Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C327/00—Thiocarboxylic acids
  • C07C327/20—Esters of monothiocarboxylic acids
  • C07C327/26—Esters of monothiocarboxylic acids having carbon atoms of esterified thiocarboxyl groups bound to carbon atoms of six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/38—Esters containing sulfur
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16

Definitions

• the present invention relates to a compound, a polymerizable composition, an adhesive, a cured resin, a molded product, a film, a pressure-sensitive adhesive, and a method for producing the compound.
• (Meth)acrylic resins are widely used in various industrial fields, for example, as adhesives, molded products, films, and pressure sensitive adhesives.
• (Meth)acrylic resins are formed, for example, by radical polymerization of monomers containing (meth)acrylic groups.
• phenoxybenzyl acrylate (POB-A) is known as a monomer containing a (meth)acrylic group.
• a homopolymer of phenoxybenzyl acrylate (POB-A) has been proposed as a (meth)acrylic resin (see, for example, Patent Document 1 (Example 3)).
• (Meth)acrylic resins are also sometimes used in the optical field. In such cases, (meth)acrylic resins with a relatively high refractive index are required to suppress light reflection. Furthermore, in the optical field, curability is required. However, homopolymers of phenoxybenzyl acrylate (POB-A) do not have sufficient refractive index and curability.
• a thio(meth)acrylate compound as a monomer containing a (meth)acrylic group.
• a trisacrylate of 1,2-bis((2-mercaptoethyl)thio)-3-mercaptopropane has been proposed as a thio(meth)acrylate compound.
• the trisacrylate of 1,2-bis((2-mercaptoethyl)thio)-3-mercaptopropane is produced by reacting 1,2-bis((2-mercaptoethyl)thio)-3-mercaptopropane with ⁇ -chloropropionic acid chloride and treating the reaction product with triethylamine (see, for example, Patent Document 2 (Example 3)).
• a thio(meth)acrylate compound to improve the refractive index and curability is being considered. More specifically, the use of a thio(meth)acrylate compound described in Patent Document 2 in combination with a monomer containing a (meth)acrylic group described in Patent Document 1 is being considered to obtain a cured product with excellent refractive index and curability.
• the present invention relates to a compound capable of producing a cured resin having both excellent refractive index and curability as well as excellent flexibility, an adhesive, a cured resin, a molded product, a film, and a pressure-sensitive adhesive obtained using the compound, and a method for producing the compound.
• the present invention includes a compound represented by the following formula (1).
• Formula (1)
• A represents an m+n valent organic group containing a sulfur atom.
• m represents an integer of 1 or more.
• n represents an integer of 1 or more.
• m+n represents an integer of 3 or more.
• S represents a sulfur atom.
• X represents a single bond or a carbonyl group.
• R represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or an araliphatic hydrocarbon group.
• R' represents a hydrogen atom or a methyl group.
• the present invention [2] includes the compound described in [1] above, in which A represents an organic group containing a sulfur atom and a typical element atom (excluding sulfur and hydrogen atoms), and the ratio of the number of sulfur atoms to the total number of sulfur atoms and the typical element atoms (excluding sulfur and hydrogen atoms) in A exceeds 20%.
• the present invention [3] includes the compound according to the above [1] or [2], in which A in formula (1) is represented by the following formula (2) or the following formula (3).
• the present invention [4] includes a compound according to any one of the above [1] to [3], in which, in formula (A), X represents a carbonyl group and R represents a methyl group, a phenyl group, or a 2-phenylethyl group.
• the present invention [5] includes a polymerizable composition containing the compound described in any one of [1] to [4] above.
• the present invention [7] includes the polymerizable composition according to the above [5] or [6], further comprising another polymerizable compound, the other polymerizable compound including a compound represented by the following formula (7): Formula (7);
• A, S, R', m and n have the same meanings as A, S, R', m and n in formula (1).
• the present invention [8] includes the polymerizable composition described in [7] above, in which the average number of (meth)acryloyl groups in the total amount of the compound represented by the above formula (1) and the compound represented by the above formula (7) is 1.4 or less.
• the present invention [9] further includes the polymerizable composition according to any one of the above [5] to [8], which further includes other polymerizable compounds, and the other polymerizable compounds include a monofunctional (meth)acrylate and/or a polyfunctional (meth)acrylate.
• the present invention includes the polymerizable composition according to any one of the above [5] to [9], which contains a plasticizer, and the plasticizer contains a compound represented by the following formula (4): Formula (4);
• the present invention [11] includes an adhesive containing the polymerizable composition described in any one of [5] to [10] above.
• the present invention [12] includes the adhesive described in [11] above, which is an optical adhesive.
• the present invention [13] includes a resin cured product, which includes a cured product of the polymerizable composition described in any one of [5] to [10] above.
• the present invention [14] includes the resin cured product described in [13] above, which has a refractive index of 1.60 or more and a tensile storage modulus of 10 MPa or less.
• the present invention [15] includes a molded article that contains the resin cured product described in [13] or [14] above.
• the present invention [16] includes the molded article described in [15] above, which is an optical component.
• the present invention [17] includes a film containing the resin cured product described in [13] or [14] above.
• the present invention [18] includes the film described in [17] above, which is an optical film.
• the present invention [19] includes an adhesive containing the resin cured product described in [14] or [15] above.
• the present invention [20] includes the adhesive described in [19] above, which is an optical adhesive.
• the present invention [21] is a method for producing the compound according to any one of the above [1] to [3], and includes a method for producing the compound, comprising a preparation step of preparing a polythiol having a valence of m+n (m+n is an integer of 3 or more) containing a sulfur atom, and a reaction step of reacting the polythiol with a first modifier that caps the molecular ends of the polythiol and does not form (meth)acryloyl groups, and a second modifier that caps the molecular ends of the polythiol and forms (meth)acryloyl groups.
• the present invention includes the method for producing the compound according to the above [21], wherein the polythiol is represented by the following formula (5) or the following formula (6).
• the present invention includes a method for producing the compound described in the above [21] or [22], in which the reaction step includes a first reaction step in which the polythiol is reacted with the first modifying agent, and a second reaction step in which, after the first reaction step, the reaction product of the first reaction step is reacted with the second modifying agent.
• the compound, polymerizable composition, and adhesive of the present invention can produce a cured resin that has excellent refractive index and curability as well as excellent flexibility.
• the resin cured products, molded articles, films and adhesives of the present invention have excellent refractive index and curability as well as excellent flexibility.
• the compound manufacturing method of the present invention makes it possible to efficiently obtain the above-mentioned compound.
• A represents an m+n valent organic group containing a sulfur atom.
• m represents an integer of 1 or more.
• n represents an integer of 1 or more.
• m+n represents an integer of 3 or more.
• S represents a sulfur atom.
• X represents a single bond or a carbonyl group.
• R represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or an araliphatic hydrocarbon group.
• R' represents a hydrogen atom or a methyl group.
• the compound represented by the above formula (1) is a polythiol modification in which some of the mercapto groups of a trifunctional or higher sulfur-containing polythiol (described below) form thio(meth)acryloyl groups and the remaining mercapto groups form SXR groups.
• the compound represented by the above formula (1) may be referred to as a partial thio(meth)acryloyl modification.
• Thio(meth)acryloyl refers to thioacryloyl and/or thiomethacryloyl.
• (meth)acryloyl refers to acryloyl and/or methacryloyl.
• (meth)acryl refers to acryloyl and/or methacryl.
• (meth)acryl refers to acryl and/or methacryl.
• a in the formula in the above formula (1) represents an m+n valent organic group containing a sulfur atom.
• A represents an organic group containing a sulfur atom and a typical element atom (excluding sulfur and hydrogen atoms).
• typical elements refer to elements with atomic numbers 2 to 15, elements with atomic numbers 17 to 20, elements with atomic numbers 31 to 38, elements with atomic numbers 49 to 56, and elements with atomic numbers 81 to 88.
• typical elements preferably elements with atomic numbers 2 to 15 are used, more preferably elements with atomic numbers 6 to 9 are used, and more specifically, carbon, nitrogen, oxygen, and fluorine are used. These may be used alone or in combination of two or more types.
• typical elements include carbon and oxygen, and particularly preferably, carbon.
• typical elements include carbon and oxygen, and particularly preferably, carbon.
• A represents an organic group containing a sulfur atom and a carbon atom, and even more preferably, A represents an organic group consisting of a sulfur atom and a carbon atom.
• n+n is the valence of the organic group A. More specifically, m is an integer of 1 or more. Also, n is an integer of 1 or more. And m+n is an integer of 3 or more.
• m may be 1 or an integer of 2 or more.
• n is an integer of 2 or more.
• m+n is an integer of 3 or more.
• n may be 1 or an integer of 2 or more.
• n is 1, m is an integer of 2 or more.
• m+n is an integer of 3 or more.
• n is preferably 1.
• the valence (m+n) of the organic group A is preferably an integer of 3 or more and 8 or less, more preferably an integer of 3 or more and 6 or less, and even more preferably 3 or 4.
• the organic group A can be, for example, a residue of an m+n functional thiol. More specifically, the organic group A can be a residue obtained by removing a mercapto group from a sulfur-containing polythiol having three or more functional groups (hereinafter, referred to as a sulfur-containing polythiol residue having three or more functional groups).
• a trifunctional or higher sulfur-containing polythiol is an organic compound that contains three or more mercapto groups in one molecule and one or more (preferably two or three) sulfur atoms other than the mercapto groups.
• Examples of trifunctional or higher sulfur-containing polythiols include sulfur-containing trithiol, sulfur-containing tetrathiol, sulfur-containing pentathiol, sulfur-containing hexathiol, and sulfur-containing octathiol.
• Sulfur-containing trithiols are trifunctional thiols that contain a sulfur atom in addition to a mercapto group.
• sulfur-containing trithiols include 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(2-mercaptoethylthio)propane, 1,2,3-tris(3-mercaptopropylthio)propane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (GST), 2,2-bis(mercaptomethylthio)ethanethiol, 3-mercaptomethylthio-1,7-dimercapto-2,6-dithiaheptane, 3-mercaptomethylthio-1,6-dimercapto-2,5-dithiahexane, and 4,6-bis[4-(6-mercaptomethylthio)-1,3-dithianylthio].
• Sulfur-containing tetrathiols are tetrafunctional thiols that contain sulfur atoms in addition to mercapto groups.
• sulfur-containing tetrathiols include 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (FSH), 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, bis(2,3-dimercaptopropyl)sulfide, thiodipropionic acid bis(2,3-dimercaptopropy
• Sulfur-containing pentathiols are pentafunctional thiols that contain sulfur atoms in addition to mercapto groups.
• sulfur-containing pentathiols include 1-[4-(6-mercaptomethylthio)-1,3-dithianylthio]-3-[2,2-bis(mercaptomethylthio)ethyl]-7,9-bis(mercaptomethylthio)-2,4,6,10-tetrathiaundecane and bis[4,4-bis(mercaptomethylthio)-1,3-dithiabutyl]-(mercaptomethylthio)methane.
• Sulfur-containing hexathiols are hexafunctional thiols that contain sulfur atoms in addition to mercapto groups.
• sulfur-containing hexathiols include 1,1,9,9-tetrakis(mercaptomethylthio)-5-(3,3-bis(mercaptomethylthio)-1-thiapropyl)-3,7-dithianonane, tris(2,2-bis(mercaptomethylthio)ethyl)methane, tris(4,4-bis(mercaptomethylthio)-2-thiabutyl)methane, 3,5,9,11-tetrakis(mercaptomethylthio)-1,13-dimercapto-2,6,8,12-tetrathiatridecane, and 3,4,8,9-tetrakis(mercaptomethylthio)-1,11-dimercapto-2,5,7,10-tetrathiatridecane.
• Sulfur-containing octathiols are octafunctional thiols that contain sulfur atoms in addition to mercapto groups.
• sulfur-containing octathiols include tetrakis(4,4-bis(mercaptomethylthio)-2-thiabutyl)methane, 3,5,9,11,15,17-hexakis(mercaptomethylthio)-1,19-dimercapto-2,6,8,12,14,18-hexathianonadecane, 9-(2,2-bis(mercaptomethylthio)ethyl)-3,5,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane, tetrakis(2,2 -bis(mercaptomethylthio)ethyl)methane, 3,4,8,9,13,14-hexakis(mercapto
• trifunctional or higher sulfur-containing polythiol residue preferably, trifunctional to hexafunctional sulfur-containing polythiol residues are used, more preferably, trifunctional to tetrafunctional sulfur-containing polythiol residues are used, and even more preferably, trifunctional sulfur-containing polythiol residues are used.
• A is preferably a trifunctional to hexafunctional sulfur-containing polythiol residue, more preferably a trifunctional to tetrafunctional sulfur-containing polythiol residue, and even more preferably a trifunctional sulfur-containing polythiol residue.
• A is preferably a trivalent to hexavalent organic group containing one or more sulfur atoms (preferably two or three).
• A is more preferably a trivalent organic group containing one or more sulfur atoms (preferably two or three), and a tetravalent organic group containing one or more sulfur atoms (preferably two or three), and even more preferably a trivalent organic group containing a sulfur atom.
• A preferably contains sulfur atoms at a predetermined ratio or more. More specifically, in A, the ratio of the number of sulfur atoms to the total number of sulfur atoms and the number of typical element atoms (excluding sulfur atoms and hydrogen atoms) is, for example, more than 20%, preferably 21% or more, and more preferably 22% or more.
• the ratio of the number of sulfur atoms to the total number of sulfur atoms and the number of typical element atoms (excluding sulfur atoms and hydrogen atoms) is, for example, 80% or less, preferably 50% or less, more preferably 30% or less, and even more preferably 25% or less.
• the ratio of the number of sulfur atoms to the total number of sulfur atoms and the number of typical element atoms (excluding sulfur atoms and hydrogen atoms) is calculated by the following formula.
• a preferred example is a residue obtained by removing a mercapto group from the above-mentioned sulfur-containing trithiol
• a more preferred example is a residue obtained by removing a mercapto group from 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (GST) (GST residue).
• the residue (GST residue) obtained by removing the mercapto group from 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (GST) is shown, for example, in the following formula (2).
• a in the above formula (1) is a GST residue, a cured resin product can be obtained that has particularly excellent refractive index and curability, as well as particularly excellent flexibility.
• the GST residue is an organic group consisting of two sulfur atoms and seven carbon atoms.
• the ratio of the number of sulfur atoms to the total number of sulfur atoms and main group atoms (excluding sulfur and hydrogen atoms) is approximately 22% (2/[2+7] x 100).
• a preferred example is a residue obtained by removing a mercapto group from the above-mentioned sulfur-containing tetrathiol
• a more preferred example is a residue obtained by removing a mercapto group from 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (FSH) (FSH residue).
• the residue (FSH residue) obtained by removing the mercapto group from 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (FSH) is, for example, represented by the following formula (3).
• a in the above formula (1) is an FSH residue, a cured resin product can be obtained that has particularly excellent refractive index and curability, as well as particularly excellent flexibility.
• the FSH residue is an organic group consisting of three sulfur atoms and ten carbon atoms.
• the ratio of the number of sulfur atoms to the total number of sulfur atoms and main group atoms (excluding sulfur and hydrogen atoms) is approximately 23% (3/[3+10] x 100).
• a in the above formula (1) is preferably a GST residue shown in the above formula (2) and an FSH residue shown in the above formula (3), and more preferably a GST residue.
• S represents a sulfur atom.
• X represents a single bond or a carbonyl group.
• the compound represented by the above formula (1) has one or more SXR groups depending on the values of m and n.
• the above formula (1) may contain one X, or may contain multiple (two or more) Xs.
• each X may be the same as each other, or may be different from each other.
• each X is the same as each other.
• R in the formula In the above formula (1) R represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or an araliphatic hydrocarbon group.
• aliphatic hydrocarbon group examples include aliphatic hydrocarbon groups having 1 to 20 carbon atoms. More specific examples of the aliphatic hydrocarbon group include linear aliphatic hydrocarbon groups having 1 to 20 carbon atoms and cyclic aliphatic hydrocarbon groups having 3 to 20 carbon atoms.
• linear aliphatic hydrocarbon groups having 1 to 20 carbon atoms include linear saturated aliphatic hydrocarbon groups having 1 to 20 carbon atoms, and linear unsaturated aliphatic hydrocarbon groups having 1 to 20 carbon atoms.
• linear saturated aliphatic hydrocarbon groups having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, 2-butyl, 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, isopentyl, tert-pentyl, 3-methyl-2-butyl, neopentyl, n-hexyl, 4-methyl-5-butyl, 5-methyl-6-butyl, 5-methyl-7-butyl, 5-methyl-8-butyl, 5-methyl-9-butyl, 5-methyl-1-butyl, isopentyl, tert-pentyl, 3-
• linear unsaturated aliphatic hydrocarbon groups having 1 to 20 carbon atoms include vinyl and 2-propenyl groups. These groups can be used alone or in combination of two or more.
• Examples of cyclic aliphatic hydrocarbon groups having 3 to 20 carbon atoms include cyclic saturated aliphatic hydrocarbon groups having 3 to 20 carbon atoms, and cyclic unsaturated aliphatic hydrocarbon groups having 3 to 20 carbon atoms.
• Examples of cyclic saturated aliphatic hydrocarbon groups having 3 to 20 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl groups.
• Examples of cyclic unsaturated aliphatic hydrocarbon groups having 3 to 20 carbon atoms include cyclopentenyl and cyclohexenyl groups. These can be used alone or in combination of two or more types.
• aromatic hydrocarbon groups include aromatic hydrocarbon groups having 6 to 20 carbon atoms.
• aromatic hydrocarbon groups having 6 to 20 carbon atoms include phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl, 2,3,4-trimethylphenyl, 3,4,5-trimethylphenyl, 2,4,6-trimethylphenyl, 2,3,4,5-tetramethylphenyl, 2,3,4,6-tetramethylphenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 1-naphthyl, and 2-naphthyl groups. These can be used alone or in combination of two or more types.
• aromatic aliphatic hydrocarbon groups include aromatic aliphatic hydrocarbon groups having 7 to 20 carbon atoms.
• aromatic aliphatic hydrocarbon groups having 7 to 20 carbon atoms include benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylpropyl, 2-phenylpropyl, 3-phenylpropyl, o-methylbenzyl, m-methylbenzyl, p-methylbenzyl, o-ethylbenzyl, m-ethylbenzyl, p-ethylbenzyl, o-isopropylbenzyl, m-isopropylbenzyl, p-isopropylbenzyl, 2,3,4-trimethylbenzyl, 3,4,5-trimethylbenzyl, and 2,4,6-trimethylbenzyl. These can be used alone or in combination of two or more types.
• the aliphatic hydrocarbon group, aromatic hydrocarbon group, and araliphatic hydrocarbon group may have a substituent.
• substituents include a halogeno group, a cyano group, an amino group, a carboxy group, a sulfonyl group, and an alkoxy group. These may be used alone or in combination of two or more types.
• the number of substituents is appropriately set depending on the purpose and application.
• the substitution position is appropriately set depending on the purpose and application.
• the compound represented by the above formula (1) has one or more SXR groups depending on the values of m and n.
• the above formula (1) may contain one R or may contain multiple (two or more) R.
• each R may be the same as each other or may be different from each other.
• each R is the same as each other.
• R represents an aliphatic hydrocarbon group
• it is preferably a linear aliphatic hydrocarbon group having 1 to 10 carbon atoms, more preferably a linear aliphatic hydrocarbon group having 1 to 4 carbon atoms, even more preferably a linear aliphatic hydrocarbon group having 1 to 2 carbon atoms, and particularly preferably a methyl group.
• R represents an aromatic hydrocarbon group
• it is preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 8 carbon atoms, and even more preferably a phenyl group.
• R represents an aromatic aliphatic hydrocarbon group
• it is preferably an aromatic aliphatic hydrocarbon group having 7 to 15 carbon atoms, more preferably an aromatic hydrocarbon group having 7 to 10 carbon atoms, and even more preferably a benzyl group or a 2-phenylethyl group.
• X represents a carboxy group and R represents a methyl group, a phenyl group, or a 2-phenylethyl group.
• R' in formula (6) In the above formula (1), R' represents a hydrogen atom or a methyl group. R' constitutes a thio(meth)acryloyl group in the above formula (1).
• R' represents a methyl group
• the compound represented by the above formula (1) has one or more thio(meth)acryloyl groups depending on the values of m and n.
• the above formula (1) may contain one R' or may contain multiple (two or more) R'.
• each R' may be the same as each other or may be different from each other.
• each R' is the same as each other.
• Specific examples of the compound represented by the above formula (1) include, preferably, a compound in which the organic group A in formula (1) is a GST residue, and a compound in which A in formula (1) is an FSH residue. More preferably, the compound represented by the above formula (1) includes a compound in which A in formula (1) is a GST residue.
• Examples of compounds in which the organic group A in formula (1) is a GST residue include compounds represented by the following formula (1-1) and compounds represented by the following formula (1-2).
• the compound represented by the above formula (1-1) is a compound in which m in the above formula (1) is 2 and n is 1.
• the compound represented by the above formula (1-1) may be referred to as a monothio(meth)acryloyl modified form of GST (di-SXR modified form).
• the compound represented by the above formula (1-1) (monothio(meth)acryloyl modified GST) has one thio(meth)acryloyl group. Therefore, the compound represented by the above formula (1-1) forms a linear structure by radical polymerization (described later).
• the compound represented by the above formula (1-1) (monothio(meth)acryloyl modified GST) has two SXR groups. Therefore, the compound represented by the above formula (1-1) can provide a cured resin that has both an excellent refractive index and curability, as well as excellent flexibility.
• the compound represented by the above formula (1-2) is a compound in which m in the above formula (1) is 1 and n is 2.
• the compound represented by the above formula (1-2) may be referred to as a dithio(meth)acryloyl modified form of GST (mono-SXR modified form).
• the compound represented by the above formula (1-2) (dithio(meth)acryloyl modified GST) has two thio(meth)acryloyl groups. Therefore, the compound represented by the above formula (1-2) forms a two-dimensional crosslinked structure by radical polymerization (described later).
• the compound represented by the above formula (1-2) (dithio(meth)acryloyl modified GST) has one SXR group. Therefore, the compound represented by the above formula (1-2) can provide a resin cured product that has both an excellent refractive index and curability, as well as excellent flexibility.
• the compound represented by the above formula (1) can be used alone or in combination of two or more types.
• the compound represented by the above formula (1) is a novel compound having a specific structure. With the above compound, a resin cured product (described below) that has both a refractive index and flexibility can be obtained. Therefore, the compound represented by the above formula (1) is preferably used as a polymerizable compound, as described in detail below.
• Polymerizable Composition (1) Polymerizable Compound
• the polymerizable composition is a raw material composition capable of radical polymerization.
• the polymerizable composition contains a compound capable of radical polymerization (hereinafter, polymerizable compound).
• the compound represented by the above formula (1) (partially thio(meth)acryloyl modified product) can be mentioned.
• the polymerizable composition contains the compound represented by the above formula (1) (partially thio(meth)acryloyl modified product) as the polymerizable compound.
• the polymerizable compound there is a compound represented by the above formula (1) in which the organic group A is a GST residue.
• a preferred polymerizable compound there is also a compound represented by the above formula (1) in which the organic group A is a FSH residue. From the viewpoint of refractive index and flexibility, it is more preferred that the polymerizable compound is a compound represented by the above formula (1) in which the organic group A is a GST residue, which is used alone.
• polymerizable compounds include the compound represented by the above formula (1-1) (monothio(meth)acryloyl modified GST) and the compound represented by the above formula (1-2) (dithio(meth)acryloyl modified GST). These may be used alone or in combination.
• the polymerizable composition preferably contains both a monothio(meth)acryloyl modified GST and a dithio(meth)acryloyl modified GST as polymerizable compounds.
• the content (total amount) of the compound represented by the above formula (1) is appropriately set according to the purpose and application.
• the content ratio (total mass) of the compound represented by the above formula (1) relative to the total amount of the polymerizable composition is, from the viewpoint of flexibility, for example, 1 mass% or more, preferably 10 mass% or more, more preferably 20 mass% or more, even more preferably 40 mass% or more, even more preferably 50 mass% or more, and particularly preferably 60 mass% or more.
• the content ratio (total moles) of the compound represented by the above formula (1) relative to the total amount of the polymerizable composition is, from the viewpoint of flexibility, for example, 100 mass% or less, preferably 99 mass% or less, more preferably 95 mass% or less, even more preferably 90 mass% or less, even more preferably 85 mass% or less, and particularly preferably 80 mass% or less.
• the polymerizable composition contains both a monothio(meth)acryloyl modified GST and a dithio(meth)acryloyl modified GST as the compound represented by the above formula (1), the content ratio of these is appropriately set according to the purpose and application.
• the content ratio of the monothio(meth)acryloyl modified GST relative to the total moles of the polymerizable compounds is, from the viewpoint of flexibility, for example, 0.1 mol % or more, preferably 1 mol % or more.
• the content ratio of the monothio(meth)acryloyl modified GST relative to the total moles of the polymerizable compounds is, from the viewpoint of flexibility, for example, 99 mol % or less, preferably 90 mol % or less.
• the content ratio of the dithio(meth)acryloyl modified GST relative to the total moles of the polymerizable compound is, from the viewpoint of flexibility, for example, 0.1 mol% or more, preferably 1 mol% or more.
• the content ratio of the dithio(meth)acryloyl modified GST relative to the total moles of the polymerizable compound is, from the viewpoint of flexibility, for example, 99 mol% or less, preferably 90 mol% or less.
• the monothio(meth)acryloyl modified GST accounts for, for example, 25 mol% or more, preferably 50 mol% or more, of the total moles of the monothio(meth)acryloyl modified GST and the dithio(meth)acryloyl modified GST, from the viewpoint of flexibility. Furthermore, the monothio(meth)acryloyl modified GST accounts for, for example, less than 100 mol% of the total moles of the monothio(meth)acryloyl modified GST and the dithio(meth)acryloyl modified GST, from the viewpoint of curability.
• the dithio(meth)acryloyl modified GST usually exceeds 0 mol% relative to the total moles of the monothio(meth)acryloyl modified GST and the dithio(meth)acryloyl modified GST.
• the dithio(meth)acryloyl modified GST is, for example, 75 mol% or less, preferably 50 mol% or less, relative to the total moles of the monothio(meth)acryloyl modified GST and the dithio(meth)acryloyl modified GST.
• the molar amount of the dithio(meth)acryloyl modified GST relative to 100 moles of the monothio(meth)acryloyl modified GST is, from the viewpoint of curability, for example, 10 moles or more, preferably 20 moles or more.
• the molar amount of the dithio(meth)acryloyl modified GST relative to 100 moles of the monothio(meth)acryloyl modified GST is, from the viewpoint of flexibility, for example, 50 moles or less, preferably 40 moles or less.
• the average number of (meth)acryloyl groups exceeds, for example, 1.0 from the viewpoint of curability.
• the average number of (meth)acryloyl groups is, for example, less than 1.5, preferably 1.4 or less, and more preferably 1.35 or less, from the viewpoint of flexibility.
• Such a polymerizable composition contains a compound represented by the above formula (1). Therefore, the polymerizable composition can provide a resin cured product that has both an excellent refractive index and curability, as well as excellent flexibility.
• a polymerizable composition containing such a partially thio(meth)acryloyl modified product can be obtained, for example, as a reaction product (reaction product composition) in the production (described later) of the compound represented by the above formula (1).
• the polymerizable composition may contain other polymerizable compounds, as necessary, in addition to the compound represented by the above formula (1) (partially thio(meth)acryloyl-modified compound).
• polymerizable compounds include, for example, compounds in which all of the mercapto groups of a trifunctional or higher sulfur-containing polythiol form thio(meth)acryloyl groups.
• the thio(meth)acryloyl group is bonded (added) to all of the bonds (m+n) of the organic group A in the above formula (1).
• A, S, R', m and n have the same meanings as A, S, R', m and n in formula (1).
• Preferred examples of the compound represented by the above formula (7) include a compound in which the organic group A in formula (7) is a GST residue, and a compound in which the organic group A in formula (7) is an FSH residue.
• the compound represented by the above formula (7) is a compound in which A in formula (7) is a GST residue.
• Examples of such compounds include the compound represented by the following formula (7-1).
• the compound represented by the above formula (7-1) is a compound in which m in the above formula (1) is 0 and n is 3.
• the compound represented by the above formula (7-1) may be referred to as a trithio(meth)acryloyl modified product of GST.
• trithio(meth)acryloyl modified GST is 1,8-bis(meth)acryloylthio-(4-(meth)acryloylthiomethyl-3,6-dithiaoctane) (GST(M)A).
• GST(M)A 1,8-bis(meth)acryloylthio-(4-(meth)acryloylthiomethyl-3,6-dithiaoctane)
• GSTA 1,8-bisacryloylthio-(4-acryloylthiomethyl-3,6-dithiaoctane
• 1,8-bis(meth)acryloylthio-(4-(meth)acryloylthiomethyl-3,6-dithiaoctane) is synthesized, for example, based on the description in JP-A-4-29967.
• Completely thio(meth)acryloyl modified compounds can be used alone or in combination of two or more types.
• a fully thio(meth)acryloyl modified product has three or more (m + n) thio(meth)acryloyl groups. Therefore, a fully thio(meth)acryloyl modified product forms a three-dimensional crosslinked structure by radical polymerization (described below).
• the method for obtaining the complete thio(meth)acryloyl modified product is not particularly limited.
• the complete thio(meth)acryloyl modified product can be obtained as a by-product in the synthesis reaction (described later) of the compound represented by the above formula (1).
• the complete thio(meth)acryloyl modified product can be obtained, for example, in accordance with the method described in JP-A-4-29967.
• the polymerizable composition containing the complete thio(meth)acryloyl modification can be obtained, for example, as a reaction product (reaction product composition) in the production of the compound represented by the above formula (1).
• the content of the completely thio(meth)acryloyl modified product in the polymerizable composition is appropriately set according to the purpose and application.
• the content ratio (total moles) of the completely thio(meth)acryloyl modified compound relative to the total moles of the polymerizable compound is usually 0 mole % or more, preferably 0.1 mole % or more.
• the content ratio (total amount) of the completely thio(meth)acryloyl modified compound relative to the total moles of the polymerizable compound is, for example, 80 mole % or less, preferably 50 mole % or less, more preferably 20 mole % or less.
• the content (total amount) of the compound represented by the above formula (7) (complete thio(meth)acryloyl modified product) relative to a total amount of 100 parts by mass of the compound represented by the above formula (1) (partial thio(meth)acryloyl modified product) is usually 0 parts by mass or more, preferably 0.1 parts by mass or more.
• the content (total amount) of the compound represented by the above formula (7) (complete thio(meth)acryloyl modified product) relative to a total amount of 100 parts by mass of the compound represented by the above formula (1) (partial thio(meth)acryloyl modified product) is, for example, 500 parts by mass or less, preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 20 parts by mass or less.
• the average number of (meth)acryloyl groups exceeds, for example, 1.0 from the viewpoint of curability.
• the average number of (meth)acryloyl groups is, for example, less than 1.5, preferably 1.3 or less, from the viewpoint of flexibility. If the average number of (meth)acryloyl groups is within the above range, a particularly flexible cured resin product can be obtained. Therefore, the cured resin product can be suitably used, in particular, as an adhesive.
• polymerizable compounds include, for example, monofunctional (meth)acrylates and/or polyfunctional (meth)acrylates.
• the polymerizable composition can contain monofunctional (meth)acrylates and/or polyfunctional (meth)acrylates.
• the polymerizable composition preferably contains a monofunctional (meth)acrylate and/or a polyfunctional (meth)acrylate to obtain the desired physical properties depending on the application.
• Monofunctional (meth)acrylates include aromatic ring-containing mono(meth)acrylates and aromatic ring-free mono(meth)acrylates.
• aromatic ring-containing mono(meth)acrylates examples include benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, nonylphenoxyethyl (meth)acrylate, (o-, m- or p-)phenoxybenzyl (meth)acrylate (POB-(M)A), 2-hydroxy-3-phenoxypropyl (meth)acrylate, nonylphenoxyethyl tetrahydrofurfuryl (meth)acrylate, and 1-naphthylmethyl (meth)acrylate. These can be used alone or in combination of two or more.
• Examples of mono(meth)acrylates not containing an aromatic ring include ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate (2EH(M)A), nonyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, hexadecyl (meth)acrylate, octadecyl (meth)acrylate, isoamyl (meth)acrylate, isodecyl (meth)acrylate, isostearyl (meth)acrylate, cyclohexyl (meth)acrylate, and methoxyethyl.
• EH(M)A 2-ethylhexyl (meth)acrylate
• nonyl (meth)acrylate lauryl (meth)acrylate
• tridecyl (meth)acrylate hexadecyl (meth)acryl
• monofunctional (meth)acrylates can be used alone or in combination of two or more.
• monofunctional (meth)acrylate preferred examples include the use of an aromatic ring-containing mono(meth)acrylate alone and the use of a non-aromatic ring-containing mono(meth)acrylate alone.
• an aromatic ring-containing mono(meth)acrylate is used, more preferably, (o, m or p-)phenoxybenzyl (meth)acrylate (POB-(M)A), and even more preferably, (o, m or p-)phenoxybenzyl acrylate (POB-A), and from the viewpoint of flexibility, particularly preferably, o-phenoxybenzyl acrylate is used.
• the monofunctional (meth)acrylate is preferably a mono(meth)acrylate that does not contain an aromatic ring, more preferably 2-ethylhexyl (meth)acrylate (2EH(M)A), and even more preferably 2-ethylhexyl acrylate (2EHA).
• the content of the monofunctional (meth)acrylate in the polymerizable composition is appropriately set depending on the purpose and application.
• the content ratio (total amount) of the monofunctional (meth)acrylate relative to the total moles of the polymerizable compound is, for example, 0 mol% or more, preferably 5 mol% or more. Also, the content ratio (total amount) of the monofunctional (meth)acrylate relative to the total moles of the polymerizable compound is, for example, 80 mol% or less, preferably 50 mol% or less.
• the content ratio (total amount) of the monofunctional (meth)acrylate relative to a total amount of 100 parts by mass of the compound represented by the above formula (1) (partial thio(meth)acryloyl modified product) is, for example, 0 parts by mass or more, and preferably 5 parts by mass or more.
• the content ratio (total amount) of the monofunctional (meth)acrylate relative to a total amount of 100 parts by mass of the compound represented by the above formula (1) (partial thio(meth)acryloyl modified product) is, for example, 500 parts by mass or less, and preferably 200 parts by mass or less.
• polyfunctional (meth)acrylates examples include bifunctional (meth)acrylates and trifunctional or higher (meth)acrylates.
• bifunctional (meth)acrylates include 1,4-butanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and tris(2-hydroxyethyl
• trifunctional or higher (meth)acrylates examples include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and dipentaerythritol-poly(meth)acrylate. These can be used alone or in combination of two or more types.
• polyfunctional (meth)acrylates can be used alone or in combination of two or more types.
• the content of the polyfunctional (meth)acrylate in the polymerizable composition is set appropriately depending on the purpose and application.
• the content ratio (total amount) of the polyfunctional (meth)acrylate relative to the total moles of the polymerizable compound is, for example, 0 mol% or more, preferably 3 mol% or more. Also, the content ratio (total amount) of the polyfunctional (meth)acrylate relative to the total moles of the polymerizable compound is, for example, 50 mol% or less, preferably 20 mol% or less.
• the content ratio (total amount) of the polyfunctional (meth)acrylate relative to a total amount of 100 parts by mass of the compound represented by the above formula (1) (partially thio(meth)acryloyl modified product) is, for example, 0 parts by mass or more, and preferably 3 parts by mass or more.
• the content ratio (total amount) of the polyfunctional (meth)acrylate relative to a total amount of 100 parts by mass of the compound represented by the above formula (1) (partially thio(meth)acryloyl modified product) is, for example, 100 parts by mass or less, and preferably 50 parts by mass or less.
• polymerizable compounds include, for example, styrene, ⁇ -methylstyrene, vinyltoluene, vinylbiphenyl, and divinylbenzene. These can be used alone or in combination of two or more. The content ratio of these is set appropriately depending on the purpose and application.
• the other polymerizable compounds can be used alone or in combination of two or more kinds.
• Preferred examples of the other polymerizable compounds include fully thio(meth)acryloyl modified compounds and monofunctional (meth)acrylates.
• the other polymerizable compounds are preferably fully thio(meth)acryloyl modified compounds.
• the other polymerizable compounds are preferably monofunctional (meth)acrylates (excluding methyl methacrylate).
• the content ratio of the other polymerizable compounds is appropriately set depending on the purpose and application.
• the content ratio (total amount) of the other polymerizable compounds relative to the total moles of the polymerizable compounds is, for example, 0 mol% or more, preferably 5 mol% or more.
• the content ratio (total amount) of the other polymerizable compounds relative to the total moles of the polymerizable compounds is, for example, 80 mol% or less, preferably 50 mol% or less.
• the content ratio (total amount) of the other polymerizable compounds relative to a total of 100 parts by mass of the compound represented by the above formula (1) (partially thio(meth)acryloyl modified product) is, for example, 0 parts by mass or more, and preferably 5 parts by mass or more.
• the content ratio (total amount) of the other polymerizable compounds relative to a total of 100 parts by mass of the compound represented by the above formula (1) (partially thio(meth)acryloyl modified product) is, for example, 500 parts by mass or less, and preferably 200 parts by mass or less.
• the polymerizable composition may contain additives as components that do not undergo radical polymerization, if necessary.
• additives include plasticizers, radical polymerization initiators, crosslinking agents, silane coupling agents, defoamers, leveling agents, mildew inhibitors, rust inhibitors, matting agents, flame retardants, thixotropic agents, tackifiers, thickeners, lubricants, antistatic agents, surfactants, reaction retarders, antioxidants, UV absorbers, hydrolysis inhibitors, weather stabilizers, heat stabilizers, dyes, inorganic pigments, organic pigments, tack inhibitors, inorganic fillers, and organic fillers. These may be used alone or in combination of two or more. The amount and timing of addition of the additives may be appropriately set according to the purpose and application.
• the additive preferably includes a plasticizer. That is, the polymerizable composition preferably includes a plasticizer.
• plasticizer is a compound in which all of the mercapto groups of a trifunctional or higher sulfur-containing polythiol form SXR groups.
• the thio(meth)acryloyl group is not bonded (added) to any of the bonds of the organic group A in the above formula (1), and the SXR group is bonded (added) to all (m+n) of the bonds of the organic group A in the above formula (1).
• the compound represented by the above formula (4) is a compound in which the organic group A in formula (4) is a GST residue, and a compound in which the organic group A in formula (4) is an FSH residue. More preferably, the compound represented by the above formula (4) is a compound in which the organic group A in formula (4) is a GST residue. Examples of such compounds include the compound represented by the following formula (4-1).
• the compound represented by the above formula (4-1) is a compound in which m is 3 and n is 0 in the above formula (1).
• the compound represented by the above formula (4-1) may be referred to as an unmodified thio(meth)acryloyl form of GST.
• Examples of unmodified thio(meth)acryloyl GST include 4-benzylthiomethyl-1,8-bisbenzylthio-3,6-dithiaoctane (Bn-GST), 4-benzoylthiomethyl-1,8-bisbenzoylthio-3,6-dithiaoctane (Bz-GST), and 4-acetylthiomethyl-1,8-bisacetylthio-3,6-dithiaoctane (Ac-GST).
• Bn-GST 4-benzylthiomethyl-1,8-bisbenzylthio-3,6-dithiaoctane
• Bz-GST 4-benzoylthiomethyl-1,8-bisbenzoylthio-3,6-dithiaoctane
• Ac-GST 4-acetylthiomethyl-1,8-bisacetylthio-3,6-dithiaoctane
• unmodified thio(meth)acryloyl GST examples include 4-(3-phenylpropionyl)thiomethyl-1,8-bis(3-phenylpropionyl)thio-3,6-dithiaoctane (PP-GST), and 4-phenylacetylthiomethyl-1,8-bisphenylacetylthio-3,6-dithiaoctane (PA-GST).
• Thio(meth)acryloyl unmodified compounds can be used alone or in combination of two or more types.
• Thio(meth)acryloyl unmodified has three or more (m+n) SXR groups. Therefore, thio(meth)acryloyl unmodified is used as a plasticizer that does not undergo radical polymerization.
• the method for obtaining the unmodified thio(meth)acryloyl compound is not particularly limited.
• the unmodified thio(meth)acryloyl compound can be obtained as a by-product in the synthesis reaction (described below) of the compound represented by the above formula (1).
• the polymerizable composition containing the unmodified thio(meth)acryloyl compound can be obtained, for example, as a reaction product (reaction product composition) in the production of the compound represented by formula (1) above.
• plasticizers can also be used.
• known plasticizers include benzoate esters, phthalate esters, terephthalate esters, isophthalate esters, adipate esters, sebacate esters, trimellitate esters, pyromellitate esters, phosphate esters, epoxy esters, glycol esters, and waxes. These can be used alone or in combination of two or more types.
• an unmodified thio(meth)acryloyl compound can be used. If the plasticizer contains an unmodified thio(meth)acryloyl compound, the plasticizer can improve the flexibility of the cured resin (described below) and can suppress a decrease in the refractive index of the cured resin (described below) or can improve the refractive index.
• the content of the plasticizer (preferably unmodified thio(meth)acryloyl) in the polymerizable composition is appropriately set according to the purpose and application.
• the content ratio of the plasticizer (preferably, thio(meth)acryloyl unmodified) relative to the total moles of the polymerizable compound is, for example, 0 mol% or more, preferably 5 mol% or more.
• the content ratio of the plasticizer (preferably, thio(meth)acryloyl unmodified) relative to the total moles of the polymerizable compound is, for example, 80 mol% or less, preferably 50 mol% or less.
• the content of the plasticizer (preferably, thio(meth)acryloyl unmodified) relative to a total of 100 parts by mass of the compound represented by the above formula (1) (partially thio(meth)acryloyl modified product) is, for example, 0 parts by mass or more, preferably 5 parts by mass or more.
• the content of the plasticizer (preferably, thio(meth)acryloyl unmodified product) relative to a total of 100 parts by mass of the compound represented by the above formula (1) (partially thio(meth)acryloyl modified product) is, for example, 500 parts by mass or less, preferably 50 parts by mass or less.
• the above polymerizable composition is suitable for use in various industrial fields. Therefore, the above polymerizable composition (uncured resin) is suitable for use as an optical polymerizable composition.
• An example of an application of the polymerizable composition is an adhesive.
• An adhesive is an uncured resin composition that hardens to form a cured adhesive (a cured resin product, described below).
• the cured adhesive adheres to an adherend.
• adherend There are no particular limitations on the adherend to which the adhesive can be applied, but examples include paper, cloth, leather, resin sheets, rubber sheets, foams, metal foils, glass, and wood.
• Such an adhesive contains the above-mentioned polymerizable composition.
• the above-mentioned adhesive produces a resin cured product that has an excellent refractive index and excellent flexibility. Therefore, the above-mentioned adhesive is suitable for use as an optical adhesive.
• the use of the polymerizable composition is not limited to adhesives.
• polymerizable compositions include, for example, coating agents and paints, preferably optical coating agents and optical paints.
• polymerizable compositions include materials for molded products and adhesive materials, preferably materials for optical molded products and adhesive materials for optical products.
• the polythiol may be the above-mentioned sulfur-containing polythiol having three or more functionalities. That is, the polythiol is a polythiol containing a sulfur atom and having a valence of m+n (m+n is an integer of 3 or more).
• examples of polythiols include the above-mentioned sulfur-containing trithiol, sulfur-containing tetrathiol, sulfur-containing pentathiol, sulfur-containing hexathiol, and sulfur-containing octathiol. From the viewpoints of availability and reactivity, the above-mentioned sulfur-containing trithiol and sulfur-containing tetrathiol are preferable as polythiols.
• 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane is more preferred as a sulfur-containing trithiol.
• 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (GST) is, for example, represented by the following formula (5).
• 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane is more preferred as a sulfur-containing tetrathiol.
• 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (FSH) is, for example, represented by the following formula (6).
• the polythiol can be used alone or in combination of two or more kinds.
• the polythiol is preferably used alone.
• the polythiol preferably, the polythiol represented by the above formula (5) is used alone, and the polythiol represented by the above formula (6) is used alone.
• the polythiol is more preferably represented by the above formula (5) or (6).
• the polythiol is preferably a sulfur-containing trithiol, and particularly preferably a polythiol represented by the above formula (5) (4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (GST)).
• the first modifier is a compound that caps the molecular terminals of the polythiol and does not form a (meth)acryloyl group.
• the first modifier is a compound that modifies the mercapto group of the sulfur-containing polythiol having three or more functional groups to an SXR group.
• An example of the first denaturant is a compound represented by the following formula (8).
• X and R have the same meanings as X and R in formula (1).
• Y represents a halogen or a hydroxyl group.
• halogen include fluorine, chlorine, bromine, and iodine.
• Preferred examples of halogen include chlorine and bromine.
• examples of the first modifying agent include halogenated hydrocarbons.
• examples of the first modifying agent include alkyl halides, aryl halides, and aralkyl halides.
• alkyl halides include methyl fluoride, methyl chloride, methyl bromide, methyl iodide, ethyl fluoride, ethyl chloride, ethyl bromide, and ethyl iodide.
• examples of the aryl halides include phenyl fluoride, phenyl chloride, phenyl bromide, and phenyl iodide.
• aralkyl halides examples include benzyl fluoride, benzyl chloride, benzyl bromide (benzyl bromide), and benzyl iodide. These are used alone or in combination of two or more.
• an aralkyl halide is used, and more preferably, benzyl bromide (benzyl bromide).
• the first modifying agent when Y is a halogen and X is a carbonyl group, the first modifying agent may be an acyl halide.
• acyl halide include acetyl fluoride, acetyl chloride, acetyl bromide, acetyl iodide, benzoyl fluoride, benzoyl chloride, phenylacetyl chloride (phenylacetyl chloride), phenylpropionyl chloride (phenylpropionyl chloride), benzoyl bromide, and benzoyl iodide. These may be used alone or in combination of two or more.
• Preferred examples of the first modifying agent include benzoyl chloride, phenylacetyl chloride (phenylacetyl chloride), and phenylpropionyl chloride (phenylpropionyl chloride).
• the first modifier when Y is a hydroxyl group and X is a carbonyl group, the first modifier may be a carboxylic acid.
• carboxylic acid include monocarboxylic acids and their anhydrides.
• monocarboxylic acid include aliphatic monocarboxylic acids, aromatic monocarboxylic acids, and araliphatic monocarboxylic acids.
• aliphatic monocarboxylic acids examples include acetic acid, propionic acid, butyric acid, caproic acid, octylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, 2-ethylhexanoic acid, cyclohexane carboxylic acid, and cyclopentane carboxylic acid.
• aromatic monocarboxylic acids examples include benzoic acid and toluic acid.
• araliphatic monocarboxylic acids examples include diphenylacetic acid. These may be used alone or in combination of two or more.
• aliphatic monocarboxylic acids and their anhydrides may be used, more preferably, acetic acid and its anhydrides may be used, and even more preferably, acetic anhydride may be used.
• the second modifier is a compound that caps the molecular terminals of the polythiol to form (meth)acryloyl groups.
• the second modifier is a compound that modifies the mercapto groups of the sulfur-containing polythiol having three or more functional groups to thio(meth)acryloyl groups.
• Examples of the second modifying agent include (meth)acrylic acid halides and (meth)acrylic acid anhydrides.
• Examples of the (meth)acrylic acid halides include (meth)acrylic acid chloride, (meth)acrylic acid bromide, and (meth)acrylic acid iodide.
• Examples of the (meth)acrylic acid anhydrides include acrylic acid anhydride and methacrylic acid anhydride. These can be used alone or in combination of two or more types.
• two or more types of compounds can be used in combination as the second modifier in such a way that they can form a (meth)acryloyl group.
• the second modifying agent may contain, for example, (meth)acrylic acid and a dehydrating condensing agent.
• the dehydrating condensing agent include imidazole-based condensing agents, triazine-based condensing agents, phosphonium-based condensing agents, uronium-based condensing agents, and haluronium-based condensing agents. These may be used alone or in combination of two or more types.
• the second denaturant may contain, for example, a propionic acid derivative and a base compound.
• the propionic acid derivative include the propionic acid derivatives described in JP-A-4-29967. More specifically, examples of the propionic acid derivative include ⁇ -chloropropionic acid, ⁇ -bromopropionic acid, ⁇ -hydroxypropionic acid toluenesulfonyl ester, ⁇ -hydroxypropionic acid benzenesulfonyl ester, ⁇ -hydroxypropionic acid methanesulfonyl ester, ⁇ -methyl- ⁇ -chloropropionic acid, ⁇ -methyl- ⁇ -bromopropionic acid, ⁇ -methyl- ⁇ -hydroxypropionic acid toluenesulfonyl ester, ⁇ -methyl- ⁇ -hydroxypropionic acid benzenesulfonyl ester, ⁇ -methyl- ⁇ -hydroxypropionic acid methanesulfonyl ester, and
• examples of acid halides include ⁇ -chloropropionic acid chloride (3-chloropropionic acid chloride), ⁇ -bromopropionic acid chloride, ⁇ -methyl- ⁇ -chloropropionic acid chloride, and ⁇ -methyl- ⁇ -bromopropionic acid chloride. These can be used alone or in combination of two or more.
• bases include sodium hydroxide, potassium hydroxide, triethylamine, and pyridine. These can be used alone or in combination of two or more.
• the above-mentioned tri- or higher functional sulfur-containing polythiol (polythiol containing sulfur atoms and having m+n valences (m+n is an integer of 3 or more)) is prepared (preparation step).
• the order of reaction of the first and second modifiers is not particularly limited.
• a sulfur-containing polythiol having three or more functionalities may be reacted with the first and second modifiers at the same time.
• a sulfur-containing polythiol having three or more functionalities may be reacted with the first modifier first, and then the reaction product of these may be reacted with the second modifier.
• a sulfur-containing polythiol having three or more functionalities may be reacted with the second modifier first, and then the reaction product of these may be reacted with the first modifier.
• a trifunctional or higher sulfur-containing polythiol is first modified with a first modifying agent to add SXR groups. Then, these reaction products are modified with a second modifying agent to add thio(meth)acryloyl groups.
• reaction step the above-mentioned tri- or higher functional sulfur-containing polythiol is first reacted with the above-mentioned first modifier by an appropriate method (first reaction step).
• the compounding formulation, reaction method, and reaction conditions in the first reaction step are appropriately selected depending on, for example, the type of the first modifier.
• Examples of reactions between a trifunctional or higher sulfur-containing polythiol and a first modifier include nucleophilic substitution reactions, nucleophilic acylation reactions, cross-coupling reactions, and dehydration condensation reactions.
• the sulfur-containing polythiol having three or more functionalities and the first modifier undergo a nucleophilic substitution reaction in the presence of a known basic compound to produce a compound represented by the above formula (1).
• the basic compound eliminates protons from the sulfur-containing polythiol having three or more functionalities to produce a nucleophile.
• the nucleophile derived from the sulfur-containing polythiol having three or more functionalities and the halogenated hydrocarbon undergo a nucleophilic substitution reaction.
• Examples of basic compounds include metal alcoholates and amine compounds.
• the blending ratio of the sulfur-containing polythiol having three or more functionalities and the first modifier is adjusted based on the equivalent ratio of halogen atoms in the first modifier (halogenated hydrocarbon) to mercapto groups in the sulfur-containing polythiol.
• the equivalent ratio (halogen atom/mercapto group) of the halogen atoms in the first modifier (halogenated hydrocarbon) to the mercapto groups in the sulfur-containing polythiol is, for example, 0.1 or more, preferably 0.3 or more.
• the equivalent ratio (halogen atom/mercapto group) of the halogen atoms in the first modifier (halogenated hydrocarbon) to the mercapto groups in the sulfur-containing polythiol is, for example, 0.9 or less, preferably 0.8 or less.
• the reaction conditions for the nucleophilic substitution reaction are appropriately selected depending on the type of tri- or higher functional sulfur-containing polythiol and the type of the first modifying agent.
• the reaction temperature is, for example, -20°C or higher, preferably -10°C or higher.
• the reaction temperature is, for example, 50°C or lower, preferably 30°C or lower.
• the reaction time is, for example, 3 hours or higher, preferably 6 hours or higher.
• the reaction time is, for example, 48 hours or lower, preferably 24 hours or lower.
• the sulfur-containing polythiol having three or more functional groups and the first modifying agent may react in the absence of a solvent, or may react in the presence of a known solvent.
• the type and amount of the solvent are appropriately set.
• the sulfur-containing polythiol having three or more functional groups and the first modifying agent may react in the absence of a catalyst, or may react in the presence of a known catalyst.
• the type and amount of the catalyst are appropriately set.
• the trifunctional or higher sulfur-containing polythiol and the first modifying agent undergo a nucleophilic acylation reaction in the presence of the basic compound described above to produce a compound represented by the above formula (1).
• the basic compound causes the proton of the trifunctional or higher sulfur-containing polythiol to be eliminated to produce a nucleophile.
• the nucleophile derived from the trifunctional or higher sulfur-containing polythiol and the acyl halide undergo a nucleophilic acylation reaction.
• the blending ratio of the trifunctional or higher sulfur-containing polythiol and the first modifying agent is adjusted based on the equivalent ratio of the halogen atoms in the first modifying agent (acyl halide) to the mercapto groups in the sulfur-containing polythiol.
• the equivalent ratio (halogen atom/mercapto group) of the halogen atoms in the first modifying agent (acyl halide) to the mercapto groups in the sulfur-containing polythiol is, for example, 0.1 or more, preferably 0.3 or more.
• the equivalent ratio (halogen atom/mercapto group) of the halogen atoms in the first modifying agent (acyl halide) to the mercapto groups in the sulfur-containing polythiol is, for example, 0.9 or less, preferably 0.8 or less.
• the reaction conditions for the nucleophilic acylation reaction are appropriately selected depending on the type of sulfur-containing polythiol having three or more functionalities and the type of the first modifying agent.
• the reaction temperature is, for example, -20°C or higher, preferably -10°C or higher.
• the reaction temperature is, for example, 50°C or lower, preferably 30°C or lower.
• the reaction time is, for example, 3 hours or more, preferably 6 hours or more.
• the reaction time is, for example, 48 hours or less, preferably 24 hours or less.
• the sulfur-containing polythiol having three or more functionalities and the first modifying agent may react without a solvent or may react with a known solvent.
• the type and amount of the solvent are appropriately set.
• the sulfur-containing polythiol having three or more functionalities and the first modifying agent may react without a catalyst or may react with a known catalyst.
• the type and amount of the catalyst are appropriately set.
• the sulfur-containing polythiol having three or more functionalities and the first modifier undergo a dehydration condensation reaction in the presence of the basic compound to produce a compound represented by the above formula (1).
• the blending ratio of the sulfur-containing polythiol having three or more functionalities and the first modifier is adjusted based on the equivalent ratio of the carboxyl group in the first modifier (carboxylic acid) to the mercapto group in the sulfur-containing polythiol.
• the equivalent ratio (carboxyl group/mercapto group) of the carboxyl group in the first modifier (carboxylic acid) to the mercapto group in the sulfur-containing polythiol is, for example, 0.1 or more, preferably 0.5 or more.
• the equivalent ratio (carboxyl group/mercapto group) of the carboxyl group in the first modifier (carboxylic acid) to the mercapto group in the sulfur-containing polythiol is, for example, 0.9 or less, preferably 0.8 or less.
• the reaction conditions for the dehydration condensation reaction are appropriately selected depending on the type of sulfur-containing polythiol having three or more functionalities and the type of the first modifier.
• the reaction temperature is, for example, -20°C or higher, preferably -10°C or higher.
• the reaction temperature is, for example, 50°C or lower, preferably 30°C or lower.
• the reaction time is, for example, 3 hours or more, preferably 6 hours or more.
• the reaction time is, for example, 48 hours or less, preferably 24 hours or less.
• the sulfur-containing polythiol having three or more functionalities and the first modifier may react without a solvent or may react with a known solvent.
• the type and amount of the solvent are appropriately set.
• the sulfur-containing polythiol having three or more functionalities and the first modifier may react without a catalyst or may react with a known catalyst.
• the type and amount of the catalyst are appropriately set.
• the first reaction step at least a portion of the mercapto groups (SH groups) of the polythiol are modified by the first modifying agent to form SXR groups. Furthermore, the remainder of the mercapto groups (SH groups) of the polythiol (hereinafter, the remaining mercapto groups) remain without being modified. This results in a primary reaction product.
• the primary reaction product is the reaction product in the first reaction step.
• reaction product from the first reaction step (primary reaction product) is reacted with the second modifier by an appropriate method (second reaction step).
• the compounding formulation, reaction method, and reaction conditions in the second reaction step are appropriately selected depending on, for example, the type of second modifier.
• the second modifying agent contains a (meth)acrylic acid halide
• the remaining mercapto groups of the primary reaction product undergo a condensation reaction with the halogen atoms of the (meth)acrylic acid halide. This results in the formation of thio(meth)acryloyl groups.
• the blending ratio of the second modifying agent is adjusted based on the equivalent ratio of the halogen atoms in the second modifying agent ((meth)acrylic acid halide) to the remaining mercapto groups of the primary reaction product.
• the equivalent ratio (halogen atom/residual mercapto group) of the halogen atom in the second modifying agent ((meth)acrylic acid halide) to the residual mercapto group in the primary reaction product is, for example, 0.8 or more, preferably 0.9 or more.
• the equivalent ratio (halogen atom/residual mercapto group) of the halogen atom in the second modifying agent ((meth)acrylic acid halide) to the residual mercapto group in the primary reaction product is, for example, 1.5 or less, preferably 1.3 or less.
• the reaction conditions are appropriately selected according to the type of trifunctional or higher sulfur-containing polythiol, the type of first modifier, and the type of second modifier.
• the primary reaction product and the second modifier may react in the absence of a solvent or in the presence of a known solvent.
• the type and amount of the solvent are appropriately set.
• the primary reaction product and the second modifier may react in the absence of a catalyst or in the presence of a known catalyst.
• the type and amount of the catalyst are appropriately set.
• the second modifier contains (meth)acrylic anhydride
• the remaining mercapto groups of the primary reaction product undergo a condensation reaction with the (meth)acrylic anhydride by a known method. This results in the formation of thio(meth)acryloyl groups.
• the blending ratio of the second modifier is adjusted based on the equivalent ratio of the second modifier ((meth)acrylic anhydride) to the remaining mercapto groups of the primary reaction product.
• the equivalent ratio ((meth)acrylic anhydride) of the second modifying agent to the residual mercapto groups of the primary reaction product ((meth)acrylic anhydride/residual mercapto groups) is, for example, 0.8 or more, preferably 0.9 or more.
• the equivalent ratio ((meth)acrylic anhydride/residual mercapto groups) of the second modifying agent to the residual mercapto groups of the primary reaction product is, for example, 1.5 or less, preferably 1.3 or less.
• the reaction conditions are appropriately selected according to the type of trifunctional or higher sulfur-containing polythiol, the type of first modifier, and the type of second modifier.
• the primary reaction product and the second modifier may react in the absence of a solvent or in the presence of a known solvent.
• the type and amount of the solvent are appropriately set.
• the primary reaction product and the second modifier may react in the absence of a catalyst or in the presence of a known catalyst.
• the type and amount of the catalyst are appropriately set.
• the second modifier contains (meth)acrylic anhydride
• the remaining mercapto groups of the primary reaction product undergo a condensation reaction with the (meth)acrylic anhydride by a known method.
• the blending ratio of the second modifier is adjusted based on the equivalent ratio of the second modifier ((meth)acrylic anhydride) to the remaining mercapto groups of the primary reaction product.
• the equivalent ratio ((meth)acrylic anhydride) of the second modifying agent to the residual mercapto groups of the primary reaction product ((meth)acrylic anhydride/residual mercapto groups) is, for example, 0.8 or more, preferably 0.9 or more.
• the equivalent ratio ((meth)acrylic anhydride/residual mercapto groups) of the second modifying agent to the residual mercapto groups of the primary reaction product is, for example, 1.5 or less, preferably 1.3 or less.
• the reaction conditions are appropriately selected depending on the type of trifunctional or higher sulfur-containing polythiol, the type of first modifier, and the type of second modifier.
• the primary reaction product and the second modifier may react in the absence of a solvent or in the presence of a known solvent.
• the type and amount of the solvent are appropriately set.
• the primary reaction product and the second modifier may react in the absence of a catalyst or in the presence of a known catalyst.
• the type and amount of the catalyst are appropriately set.
• the second modifier contains (meth)acrylic acid and a dehydrating condensing agent
• the residual mercapto groups of the primary reaction product undergo a condensation reaction with (meth)acrylic acid in the presence of the dehydrating condensing agent. This results in the formation of thio(meth)acryloyl groups.
• the blending ratio of the second modifier is adjusted based on the equivalent ratio of (meth)acrylic acid in the second modifier to the residual mercapto groups of the primary reaction product.
• the equivalent ratio of (meth)acrylic acid in the second modifying agent to the residual mercapto groups of the primary reaction product ((meth)acrylic acid/residual mercapto groups) is, for example, 0.8 or more, preferably 0.9 or more.
• the equivalent ratio of (meth)acrylic acid in the second modifying agent to the residual mercapto groups of the primary reaction product ((meth)acrylic acid/residual mercapto groups) is, for example, 1.5 or less, preferably 1.3 or less.
• the reaction conditions are appropriately selected according to the type of trifunctional or higher sulfur-containing polythiol, the type of first modifier, and the type of second modifier.
• the primary reaction product and the second modifier may react in the absence of a solvent or in the presence of a known solvent.
• the type and amount of the solvent are appropriately set.
• the primary reaction product and the second modifier may react in the absence of a catalyst or in the presence of a known catalyst.
• the type and amount of the catalyst are appropriately set.
• the second modifier contains a propionic acid derivative and a base compound
• the remaining mercapto groups of the primary reaction product react with the propionic acid derivative and the base compound in accordance with the method described in JP-A-4-29967. More specifically, first, the remaining mercapto groups of the primary reaction product undergo a condensation reaction with the propionic acid derivative. Next, the halogens of these reaction products (condensates) are treated (elimination treatment) with the base compound to form ethylenically unsaturated bonds. This results in the formation of thio(meth)acryloyl groups. In such a reaction, the blending ratio of the second modifier is adjusted based on the equivalent ratio of the propionic acid derivative in the second modifier to the remaining mercapto groups of the primary reaction product.
• the equivalent ratio of the propionic acid derivative in the second modifying agent to the residual mercapto groups of the primary reaction product is, for example, 0.8 or more, preferably 0.9 or more.
• the equivalent ratio of the propionic acid derivative in the second modifying agent to the residual mercapto groups of the primary reaction product is, for example, 1.5 or less, preferably 1.3 or less.
• the reaction conditions are appropriately selected according to the type of trifunctional or higher sulfur-containing polythiol, the type of first modifier, and the type of second modifier.
• the primary reaction product and the second modifier may react in the absence of a solvent or in the presence of a known solvent.
• the type and amount of the solvent are appropriately set.
• the primary reaction product and the second modifier may react in the absence of a catalyst or in the presence of a known catalyst.
• the type and amount of the catalyst are appropriately set.
• the remaining mercapto groups in the primary reaction product are modified to form thio(meth)acryloyl groups. This results in a secondary reaction product.
• the secondary reaction product is the reaction product in the second reaction step.
• some of the mercapto groups of the trifunctional or higher sulfur-containing polythiol are modified by the first modifying agent. This causes the SXR group to bond to the residue (organic group A) of the trifunctional or higher sulfur-containing polythiol.
• the remainder of a portion of the mercapto groups of the trifunctional or higher sulfur-containing polythiol is modified with the second modifying agent.
• a thio(meth)acryloyl group is bonded to the residue (organic group A) of the trifunctional or higher sulfur-containing polythiol.
• the compound represented by formula (1) above (partially thio(meth)acryloyl modified product) is formed by the above method.
• reaction product of the tri- or higher functional sulfur-containing polythiol, the first modifier, and the second modifier contains the compound represented by the above formula (1) (partially thio(meth)acryloyl modified product).
• reaction product of the tri- or higher functional sulfur-containing polythiol, the first modifier, and the second modifier is a polymerizable composition.
• the content of the compound represented by the above formula (1) (partially thio(meth)acryloyl modified product) in the reaction product (polymerizable composition) is, for example, within the above range. If necessary, the reaction product can be purified by an appropriate method to adjust the content of the compound represented by the above formula (1) (partially thio(meth)acryloyl modified product) to within the above range.
• a completely thio(meth)acryloyl modified product may be formed as a by-product.
• the above reaction product polymerizable composition
• the content of the completely thio(meth)acryloyl modified product in the reaction product (polymerizable composition) is, for example, within the above range. If necessary, the reaction product can be purified by an appropriate method to adjust the content of the completely thio(meth)acryloyl modified product to within the above range.
• an unmodified thio(meth)acryloyl compound may be formed as a by-product.
• the above reaction product (polymerizable composition) contains the unmodified thio(meth)acryloyl compound as a plasticizer.
• the content of the unmodified thio(meth)acryloyl in the reaction product (polymerizable composition) is, for example, within the above range. If necessary, the content of the unmodified thio(meth)acryloyl can be adjusted to within the above range by purifying the reaction product using an appropriate method.
• the first and second modifiers and the method of reacting them are not limited to those mentioned above.
• an ene-thiol reaction can be mentioned as a reaction between a sulfur-containing polythiol having three or more functionalities and the first modifier.
• an example of the first modifier is a compound capable of undergoing an ene-thiol reaction with the above-mentioned sulfur-containing polythiol having three or more functionalities.
• examples of such compounds include vinyl compounds. Examples of vinyl compounds include styrene, methylstyrene, and butylstyrene. These can be used alone or in combination of two or more types.
• the sulfur-containing polythiol having three or more functionalities and the first modifier undergo an ene-thiol reaction in the presence of a known radical initiator, modifying the mercapto group of the sulfur-containing polythiol having three or more functionalities to an SXR group, where X is a single bond and R is a hydrocarbon group derived from the vinyl compound.
• the cured resin is formed by curing the above-mentioned polymerizable composition by a known method. That is, the cured resin includes a cured product of the above-mentioned polymerizable composition, and preferably consists of a cured product of the above-mentioned polymerizable composition.
• a polymerizable composition having a desired shape is irradiated with active energy rays and/or a polymerizable composition having a desired shape is heated.
• Examples of active energy rays include ultraviolet rays and electron beams.
• the wavelength of the active energy rays is appropriately set according to the purpose and use.
• the integrated light amount is, for example, 0.1 mJ/ cm2 or more.
• the integrated light amount is, for example, 5000 mJ/ cm2 or less, preferably 3000 mJ/ cm2 or less.
• the illuminance is, for example, 0.01 mW/ cm2 or more.
• the illuminance is, for example, 500 mW/ cm2 or less, preferably 300 mW/ cm2 or less.
• the heating conditions are set appropriately depending on the purpose and application.
• the heating temperature is, for example, 40°C or higher, preferably 50°C or higher.
• the heating temperature is, for example, 200°C or lower, preferably 100°C or lower.
• the heating time is, for example, 1 minute or longer, preferably 5 minutes or longer.
• the heating time is, for example, 10 hours or shorter, preferably 5 hours or shorter.
• the polymerizable composition can undergo radical polymerization (photoradical polymerization and/or thermal radical polymerization).
• the polymerizable composition can be cured by active energy rays and/or heat.
• a resin cured product (a cured product of the polymerizable composition) is obtained.
• the method for obtaining the cured resin is not limited to the above.
• the above polymerizable composition can be used to prepare a two-component curing resin composition. More specifically, the above polymerizable composition is reacted with a hydroxyl group-containing (meth)acrylate to prepare an acrylic polyol. Then, the acrylic polyol (base) is reacted with a known curing agent (e.g., polyisocyanate) and cured. As a result, the above cured resin is obtained.
• a known curing agent e.g., polyisocyanate
• the cured resin contains the cured product of the polymerizable composition.
• the polymerizable composition contains the compound. Therefore, the cured resin has both an excellent refractive index and excellent flexibility.
• the refractive index of the cured resin is relatively high.
• the refractive index of the cured resin is, for example, 1.45 or more, preferably 1.50 or more, more preferably 1.55 or more, even more preferably 1.60 or more, and particularly preferably 1.61 or more.
• the refractive index of the cured resin is, for example, 1.80 or less, preferably 1.70 or less. The refractive index is measured in accordance with the examples described later.
• the tensile storage modulus (E') of the cured resin at 25°C is relatively low.
• the tensile storage modulus (E') of the cured resin at 25°C is, for example, 2000 MPa or less, preferably 1000 MPa or less, more preferably 500 MPa or less, even more preferably 100 MPa or less, even more preferably 50 MPa or less, even more preferably 10 MPa or less, and particularly preferably 5 MPa or less.
• the tensile storage modulus (E') of the cured resin at 25°C is, for example, 1 MPa or more.
• the tensile storage modulus (E') is measured in accordance with the examples described later.
• the above-mentioned resin cured product (cured product of the polymerizable composition) is suitable for use in various industrial fields.
• examples of uses of the resin cured product include molded products (resin molded products) and adhesives.
• a preferred use of the resin cured product is as an adhesive.
• the molded article can be obtained by curing the polymerizable composition into any shape. There are no particular limitations on the shape of the molded article (resin molded article). Examples of molded articles include lenses, films, sheets, and boards, and preferably, lenses and films.
• An adhesive is a hardened polymerizable composition. It has a relatively low glass transition temperature (0°C or less) and is sticky (tacky).
• the substrate to which the adhesive can be applied examples include paper, cloth, leather, resin sheets, rubber sheets, foams, metal foils, glass, and wood.
• the above-mentioned resin cured products, molded articles, films and adhesives have both an excellent refractive index and excellent flexibility.
• the above-mentioned resin cured product, molded product, film, and adhesive are preferably used in the optical field. More specifically, the above-mentioned resin cured product is preferably used as an optical resin cured product. Fields in which the above-mentioned resin cured product is used include, for example, optically transparent adhesives, coating agents for optical elements, adhesives for film-like thin glass, protective films for film-like thin glass, polarizing films for liquid crystal display devices, and polarizing films for organic EL display devices.
• the above-mentioned molded product is preferably used as an optical member (for example, optical lenses and optical fibers).
• the above-mentioned film is preferably used as an optical film.
• the above-mentioned adhesive is preferably used as an optical adhesive.
• the resin compound contains sulfur atoms, and therefore the resin cured product, molded product, film, and adhesive have excellent adhesion to metal substrates. Therefore, the resin cured product, molded product, film, and adhesive are preferably used in, for example, the building materials field, the electronic parts field, the semiconductor field, the component sealing field, the automotive parts field, the aviation parts field, and the sporting goods field.
• building materials include barrier materials, roofing materials, solar panel materials, battery packaging materials, window materials, outdoor flooring materials, lighting protection materials, automotive parts, signs, and stickers.
• Examples of electronic parts include electronic materials and laminates for electrical and electronic circuits, and more specifically, examples of electronic parts include flexible copper-clad laminates, coverlays, bonding sheets, resin-coated copper foils, multilayer printed wiring boards, capacitors, underfill materials, interchip fills for 3D-LSIs, insulating sheets, heat dissipation boards, and metal foil adhesives for heat dissipation films. Note that the above fields are merely examples, and are not limited to the above.
• the crude product was diluted with 100 mL of dichloromethane to obtain a diluted liquid (solution).
• the diluted liquid was passed through 100 mL of silica gel.
• the diluted liquid was then drained using 300 mL of dichloromethane.
• the drained diluted liquid (solution) was then concentrated using an evaporator.
• 83.4 g of the primary reaction product was obtained.
• the primary reaction product was a partially benzoylated GST.
• Second reaction step 30.0 g of the above-mentioned first reaction product was placed in a four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet line, and a dropping funnel. Then, 50 mL of dichloromethane was added to the flask to dilute the first reaction product with dichloromethane.
• the reaction product liquid in the flask was then stirred at room temperature for 48 hours. Pure water (100 mL) was then added to the flask. The organic phase was then separated by a separation operation. The organic phase was then washed twice with saturated aqueous sodium bicarbonate solution (100 mL). The solvent in the organic phase was then removed using an evaporator.
• the secondary reaction product was a benzoyl and acrylate derivative of GST.
• the secondary reaction product was analyzed by high performance liquid chromatography (HPLC).
• HPLC high performance liquid chromatography
• Trithio(meth)acryloyl modified GST 1.6 mol% (LC%) Dithio(meth)acryloyl modified GST 15.2 mol% (LC%) Monothio(meth)acryloyl modified GST 41.7 mol% (LC%)
• the dithio(meth)acryloyl modified GST and the monothio(meth)acryloyl modified GST are compounds represented by the above formula (1).
• the trithio(meth)acryloyl modified GST is a compound represented by the above formula (7).
• the thio(meth)acryloyl unmodified GST is a compound represented by the above formula (4).
• the average number of (meth)acryloyl groups in the total of the trithio(meth)acryloyl modified GST, the dithio(meth)acryloyl modified GST, and the monothio(meth)acryloyl modified GST was 1.31.
• Example A2 (1) First Reaction Step A four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet line, and a dropping funnel was charged with 48.0 g (184.3 mmol) of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (trifunctional sulfur-containing polythiol (GST)). Then, 200 mL of dichloromethane was added to the flask to dissolve the GST in dichloromethane.
• GST trifunctional sulfur-containing polythiol
• the crude product was diluted with 100 mL of dichloromethane to obtain a diluted liquid (solution).
• the diluted liquid was passed through 100 mL of silica gel.
• the diluted liquid was then drained using 300 mL of dichloromethane.
• the drained diluted liquid (solution) was then concentrated using an evaporator.
• 63.2 g of the primary reaction product was obtained.
• the primary reaction product was a partially benzoylated GST.
• Second reaction step 30.0 g of the above-mentioned first reaction product was placed in a four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet line, and a dropping funnel. Then, 50 mL of dichloromethane was added to the flask to dilute the first reaction product with dichloromethane.
• the reaction product liquid in the flask was then stirred at room temperature for 48 hours. Pure water (100 mL) was then added to the flask. The organic phase was then separated by a separation operation. The organic phase was then washed twice with saturated aqueous sodium bicarbonate solution (100 mL). The solvent in the organic phase was then removed using an evaporator.
• Bz2.0-GSTA a colorless and transparent secondary reaction product
• the secondary reaction product was analyzed by high performance liquid chromatography (HPLC).
• HPLC high performance liquid chromatography
• Trithio(meth)acryloyl modified GST 40.5 mol% (LC%) Dithio(meth)acryloyl modified GST 41.2 mol% (LC%) Monothio(meth)acryloyl modified GST 11.5 mol% (LC%)
• the dithio(meth)acryloyl modified GST and the monothio(meth)acryloyl modified GST are compounds represented by the above formula (1).
• the trithio(meth)acryloyl modified GST is a compound represented by the above formula (7).
• the thio(meth)acryloyl unmodified GST is a compound represented by the above formula (4).
• the average number of (meth)acryloyl groups in the total of the trithio(meth)acryloyl modified GST, the dithio(meth)acryloyl modified GST, and the monothio(meth)acryloyl modified GST was 2.31.
• Example A3 (1) First Reaction Step Into a four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet line, and a dropping funnel, 20.0 g (76.8 mmol) of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (trifunctional sulfur-containing polythiol (GST)) was charged. Then, 100 mL of toluene was added to the flask to dissolve the GST in toluene.
• GST trifunctional sulfur-containing polythiol
• the crude product was diluted with 100 mL of toluene to obtain a diluted liquid (solution).
• the diluted liquid was passed through 20 mL of silica gel.
• the diluted liquid was then drained using 300 mL of toluene.
• the drained diluted liquid (solution) was then concentrated using an evaporator. As a result, 26.0 g of the primary reaction product was obtained.
• the primary reaction product was a partially acetylated product of GST.
• Second reaction step 20.0 g of the above primary reaction product was placed in a four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet line, and a dropping funnel. Then, 100 mL of dichloromethane was added to the flask to dilute the primary reaction product with dichloromethane.
• the reaction product liquid in the flask was then stirred at room temperature for 48 hours. Pure water (100 mL) was then added to the flask. The organic phase was then separated by a separation operation. The organic phase was then washed twice with saturated aqueous sodium bicarbonate solution (100 mL). The solvent in the organic phase was then removed using an evaporator.
• reaction product was placed in a four-neck flask equipped with a thermometer and a dropping funnel. 23 mg of 4-methoxyphenol (polymerization inhibitor) was also added to the flask. The contents of the flask were then stirred at room temperature to dissolve the 4-methoxyphenol.
• the secondary reaction product was an acetylated and acrylated product of GST.
• the secondary reaction product was analyzed by high performance liquid chromatography (HPLC).
• HPLC high performance liquid chromatography
• Trithio(meth)acryloyl modified GST 5.4 mol% (LC%) Dithio(meth)acryloyl modified GST 31.9 mol% (LC%)
• the dithio(meth)acryloyl modified GST and the monothio(meth)acryloyl modified GST are compounds represented by the above formula (1).
• the trithio(meth)acryloyl modified GST is a compound represented by the above formula (7).
• the thio(meth)acryloyl unmodified GST is a compound represented by the above formula (4).
• the average number of (meth)acryloyl groups calculated from the LC% for the total of the trithio(meth)acryloyl modified GST, the dithio(meth)acryloyl modified GST, and the monothio(meth)acryloyl modified GST was 1.28.
• Example A4 (1) First Reaction Step Into a four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet line, and a dropping funnel, 19.1 g (73.2 mmol) of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (trifunctional sulfur-containing polythiol (GST)) was charged. Then, 100 mL of toluene was added to the flask to dissolve the GST in toluene.
• GST trifunctional sulfur-containing polythiol
• the crude product was diluted with 150 mL of toluene to obtain a diluted liquid (solution).
• the diluted liquid was passed through 30 mL of activated alumina (basic, 300 mesh).
• the diluted liquid was then drained using 100 mL of toluene.
• the drained diluted liquid (solution) was then concentrated using an evaporator. As a result, 37.4 g of the primary reaction product was obtained.
• the primary reaction product was a partial 3-phenylpropionylation product of GST.
• Second reaction step 20.0 g of the above primary reaction product was placed in a four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet line, and a dropping funnel. Then, 100 mL of dichloromethane was added to the flask to dilute the primary reaction product with dichloromethane.
• the reaction product liquid in the flask was then stirred at room temperature for 48 hours. Pure water (100 mL) was then added to the flask. The organic phase was then separated by a separation operation. The organic phase was then washed twice with saturated aqueous sodium bicarbonate solution (100 mL). The solvent in the organic phase was then removed using an evaporator.
• reaction product was placed in a four-neck flask equipped with a thermometer and a dropping funnel. 22 mg of 4-methoxyphenol (polymerization inhibitor) was also added to the flask. The contents of the flask were then stirred at room temperature to dissolve the 4-methoxyphenol.
• PP2.0-GSTA a colorless and transparent secondary reaction product
• the secondary reaction product was analyzed by high performance liquid chromatography (HPLC).
• HPLC high performance liquid chromatography
• the dithio(meth)acryloyl modified GST and the monothio(meth)acryloyl modified GST are compounds represented by the above formula (1).
• the trithio(meth)acryloyl modified GST is a compound represented by the above formula (7).
• the thio(meth)acryloyl unmodified GST is a compound represented by the above formula (4).
• the average number of (meth)acryloyl groups calculated from the LC% for the total of the trithio(meth)acryloyl modified GST, the dithio(meth)acryloyl modified GST, and the monothio(meth)acryloyl modified GST was 1.01.
• the polymerizable composition was irradiated with active energy rays (wavelength 365 nm, illuminance 100 mW/cm 2 , cumulative light quantity 1000 mJ/cm 2 ) using an electrodeless light source (H bulb).
• active energy rays wavelength 365 nm, illuminance 100 mW/cm 2 , cumulative light quantity 1000 mJ/cm 2
• H bulb electrodeless light source
• the polymerizable composition was irradiated with active energy rays (wavelength 365 nm, illuminance 100 mW/cm 2 , cumulative light quantity 1000 mJ/cm 2 ). Furthermore, the polymerizable composition was peeled off from the glass substrate and heated at 80° C. for 30 minutes in a nitrogen atmosphere. This caused the polymerizable composition to be cured by the active energy rays and heat. As a result, a resin cured product (adhesive film) was obtained.
• active energy rays wavelength 365 nm, illuminance 100 mW/cm 2 , cumulative light quantity 1000 mJ/cm 2 .
• the refractive index (nC) of the cured resin at C-line was also measured at room temperature (20°C) using an Abbe refractometer (Atago Co., Ltd., DR-M4).
• the refractive index (nF) of the cured resin at F line was also measured at room temperature (20°C) using an Abbe refractometer (Atago Co., Ltd., DR-M4).
• the glass transition point (Tg) of the cured resin and the storage modulus at 25°C (E' (25°C)) were determined.
• the temperature at which the tan ⁇ value was maximum was measured as the glass transition temperature (Tg).
• POB-A o-phenoxybenzyl acrylate, manufactured by Kyoeisha Chemical Co., Ltd.
• 2EHA 2-ethylhexyl acrylate, manufactured by Toagosei Co., Ltd.
• GSTA 1,8-bisacryloylthio-(4-acryloylthiomethyl-3,6-dithiaoctane) produced in accordance with Example 3 of JP-A-4-29967.
• the compound, polymerizable composition, adhesive, cured resin, molded article, film, pressure-sensitive adhesive, and method for producing the compound of the present invention are particularly suitable for use in the optical field.

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• 2023
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