there are no particular limitations on it; examples include, for instance, 2-dimethoxy-2-phenylacetophenone.

[0091] As a hydroxyacetophenone compound, it is not particularly limited, and examples include, for example, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropanone, 1-(4-(2-hydroxyethoxy)-phenyl)-2-hydroxy-methylpropanone, 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropanoyl)benzyl)phenyl)-2-methylpropane-1-one, etc.

[0092] As an aminoacetophenone compound, it is not particularly limited, and examples include, for example, 2-benzyl-2-(dimethylamino)-1-[4-(morpholino)phenyl]-1-butanone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-dimethylamine-2-(4-methyl-benzyl)-1-(4-malino-4-phenyl)-butane-1-one, etc.

[0093] As an acylphosphine oxide, it is not particularly limited, and examples include phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (BAPO), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, ethyl(2,4,6-trimethylbenzoyl)-phenylphosphate, etc.

[0094] As cationic polymerization initiators, there are no particular limitations; examples include, for instance, photoacid generators. As photoacid generators, there are no particular limitations; examples include, for instance, iodonium salt compounds and sulfonium salt compounds. As iodonium salt compounds, there are no particular limitations; examples include, for instance, diphenyliodonium hexafluorophosphate and 4-methoxyphenyl(phenyl)iodonium trifluoroacetate. As sulfonium salt compounds, there are no particular limitations; examples include, for instance, triphenylsulfonium hexafluorophosphate, triphenylsulfonium trifluoromethanesulfonate, and diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate. The cationic moiety of these compounds can be various cations and is not limited to the examples mentioned above.

[0095] As an anionic polymerization initiator, it is not particularly limited. Examples include photo-alkali-generating agents. Specific examples include 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidine n-butyltriphenylborate and 1,2-diisopropyl-3-[bis(dimethylamino)methylene]guanidium 2-(3-Benzoylphenyl)propionate.

[0096] In the polymerization initiation composition of the present invention, the ratio of component (A) to component (C) can be set as a molar ratio of 10:1 to 1:100, preferably 1:1 to 1:100, more preferably 1:5 to 1:25, and even more preferably 1:5 to 1:10.

[0097] Although there is no particular limitation on the amount of monomers in the polymerization initiation composition of the present invention, from the viewpoint of enabling the reaction to proceed efficiently, it is preferable to use 0.01% by mass or more of component (A) and component (C), more preferably 0.05% by mass or more of component (A) and component (C), and even more preferably 0.1% by mass or more of component (A) and component (C).

[0098] Although the polymerization initiation composition of the present invention is not particularly limited in terms of the amount of monomers involved, from the viewpoint of enabling the reaction to proceed efficiently, it is preferable to involve 0.001 mol% or more of component (A) and component (C), more preferably 0.01 mol% or more of component (A) and component (C), and even more preferably 0.1 mol% or more of component (A) and component (C).

[0099] In the polymerization initiation composition of the present invention, other components besides components (A) and (C) may be incorporated without impairing the effects of the present invention. These other components are not particularly limited; examples include solvents, sensitizers other than component (C), silane coupling agents, resin additives, antistatic agents, ultraviolet absorbers, antioxidants, etc.

[0100] The polymerization initiating composition of the present invention exhibits excellent reactivity in the manufacture of photopolymerization-based resins. It is particularly suitable for photopolymerization reactions using LEDs as the light source. In recent years, due to the need to prevent ultraviolet pollution and the increasing size of curing equipment, devices irradiating longer wavelengths of ultraviolet light have been used, especially LED light sources. LEDs containing wavelengths of 295-410 nm, preferably 295-390 nm, more preferably 340-390 nm, further preferably 360-370 nm, and particularly preferably 365 nm, have become the most commonly used long-wavelength ultraviolet light sources. Therefore, there is a need to develop polymerization initiators adapted to this wavelength. A combination of benzophenone derivatives and amine compounds, incorporating two or more thioether groups bonded to an aromatic hydrocarbon skeleton, exhibits strong sensitivity to long-wavelength ultraviolet light compared to conventional hydrogen-abstracting polymerization initiators, thereby improving the reactivity of unsaturated monomers.

[0101] From the viewpoint described above, the polymerization initiation composition of the present invention is preferably characterized by a molar absorptivity of 30,000 L / (mol·cm) or higher at the maximum absorption wavelength of component (A). A higher molar absorptivity for longer wavelengths of ultraviolet light is advantageous; for example, a molar absorptivity of 3,000 L / (mol·cm) or higher at 365 nm is preferred, more preferably 4,000 L / (mol·cm) or higher, and even more preferably 5,000 L / (mol·cm) or higher.

[0102] The above disclosure also applies to methods for initiating monomer polymerization reactions using compositions containing components (A) and (B). Additionally, it also applies to methods for initiating monomer polymerization reactions using compositions containing components (A) and (C).

[0103] (Resin manufacturing method)

[0104] A resin can be manufactured by adding the polymerization initiator or photosensitizer of the present invention, particularly a polymerization initiation composition of the present invention containing the polymerization initiator or photosensitizer of the present invention, to a resin raw material containing monomers, and irradiating it with light containing a wavelength of 365 nm to polymerize the monomers through photopolymerization. The mechanism of the polymerization reaction is not particularly limited, and examples include, for instance, free radical polymerization, ionic polymerization (cationic polymerization, anionic polymerization), etc.

[0105] As polymerization initiators or photosensitizers suitable for the present invention, and particularly suitable monomers (raw materials for resins) for polymerization initiation compositions of the present invention containing the polymerization initiator or photosensitizer of the present invention, examples include compounds having polymerizable unsaturated bonds or compounds having polymerizable cyclic structures. There is no particular limitation on compounds having polymerizable unsaturated bonds; examples include, for instance, (meth)acrylate monomers, styrene monomers, vinyl monomers, allyl monomers, maleimide monomers, acrylamide monomers, olefin monomers, cyclic olefin monomers, etc. Mixtures of these monomers (raw materials for copolymers) are also applicable. There is no particular limitation on compounds having polymerizable cyclic structures; examples include, for instance, heterocyclic compounds, specifically, ethylene oxide, propylene oxide, ethyleneimine, ethylene sulfide, etc., and mixtures of these monomers (raw materials for copolymers) are also applicable.

[0106] When manufacturing resins using the polymerization initiator or photosensitizer of the present invention, particularly the polymerization initiation composition of the present invention containing the polymerization initiator or photosensitizer of the present invention, photopolymerization can be carried out by irradiating the resin raw material containing the monomers thereto with light containing light of a wavelength of 365 nm.

[0107] Furthermore, photopolymerization can be carried out in a solvent as needed. There are no particular limitations on the solvent; examples include solvents used in general chemical reactions, such as water, alcohols, and organic solvents. From the viewpoint of efficiently advancing photopolymerization, the polymerization initiator or photosensitizer of the present invention, and particularly the polymerization initiation composition of the present invention containing said polymerization initiator or photosensitizer, is useful in that it has excellent affinity for solvents. Particularly preferred is that it can be transparently mixed when added to a solvent.

[0108] From the viewpoint of solubility in monomers, solvents, etc., component (A) of the present invention is preferably a benzophenone derivative having two thioether groups bonded to aromatic hydrocarbon groups having or not having substituents, more preferably a benzophenone derivative having two thioether groups bonded to aromatic hydrocarbon groups having saturated aliphatic hydrocarbon groups. Further preferably, in the above formula (1), R... 1 and R 2 The benzophenone derivative is a branched saturated aliphatic hydrocarbon group. Another preferred embodiment is a substance in which two saturated aliphatic hydrocarbon groups are bonded to the aromatic hydrocarbon group.

[0109] Furthermore, when the aromatic hydrocarbon group is a benzene residue, it is preferable to be a substance that is bonded to a saturated aliphatic hydrocarbon group other than at the para position of the carbon atom bonded to the sulfur atom.

[0110] Example

[0111] The present invention will be described in detail below through embodiments, but the present invention is not limited to these embodiments.

[0112] 1. Benzophenone derivatives

[0113] A benzophenone derivative of component (A) as shown below was obtained.

[0114] (1) 4,4'-Diphenylthiobenzophenone

[0115] [Chemical Formula 5]

[0116] 4,4'-Dichlorobenzophenone (5.0 g), potassium carbonate (12 g), potassium iodide (1.0 g), and N,N-dimethylformamide (DMF) (15 g) were mixed and stirred. Benzylthiol (5.7 g) was added, and the mixture was heated at 110 °C for 12 hours. The mixture was then cooled to 70 °C, deionized water was added, and the mixture was cooled to room temperature. The precipitated solid was separated and dissolved in toluene at 80 °C. A 37% aqueous solution of hydrogen chloride was added, and the mixture was heated for 15 minutes. The aqueous layer was then separated, and the toluene solution was washed with water. Methanol was added to the toluene solution for recrystallization to obtain 4,4'-diphenylthiobenzophenone.

[0117] IR (KBr): 2360 cm -1 1645 cm- 1 1588 cm -1 1310 cm -1 1278 cm -1 1080cm -1 928 cm -1 740 cm -1 .

[0118] 1 HNMR (CDCl3, 400 MHz): 7.21-7.24 (d, 4H, Ph), 7.38-7.42 (d, 4H, Ph), 7.50-7.52 (d, 4H, Ph), 7.64-7.67 (d, 4H, Ph).

[0119] 13 CNMR (CDCl3, 100 MHz): 127.6, 128.8, 129.8, 130.7, 132.2, 133.7,134.8, 144.1, 194.8.

[0120] (2) 4,4'-xylmethylthiobenzophenone

[0121] [Chemical Formula 6]

[0122] 4,4'-Dichlorobenzophenone (5.0 g), potassium carbonate (12 g), potassium iodide (1.0 g), and DMF (15 g) were mixed and stirred. p-Toluenethiol (6.5 g) was added, and the mixture was heated at 110 °C for 12 hours. The mixture was then cooled to 70 °C, deionized water was added, and the mixture was cooled to room temperature. The precipitated solid was separated and dissolved in toluene at 80 °C. A 37% aqueous solution of hydrogen chloride was added, and the mixture was heated for 15 minutes. The aqueous layer was then separated, and the toluene solution was washed with water. Methanol was added to the toluene solution for recrystallization to obtain 4,4'-dimethylthiobenzophenone.

[0123] IR (KBr): 2363 cm -1 1652 cm -1 1586 cm -1 1491 cm -1 1308 cm -1 1274 cm -1 1081 cm -1 1081 cm -1 925 cm -1 825 cm -1 803 cm -1 754 cm -1 487 cm -1 .

[0124] 1 HNMR (CDCl3, 400 MHz): 2.40 (s, 6H, Me), 7.15-7.18 (d, 4H, Ph), 7.21-7.23 (d, 4H, Ph), 7.41-7.43 (d, 4H, Ph), 7.60-7.62 (d, 4H, Ph).

[0125] 13 CNMR (CDCl3, 100 MHz): 21.3 (Me), 126.5, 128.1, 130.5, 130.6, 134.4,134.6, 139.3, 145.0 (Ph), 194.8 (C=O).

[0126] (3) 4,4'-bis(p-isopropylphenylthio)benzophenone

[0127] [Chemical Formula 7]

[0128] 4,4'-Dichlorobenzophenone (5.0 g), potassium carbonate (12 g), potassium iodide (1.0 g), and DMF (15 g) were mixed and stirred. p-Isopropylbenzylthiol (7.3 g) was added, and the mixture was heated at 110 °C for 12 hours. The mixture was then cooled to 70 °C, cooled to room temperature with ion-exchange water, and the precipitated solid was separated. The solid was dissolved in toluene at 80 °C by heating with a 37% aqueous hydrogen chloride solution for 15 minutes. The aqueous layer was then separated, and the toluene solution was washed with water. Recrystallization was performed by adding methanol to the toluene solution to obtain 4,4'-bis(p-isopropylphenylthio)benzophenone.

[0129] IR (KBr): 2960 cm -1 2360 cm -1 1652 cm -1 1586 cm -1 1486 cm -1 1285 cm -1 1079 cm -1 827 cm -1 753 cm -1 .

[0130] 1 HNMR (CDCl3, 400 MHz): 1.27-1.28 (d, 6H, Me), 2.91-2.98 (m, 1H, -C H Me2), 7.17-7.19 (d, 2H, Ph), 7.26-7.28 (d, 2H, Ph), 7.43-7.46 (d, 2H, Ph), 7.63-7.65 (d, 2H, Ph).

[0131] 13 CNMR (CDCl3, 100 MHz): 23.7 (Me), 34.1 (- C HMe2), 126.5, 127.9,128.4, 130.5, 134.3, 134.6, 150.0, 197.8 (Ph).

[0132] (4) 4,4'-bis(p-tert-butylphenylthio)benzophenone

[0133] [Chemical Formula 8]

[0134] 4,4'-Dichlorobenzophenone (5.0 g), potassium carbonate (12 g), potassium iodide (1.0 g), and DMF (15 g) were mixed and stirred. p-tert-butylbenzylthiol (8.0 g) was added, and the mixture was heated at 110 °C for 12 hours. The mixture was then cooled to 70 °C, deionized water was added, and the mixture was cooled to room temperature. The precipitated solid was separated and dissolved in toluene at 80 °C. A 37% aqueous solution of hydrogen chloride was added, and the mixture was heated for 15 minutes. The aqueous layer was then separated, and the toluene solution was washed with water. Methanol was added to the toluene solution for recrystallization to obtain 4,4'-bis(p-tert-butylphenylthio)benzophenone.

[0135] IR (KBr): 2959 cm -1 2360 cm -1 1644 cm -1 1587 cm -1 1309 cm -1 1287 cm -1 834 cm -1 .

[0136] 1 HNMR (CDCl3, 400 MHz): 1.34 (s, 9H, -C Me 3), 7.18-7.20 (d, 4H, Ph), 7.43-7.45 (d, 8H, Ph), 7.63-7.65 (d, 4H, Ph).

[0137] 13 CNMR (CDCl3, 100 MHz): 31.1 (Me), 34.8 (- C Me3), 126.5, 127.0, 128.2,130.4, 133.8, 134.6, 144.8, 152.4 (Ph), 194.9 (C=O).

[0138] (5) 4-(p-Tolylthio)benzophenone

[0139] [Chemical Formula 9]

[0140] 4-Chlorobenzophenone (4.3 g), potassium carbonate (6.0 g), potassium iodide (0.5 g), and DMF (13 g) were mixed and stirred. p-Toluenethiol (3.0 g) was added, and the mixture was heated at 110 °C for 12 hours. The mixture was then cooled to 70 °C, deionized water was added, and the mixture was cooled to room temperature. The precipitated solid was separated and dissolved in toluene at 80 °C. A 37% aqueous solution of hydrogen chloride was added, and the mixture was heated for 15 minutes. The aqueous layer was then separated, and the toluene solution was washed with water. Methanol was added to the toluene solution for recrystallization to obtain 4-(p-Toluylthio)benzophenone.

[0141] IR (KBr): 2959 cm -1 2360 cm -1 1644 cm -1 1587 cm -1 1309 cm -1 1287cm- 1 834 cm -1 .

[0142] 1 HNMR (CDCl3, 400 MHz): 2.40 (s, 3H, Me), 7.16-7.24 (m, 4H, Ph), 7.42-7.48 (m, 4H, Ph), 7.55-7.58 (t, 1H, Ph), 7.67-7.68 (d, 2H, Ph), 7.74-7.77 (d,2H, Ph).

[0143] 13 CNMR (CDCl3, 100 MHz): 21.3 (Me), 126.5, 128.0, 128.3, 129.9, 130.5,130.7, 132.2, 134.4, 134.5, 137.7, 139.3, 145.3 (Ph), 195.8 (C=O).

[0144] (6) 4,4'-bis(methylthio)benzophenone

[0145] [Chemical Formula 10]

[0146] 4,4'-Dichlorobenzophenone (5.0 g), potassium carbonate (12 g), potassium iodide (1.0 g), and DMF (30 g) were mixed and stirred. A 15% sodium methanethiol aqueous solution (20 g) was added, and the mixture was heated at 110 °C for 12 hours. The mixture was then cooled to 70 °C, deionized water was added, and the mixture was cooled to room temperature. The precipitated solid was separated and dissolved in toluene at 80 °C. A 37% hydrogen chloride aqueous solution was added, and the mixture was heated for 15 minutes. The aqueous layer was then separated, and the toluene solution was washed with water. Methanol was added to the toluene solution for recrystallization to obtain 4,4'-bis(methylthio)benzophenone.

[0147] IR (KBr): 2357 cm -1 1650 cm -1 1276 cm -1 804 cm -1 726 cm -1 695 cm -1 474 cm -1 .

[0148] 1 HNMR (CDCl3, 400 MHz): 2.55 (s, 6H, Me), 7.28-7.31 (d, 4H, Ph), 7.71-7.73 (d, 4H, Ph).

[0149] 13 CNMR (CDCl3, 100 MHz): 14.9 (Me), 124.5, 130.5, 136.2, 145.0 (Ph), 194.9 (C=O).

[0150] (7) 4,4'-bis(octylthio)benzophenone

[0151] [Chemical Formula 11]

[0152] 4,4'-Dichlorobenzophenone (5.0 g), potassium carbonate (12 g), potassium iodide (1.0 g), and DMF (15 g) were mixed and stirred. Octanethiol (12 g) was added, and the mixture was heated at 110 °C for 12 hours. The mixture was then cooled to 70 °C, deionized water was added, and the mixture was cooled to room temperature. The precipitated solid was separated and dissolved in toluene at 80 °C. A 37% aqueous solution of hydrogen chloride was added, and the mixture was heated for 15 minutes. The aqueous layer was then separated, and the toluene solution was washed with water. Methanol was added to the toluene solution for recrystallization to obtain 4,4'-bis(octylthio)benzophenone.

[0153] IR (KBr): 2923 cm -1 2852 cm -1 1634 cm -1 1590 cm -1 1398 cm -1 1293 cm -1 1090 cm -1 729 cm -1 .

[0154] 1 HNMR (CDCl3, 400 MHz): 0.87-0.91 (t, 3H, Me), 1.23-1.37 (m, 16H, -C H 2-), 1.43-1.50 (m, 4H, -C H2 -), 1.68-1.76 (m, 4H, -C H2 -), 2.98-3.03 (t, 4H, -SC H2 -), 7.31-7.34 (d, 4H, Ph), 7.70-7.72 (d, 4H, Ph).

[0155] 13 CNMR (CDCl3, 100 MHz): 14.1, 22.6, 28.8, 28.9, 29.1, 31.8, 32.0, 32.1 (aliphatic chains), 126.1, 130.5, 131.2, 144.0 (Ph), 195.0 (C=O).

[0156] (9) 4,4'-Dithio(4-tert-butyl-2-methylphenyl)benzophenone

[0157] [Chemical Formula 12]

[0158] 4,4'-Dichlorobenzophenone (5.0 g), potassium carbonate (12 g), potassium iodide (1.0 g), and DMF (15 g) were mixed and stirred. 5-tert-butyl-2-methylbenzylthiol (8.7 g) was added, and the mixture was heated at 100 °C for 12 hours. The mixture was then cooled to 70 °C, deionized water was added, and the mixture was cooled to room temperature. The precipitated solid was separated and dissolved in toluene at 80 °C. A 37% aqueous solution of hydrogen chloride was added, and the mixture was heated for 15 minutes. The aqueous layer was then separated, and the toluene solution was washed with water. Methanol was added to the toluene solution for recrystallization to obtain 4,4'-dithio(4-tert-butyl-2-methylphenyl)benzophenone.

[0159] IR (KBr): 2963 cm -1 2362 cm -1 1640 cm -1 1586 cm -1 1287 cm -1 1082 cm -1 926 cm -1 754 cm -1 .

[0160] 1 HNMR (CDCl3, 400 MHz): 1.30 (s, 18H, tBu), 2.33 (s, 6H, Me), 7.05-7.07 (d, 4H, Ph), 7.25-7.28 (d, 2H, Ph), 7.36-7.37 (d, 2H, Ph), 7.56 (s, 2H, Ph), 7.61-7.63 (d, 4H, Ph).

[0161] 13 CNMR (CDCl3, 100 MHz): 20.1(Ph- C H3), 31.3 (C( C H3)3), 34.5 ( C (CH3)3),125.7, 126.9, 129.5, 130.6, 130.8, 133.2, 134.2, 139.3, 144.6, 150.4 (Ph),194.9 ( C =O).

[0162] (10) 4,4'-Dithio(3-methylphenyl)benzophenone

[0163] [Chemical Formula 13]

[0164] 4,4'-Dichlorobenzophenone (5.0 g), potassium carbonate (12 g), potassium iodide (1.0 g), and DMF (15 g) were mixed and stirred. Toluene mercaptan (6.0 g) was added, and the mixture was heated at 100 °C for 12 hours. The mixture was then cooled to 70 °C, deionized water was added, and the mixture was cooled to room temperature. The precipitated solid was separated and dissolved in toluene at 80 °C. A 37% aqueous solution of hydrogen chloride was added, and the mixture was heated for 15 minutes. The aqueous layer was then separated, and the toluene solution was washed with water. Methanol was added to the toluene solution for recrystallization to obtain 4,4'-dichloro(3-methylphenyl)benzophenone.

[0165] IR (KBr): 2358 cm -1 1642 cm -1 1310 cm -1 1282 cm -1 1077 cm -1 927 cm -1 846 cm -1 781 cm -1 750 cm -1 .

[0166] 1 HNMR (CDCl3, 400 MHz): 2.37 (s, 6H, Me), 7.21-7.23 (m, 6H, Ph), 7.27-7.31 (t, 4H, Ph), 7.34 (s, 2H, Ph), 7.64-7.66 (d, 4H, Ph).

[0167] 13 CNMR (CDCl3, 100 MHz): 21.3 (Me), 127.3, 129.5, 129.6, 130.6, 130.9,131.8, 134.4, 134.8, 139.6, 144.3 (Ph), 194.8 (C=O).

[0168] (11) 4,4'-Dithio(2,4-dimethylphenyl)benzophenone

[0169] [Chemical Formula 14]

[0170] 4,4'-Dichlorobenzophenone (5.0 g), potassium carbonate (12 g), potassium iodide (1.0 g), and DMF (15 g) were mixed and stirred. 2,4-Dimethylphenylthiol (6.0 g) was added, and the mixture was heated at 100 °C for 12 hours. The mixture was then cooled to 70 °C, deionized water was added, and the mixture was cooled to room temperature. The precipitated solid was separated and dissolved in toluene at 80 °C. A 37% aqueous solution of hydrogen chloride was added, and the mixture was heated for 15 minutes. The aqueous layer was then separated, and the toluene solution was washed with water. Methanol was added to the toluene solution for recrystallization to obtain 4,4'-dithio(2,4-dimethylphenyl)benzophenone.

[0171] IR (KBr): 2361 cm -1 1644 cm -1 1588 cm -1 1399 cm -1 1311 cm -1 1285 cm -1 1079 cm -1 928 cm -1 809 cm -1 753 cm -1 .

[0172] 1 HNMR (CDCl3, 400 MHz): 2.34 (s, 6H, Me), 2.37 (s, 6H, Me), 7.03-7.07(m, 6H, Ph), 7.16 (s, 2H, Ph), 7.42-7.44 (d, 2H, Ph), 7.59-7.61 (d, 4H, Ph).

[0173] 13 CNMR (CDCl3, 100 MHz): 20.6, 21.2 (Me), 125.6, 126.6, 128.0, 130.6,134.2, 136.3, 140.1, 142.3, 144.8 (Ph), 194.8 (C=O).

[0174] (12) 4,4'-Dithio(2,5-dimethylphenyl)benzophenone

[0175] [Chemical Formula 15]

[0176] 4,4'-Dichlorobenzophenone (5.0 g), potassium carbonate (12 g), potassium iodide (1.0 g), and DMF (15 g) were mixed and stirred. 2,5-Dimethylbenzylthiol (6.0 g) was added, and the mixture was heated at 100 °C for 12 hours. The mixture was then cooled to 70 °C, deionized water was added, and the mixture was cooled to room temperature. The precipitated solid was separated and dissolved in toluene at 80 °C. A 37% aqueous solution of hydrogen chloride was added, and the mixture was heated for 15 minutes. The aqueous layer was then separated, and the toluene solution was washed with water. Methanol was added to the toluene solution for recrystallization to obtain 4,4'-dithio(2,5-dimethylphenyl)benzophenone.

[0177] IR (KBr): 2919 cm -1 1650 cm -1 1585 cm -1 1488 cm -1 1284 cm -1 1083 cm -1 924 cm -1 754 cm -1 .

[0178] 1 HNMR (CDCl3, 400 MHz): 2.32 (s, 3H, Me), 2.33 (s, 3H, Me), 7.05-7.08(s, 4H, Ph), 7.13-7.24 (m, 6H, Ph), 7.35 (s, 2H, Me), 7.61-7.63 (d, 4H, Ph).

[0179] 13 CNMR (CDCl3, 100 MHz): 20.2, 20.8 (Me), 125.9, 128.2, 128.6, 129.1,130.6, 130.9, 134.3, 136.5, 136.8, 139.1, 144.4 (Ph), 194.8 (C=O).

[0180] 2. Ultraviolet (UV) absorption properties of component (A)

[0181] 100 μM chloroform solutions of each benzophenone derivative were prepared and contained in 10 mm quartz cuvettes. The absorption spectra were measured using a UV-Vis spectrophotometer (V-550 manufactured by Japan Spectrophotometer Co., Ltd.). The maximum absorption wavelength, its molar absorptivity, and the molar absorptivity at 365 nm are shown in Table 1.

[0182] It has been confirmed that when component (A) is A-1 to A-4, A-9 to A-12 of the examples, the molar absorptivity at the maximum absorption wavelength is 30,000 L / (mol·cm) or higher, and it can absorb light efficiently. It has also been confirmed that, particularly from the viewpoint of the molar absorptivity at 365 nm, when component (A) is A-1 to A-4, A-9 to A-12 of the examples, it is 3,000 L / (mol·cm) or higher, and its performance in absorbing light at a wavelength of 365 nm is higher than that of comparative examples A-5 to A-7. This suggests that the polymerization initiation composition containing component (A) of the present invention is useful for photoradical polymerization of LEDs as light sources.

[0183] It has also been confirmed that, in the examples, benzophenone derivatives having two thioether groups bonded to an aromatic hydrocarbon group having one saturated aliphatic hydrocarbon group as substituents, such as A-2 to A-4 and A-10, have a molar absorptivity of 4000 L / (mol·cm) or higher at 365 nm, especially if R in the above formula (1) is such as A-3 and A-4. 1 and R 2 If the branched saturated aliphatic hydrocarbon group has a molar absorptivity of 5000 L (mol·cm) or higher at 365 nm, it is more useful.

[0184] 3. Heat resistance of component (A)

[0185] The 5% weight loss temperature of each benzophenone derivative was determined as shown below. A thermogravimetric-differential thermal analysis (TG / DTA 6200) was used, with a heating rate of 10 °C / min and a measurement range of 25 °C to 550 °C. The temperature at which the weight change (TG) was 5% was recorded. The results are shown in Table 1.

[0186] The results confirm that when component (A) is A-1 to A-4, A-9 to A-12 of the examples, its 5% weight loss temperature is above 300°C, and its heat resistance is superior compared to comparative examples A-5 to A-7. This implies that the polymerization initiation composition containing component (A) of the present invention, even when component (A) is present in the resin after the polymerization reaction, does not decompose even during high-temperature molding of the resin, and problems such as exudation of decomposition products and discoloration / staining of the resin are improved.

[0187] In the examples, benzophenone derivatives having two thioether groups bonded to an aromatic hydrocarbon group having a saturated aliphatic hydrocarbon group as substituents, such as A-2 to A-4, A-9 to A-12, have a 5% weight loss temperature of 300°C or higher. In particular, if R in the above formula (1) is a substituent such as A-3, A-4, A-9, etc., then R is a thioether group bonded to an aromatic hydrocarbon group having a saturated aliphatic hydrocarbon group.1 and R 2 If it is a branched saturated aliphatic hydrocarbon group, then the 5% weight loss temperature is above 335℃, which is useful for molding temperatures that are suitable for higher temperatures.

[0188] [Table 1]

[0189] 4. Reactivity of the polymerization-initiated composition (1)

[0190] Following the combinations shown in Tables 2A, 2B, 3A, 3B, and 3C, 0.15 g of component (A) (benzophenone derivative) and 0.15 g of component (B) (amine compound) were dissolved in 3.0 g of butyl acrylate as a monomer. The polymerization reaction was carried out by irradiating the reaction solution with 365 nm light using an LED light source. Five minutes after irradiation (cumulative light intensity 500 mJ / cm²), the polymerization was completed. 2 ), 10 minutes (cumulative light intensity 1000mJ / cm²) 2 The viscous solid was dissolved in a 0.05 wt% dichloroform solution of butyl acrylate to stop the polymerization reaction, and the solution was used as a sample for nuclear magnetic resonance (NMR) measurement. The reaction rate was determined by NMR (Ultrashilede 400 Plus, BRUKER) using the peak value of the olefin derived from butyl acrylate and the reduction rate when the butyl acrylate before the reaction was taken as 100.

[0191] Tables 2A and 2B confirm that polymerization can occur when a polymerization initiating composition containing both component (A) and component (B) is used, but no reaction occurs when only one component is present, as shown in Comparative Examples 4 and 5. Tables 2A and 2B also confirm that Examples 5-8 and 28-31, where component (B) is B-1 and component (A) is A-1 to A-4, A-9 to A-12, exhibited a reaction rate of over 90% after 5 minutes of reaction initiation, compared to Comparative Examples 6-9 which used A-5 to A-8, demonstrating superior reactivity. This suggests that the polymerization initiating composition of the present invention can efficiently perform photopolymerization.

[0192] It can also be confirmed that, in the embodiments, it is useful to perform photopolymerization more efficiently if component (A) is A-3, A-4, A-9, A-11 and A-12.

[0193] Tables 3A, 3B, and 3C confirm that when component (A) is A-1, and component (B) is B-1 to B-20 as in the examples, photopolymerization can proceed. This suggests that the polymerization initiation composition of the present invention can efficiently undergo photopolymerization.

[0194] In the examples, if component (B) is B-1 (aminobenzoic acid compounds), B-2 and B-4 (amine compounds with aliphatic hydrocarbon groups and saturated aliphatic hydrocarbon groups containing hydroxyl groups bonded to nitrogen atoms), B-3 (amine compounds with saturated aliphatic hydrocarbon groups containing hydroxyl groups bonded to nitrogen atoms), B-5 ​​(amine compounds containing a heterocyclic ring with a six-membered ring having a nitrogen atom), B-10 (amine compounds with aliphatic hydrocarbon groups and aliphatic hydrocarbon groups containing unsaturated groups bonded to nitrogen atoms), B-11~B-13 and B-16~B-18 (amine compounds with aliphatic hydrocarbon groups bonded to nitrogen atoms, where there are two or more nitrogen atoms), B-14 (amine compounds with aliphatic hydrocarbon groups and aromatic groups bonded to nitrogen atoms), and B-15 (amine compounds with aliphatic hydrocarbon groups bonded to nitrogen atoms), then the reaction rate after 5 minutes (min) is over 80%, which is useful for photopolymerization. Furthermore, it is useful if component (B) is B-1, B-2, B-3, B-4, B-10, B-11~B-13 and B-14, and the reaction rate after 5 minutes is above 90%. In particular, it is useful if component (B) is B-1, B-10 and B-12, and the reaction rate after 5 minutes is above 95%.

[0195] [Table 2A]

[0196] [Table 2B]

[0197] [Table 3A]

[0198] [Table 3B]

[0199] [Table 3C]

[0200] The experimental results of the effect of the amount (mass%) of the polymerization initiating composition in the reaction solution on the reaction rate are shown in Table 4. The reaction solution contained the amounts of components (A) and (B) as described in Table 4, relative to 3 g (100 mol%) of butyl acrylate as a monomer. From the viewpoint of these results, it can be confirmed that if the polymerization initiating composition of the present invention is used in amounts of 0.1 mol% (relative to the monomer, component (A): 0.04 mol%, component (B): 0.07 mol%) or more of components (A) and (B), respectively, relative to the mass of the reaction solution, the reaction rate after 5 minutes is 40% or more. Furthermore, it has been confirmed that if 0.25 mol% (relative to the monomer, component (A): 0.1 mol%, component (B): 0.17 mol%) or more of components (A) and (B), respectively, the reaction rate after 5 minutes is 80% or more. Furthermore, it has been confirmed that if components (A) and (B) of the present invention are each 0.5% by mass (component (A): 0.2 mol%, component (B): 0.35 mol%) or more relative to the monomer, the reaction rate after 5 minutes is 95% or more, and the photopolymerization reaction can be carried out efficiently.

[0201] Furthermore, it has been confirmed that, as in Examples 43 and 44, photopolymerization can be carried out efficiently even when components (A) and (B) are not of the same mass.

[0202] This suggests that polymerization initiation compositions containing components (A) and (B) of the present invention are useful for polymerization reactions of various monomers.

[0203] [Table 4]

[0204] 5. Solubility of component (A) in monomers and solvents

[0205] Add components (A) A-1~A-4, A-9~A-12 (0.1g) to butyl acrylate (1.0g) or toluene (1.0g) and stir. Visually confirm the appearance of the mixture and evaluate its solubility as follows (Table 5).

[0206] Solubility evaluation

[0207] ◎: It dissolved transparently.

[0208] ○: It dissolved in a mostly transparent manner, but some turbidity was observed.

[0209] △: Does not dissolve.

[0210] It has also been confirmed that, as shown in Examples 20-23 and 45-48 of Table 5, when component (A) is A-2-A-4 or A-9-A-12, it is readily soluble in butyl acrylate or toluene. This suggests that if component (A) contained in the polymerization initiation composition of the present invention has an aromatic hydrocarbon group bonded to a saturated aliphatic hydrocarbon group, it will be readily soluble in monomers and solvents, which is useful for photopolymerization reactions.

[0211] In the examples, benzophenone derivatives such as A-2 to A-4, A-9 to A-12, which have two thioether groups bonded to an aromatic hydrocarbon group having a saturated aliphatic hydrocarbon group, are useful as they have good solubility in toluene. In particular, A-3, A-4, A-9 to A-12 are especially useful as they have good solubility in butyl acrylate and toluene.

[0212] [Table 5]

[0213] 6. Reactivity of the polymerization-initiated composition (2)

[0214] As shown in Table 6, component (A) A-3 (0.15 g) and component (B) B-1 (0.15 g) were dissolved in 3.0 g of each monomer to form a reaction solution. The reaction solution was irradiated with 365 nm light using an LED light source to conduct the polymerization reaction. Five minutes after irradiation (cumulative light intensity 500 mJ / cm²), the polymerization was completed. 2 ), 10 minutes (cumulative light intensity 1000mJ / cm) 2 The viscous solid was dissolved in a 0.05% by mass solution of butylated hydroxytoluene (BHT) in dichloroform to stop the polymerization reaction and serve as a sample for NMR analysis. The reaction rate was determined using an NMR spectrometer (BRUKER ULTRASHILDE 400 PLUS) by comparing the peak values ​​of the olefins derived from various monomers with the decrease in the value of each monomer before the reaction, taking 100 as the threshold value.

[0215] It was also confirmed that, as shown in Examples 8, 49-52 of Table 6, the reaction rate after 5 minutes of light exposure was over 99% in both (meth)acrylate monomers and acrylamide monomers, demonstrating high reactivity.

[0216] This suggests that the polymerization initiation composition of the present invention is useful for the polymerization of various monomers.

[0217] [Table 6]

[0218] 7. Photosensitizer test

[0219] Components (A) (0.3 g) and (C) (0.03 g) shown in Tables 7A, 7B, and 7C were dissolved in butyl acrylate (3.0 g) to prepare a reaction solution. The reaction solution was irradiated with 365 nm light using an LED light source to conduct the polymerization reaction. One minute after irradiation (cumulative light intensity 100 mJ / cm²), the reaction time was [not specified]. 2 ), 2 minutes (cumulative light intensity 200mJ / cm) 2 ), 3 minutes (cumulative light intensity 300mJ / cm) 2 The viscous solid was dissolved in a 0.05% by mass solution of butyl hydroxytoluene (BHT) in dichloroform, and used as a sample for NMR analysis while stopping the polymerization reaction. The reaction rate was determined using an NMR spectrometer (BRUKER ULTRASHILDE 400 PLUS) by the reduction rate of the peak value of the olefin derived from butyl acrylate to the value of butyl acrylate before the reaction, with butyl acrylate as 100.

[0220] It was also confirmed that, as shown in Examples 53-58 of Tables 7A, 7B, and 7C, even when component (A) was used as a photosensitizer and combined with the polymerization initiator of component (C) as a polymerization initiation composition, the polymerization reaction of butyl acrylate could proceed well compared to the comparative examples.

[0221] This suggests that the photosensitizer of the present invention, when combined with a polymerization initiator as a polymerization initiation composition, is also useful for the polymerization reactions of various monomers.

[0222] [Table 7A]

[0223] [Table 7B]

[0224] [Table 7C]

Claims

1. A polymerization initiator or photosensitizer, wherein, The polymerization initiator or photosensitizer is composed of the following component (A), Component (A): Benzophenone derivative having two or more thioether groups bonded with or without substituents of aromatic hydrocarbon groups.

2. The polymerization initiator or photosensitizer according to claim 1, wherein, The benzophenone derivative of component (A) is represented by the following formula (1): In equation (1), R 1 and R 2 Each can be used independently to represent an aromatic hydrocarbon group that has or does not have a saturated aliphatic hydrocarbon group.

3. The polymerization initiator or photosensitizer according to claim 2, wherein, The R 1 and R 2 Each is an aromatic hydrocarbon group, which is independently an aromatic hydrocarbon group having 1 to 18 carbon atoms in a saturated aliphatic hydrocarbon group.

4. The polymerization initiator or photosensitizer according to claim 1, wherein, The molar absorptivity of component (A) at 365 nm is above 3000 L / (mol·cm).

5. The polymerization initiator or photosensitizer according to claim 1, wherein, The 5% weight loss temperature of component (A) is above 300°C.

6. A polymerization initiation composition, wherein, The polymerization initiation composition contains the following components (A) and (B). Component (A): A benzophenone derivative having two or more thioether groups bonded with or without substituents of aromatic hydrocarbon groups. Component (B): An amine compound in which the carbon atom adjacent to the nitrogen atom has one or more hydrogen atoms.

7. The polymerization initiation composition according to claim 6, wherein, The amine compound as component (B) is selected from at least one of the following: aminobenzoic acid compounds, amine compounds in which an aliphatic hydrocarbon group and / or a saturated aliphatic hydrocarbon group containing a hydroxyl group is bonded to a nitrogen atom, amine compounds in which an aliphatic hydrocarbon group and an aromatic group are bonded to a nitrogen atom, amine compounds in which an aliphatic hydrocarbon group and an aliphatic hydrocarbon group having an unsaturated group are bonded to a nitrogen atom, amine compounds having two or more nitrogen atoms, and heterocyclic compounds having a nitrogen atom.

8. The polymerization initiation composition according to claim 6, wherein, The amine compound that is component (B) is represented by the following formula (2), In equation (2), R 3 and R 4 R represents a saturated aliphatic hydrocarbon group. 5 It indicates a hydrocarbon group.

9. A polymerization initiation composition, wherein, The polymerization initiation composition comprises the following components (A) and (C). Component (A): A benzophenone derivative having two or more thioether groups bonded with or without substituents of aromatic hydrocarbon groups. Component (C): Polymerization initiator, which is selected from intramolecular cleavage free radical polymerization initiators, cationic polymerization initiators and anionic polymerization initiators.

10. A method for manufacturing a resin, wherein, Add the polymerization initiator or photosensitizer according to any one of claims 1 to 5 to the resin raw material containing monomers, and irradiate it with light containing a wavelength of 365 nm to polymerize the monomers through photopolymerization.

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