Compounds, polymerizable compositions, adhesives, cured resin products, molded articles, films, tacks, and methods for producing compounds

Abstract

This compound is represented by formula (1). (In formula (1), A represents an m+n-valent organic group that includes a sulfur atom. m represents an integer equal to or greater than 1. n represents an integer equal to or greater than 1. m+n represents an integer equal to or greater than 3. 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 aromatic aliphatic hydrocarbon group. R' represents a hydrogen atom or a methyl group. When a plurality of X are contained in the formula, the X may be the same as or different from each other. Also, when a plurality of R are contained in the formula, the R may be the same as or different from each other. Also, when a plurality of R' are contained in the formula, the R' may be the same as or different from each other.

Description

[Technical Field]

[0001] The present invention relates to compounds, polymerizable compositions, adhesives, cured resin products, molded articles, films, adhesives, and methods for producing compounds. [Background technology]

[0002] (Meth)acrylic resins are widely used in various industrial fields, for example, as adhesives, molded articles, films, and tacks. (Meth)acrylic resins are formed, for example, by radical polymerization of monomers containing (meth)acrylic groups.

[0003] A monomer containing a (meth)acrylic group is known, for example, phenoxybenzyl acrylate (POB-A). Furthermore, a homopolymer of phenoxybenzyl acrylate (POB-A) has been proposed as a (meth)acrylic resin (see, for example, Patent Document 1 (Example 3)).

[0004] Furthermore, (meth)acrylic resins are sometimes used in the field of optics. In such cases, (meth)acrylic resins with a relatively high refractive index are required to suppress light reflection. In addition, curability is required in the field of optics. However, homopolymers of phenoxybenzyl acrylate (POB-A) do not have sufficient refractive index and curability.

[0005] Furthermore, it has been proposed to use thio(meth)acrylate compounds as monomers containing (meth)acrylic groups. For example, trisacrylate of 1,2-bis((2-mercaptoethyl)thio)-3-mercaptopropane has been proposed as a thio(meth)acrylate compound. Trisacrylate of 1,2-bis((2-mercaptoethyl)thio)-3-mercaptopropane is produced by reacting 1,2-bis((2-mercaptoethyl)thio)-3-mercaptopropane with β-chloropropionic acid chloride and treating the reaction product with triethylamine (see, for example, Patent Document 2 (Example 3)). [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] International Publication No. 2021 / 132699 [Patent Document 2] Japanese Patent Application Publication No. 4-29967 [Overview of the project] [Problems that the invention aims to solve]

[0007] For example, the use of thio(meth)acrylate compounds is being considered to improve refractive index and curability. More specifically, it is being considered to use 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 to obtain a cured product with excellent refractive index and curability.

[0008] On the other hand, such cured products require excellent flexibility in addition to excellent refractive index and curability, depending on the application.

[0009] However, when a thio(meth)acrylate compound described in Patent Document 2 is used in combination with a monomer containing a (meth)acrylic group described in Patent Document 1, the flexibility of the resulting cured product is not sufficient.

[0010] Therefore, there is a demand for (meth)acrylic resins (cured products) that possess excellent refractive index and curability, as well as excellent flexibility, and for raw material monomers (compounds) of such (meth)acrylic resins.

[0011] The present invention relates to a compound capable of producing a resin cured product having excellent refractive index and curability, as well as excellent flexibility; an adhesive obtained using the above compound; a resin cured product; a molded article; a film; a tack; and a method for producing the above compound. [Means for solving the problem]

[0012] The present invention [1] contains a compound represented by the following formula (1). Formula (1);

[0013] [ka] (In 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 a fragrant aliphatic hydrocarbon group. R' represents a hydrogen atom or a methyl group. If the formula contains multiple X's, each X may be the same or different from the others. Similarly, if the formula contains multiple R's, each R' may be the same or different from the others.)

[0014] The present invention [2] includes the compound described in [1] above, wherein A represents an organic group containing a sulfur atom and a main group element atom (excluding sulfur atoms and hydrogen atoms), and in A, the ratio of the number of sulfur atoms to the total number of sulfur atoms and the main group element atoms (excluding sulfur atoms and hydrogen atoms) exceeds 20%.

[0015] The present invention [3] comprises the compound according to [1] or [2] above, wherein A in formula (1) is represented by the following formula (2) or the following formula (3). Formula (2);

[0016]

Chemical Formula

[0017]

Chemical Formula

[0018] The present invention [4] comprises the compound according to any one of [1] to [3] above, wherein in formula ( 1 ), X represents a carbonyl group, and R represents a methyl group, a phenyl group, or a 2-phenylethyl group.

[0019] The present invention [5] comprises a polymerizable composition containing the compound according to any one of [1] to [4] above.

[0020] The present invention [6] comprises the polymerizable composition according to [5] above, which contains the compound wherein n=1 in formula ( 1 ).

[0021] The present invention [7] comprises the polymerizable composition according to [5] or [6] above, which further contains another polymerizable compound, and the other polymerizable compound includes a compound represented by the following formula (7). Formula (7);

[0022]

Chemical Formula

[0023] The present invention [8] includes the polymerizable composition described in [7] above, wherein the average number of (meth)acryloyl groups in the total amount of the compound represented by formula (1) and the compound represented by formula (7) above is 1.4 or less.

[0024] The present invention [9] further comprises a polymerizable composition according to any one of the above [5] to [8], wherein the other polymerizable compound comprises a monofunctional (meth)acrylate and / or a polyfunctional (meth)acrylate.

[0025] The present invention

[10] comprises a polymerizable composition according to any one of the above [5] to [9], wherein the plasticizer comprises a compound represented by the following formula (4). Formula (4);

[0026] [ka] (In equation (4), A, S, X, R, m, and n have the same meanings as A, S, X, R, m, and n in equation (1), respectively.)

[0027] The present invention

[11] includes an adhesive comprising a polymerizable composition described in any one of the above [5] to

[10] .

[0028] The present invention

[12] includes the adhesive described in

[11] above, which is an optical adhesive.

[0029] The present invention

[13] includes a resin cured product comprising a cured product of a polymerizable composition described in any one of the above [5] to

[10] .

[0030] The present invention

[14] includes the resin cured product described in

[13] above, which has a refractive index of 1.60 or higher and a tensile storage modulus of 10 MPa or less.

[0031] The present invention

[15] includes a molded article comprising a resin cured product as described in

[13] or

[14] above.

[0032] The present invention

[16] includes the molded article described in

[15] above, which is an optical component.

[0033] The present invention

[17] includes a film comprising the resin cured product described in

[13] or

[14] above.

[0034] The present invention

[18] includes the film described in

[17] above, which is an optical film.

[0035] The present invention

[19] includes an adhesive comprising the resin cured product described in

[14] or

[15] above.

[0036] The present invention

[20] includes the adhesive described in

[19] above, which is an optical adhesive.

[0037] The present invention

[21] is a method for producing a compound described in any one of the above [1] to [3], comprising a preparation step of preparing a polythiol containing a sulfur atom and having an m+n valency (where m+n is an integer of 3 or more), and a reaction step of reacting the polythiol with a first modifying agent that seals the molecular ends of the polythiol and does not form a (meth)acryloyl group, and a second modifying agent that seals the molecular ends of the polythiol and forms a (meth)acryloyl group.

[0038] The present invention

[22] includes a method for producing the compound described in

[21] above, wherein the polythiol is represented by the following formula (5) or the following formula (6). Formula (5);

[0039] [ka] Formula (6);

[0040] [ka]

[0041] The present invention

[23] includes a method for producing the compound described in

[21] or

[22] above, wherein the reaction step comprises a first reaction step of reacting the polythiol with the first modifying agent, and a second reaction step after the first reaction step of reacting the reaction product from the first reaction step with the second modifying agent. [Effects of the Invention]

[0042] According to the compounds, polymerizable compositions, and adhesives of the present invention, it is possible to obtain resin cured products that possess excellent refractive index and curability, as well as excellent flexibility.

[0043] The resin cured products, molded articles, films, and adhesives of the present invention possess excellent refractive index and curability, as well as excellent flexibility.

[0044] According to the method for producing the compound of the present invention, the above-mentioned compound can be obtained efficiently. [Modes for carrying out the invention]

[0045] 1.Compound (1) Structure of the compound The compound of the present invention is represented by the following formula (1).

[0046] [ka] (In 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 aromatic aliphatic hydrocarbon group. R' represents a hydrogen atom or a methyl group. If the formula contains multiple Xs, each X may be the same or different from the others.) Furthermore, if an expression contains multiple Rs, each R may be the same or different from the others. Furthermore, if an expression contains multiple R's, each R' may be identical or different from the others.

[0047] The compound represented by formula (1) above is a modified polythiol in which, as will be described in detail later, some of the mercapto groups of a trifunctional or more sulfur-containing polythiol (described later) form thio(meth)acryloyl groups, and the remainder of the mercapto groups form SXR groups. Hereinafter, the compound represented by formula (1) above may be referred to as a partially modified thio(meth)acryloyl compound.

[0048] Thio(meth)acryloyl refers to thioacryloyl and / or thiomethacryloyl. (Meth)acryloyl refers to acryloyl and / or methacryloyl. (Meth)acrylic refers to acrylic and / or methacrylic.

[0049] (2) A In formula (1) above, A represents an m+n valent organic group containing a sulfur atom. Preferably, A represents an organic group containing a sulfur atom and a typical element atom (excluding sulfur and hydrogen atoms).

[0050] In the context of typical element atoms (excluding sulfur and hydrogen atoms), typical elements (excluding sulfur and hydrogen) refer to elements with atomic numbers 2 to 15, 17 to 20, 31 to 38, 49 to 56, and 81 to 88. Preferably, typical elements (excluding sulfur and hydrogen) include elements with atomic numbers 2 to 15, more preferably elements with atomic numbers 6 to 9, and more specifically, carbon, nitrogen, oxygen, and fluorine. These can be used individually or in combination of two or more.

[0051] More preferably, carbon and oxygen are representative elements (excluding sulfur and hydrogen), and carbon is particularly preferred. From the viewpoint of obtaining a good balance between refractive index and flexibility, more preferably, 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.

[0052] m+n represents the valence of organic group A. More specifically, m is an integer greater than or equal to 1, n is an integer greater than or equal to 1, and m+n is an integer greater than or equal to 3.

[0053] In other words, in equation (1) above, m may be 1, or it may be an integer greater than or equal to 2. When m is 1, n is an integer greater than or equal to 2. Then, m+n is an integer greater than or equal to 3.

[0054] Furthermore, in equation (1) above, n may be 1 or an integer of 2 or more. When n is 1, m represents an integer of 2 or more. Then, m+n represents an integer of 3 or more. Preferably, n represents 1.

[0055] The valency (m+n) of organic group A is preferably an integer between 3 and 8, more preferably an integer between 3 and 6, and even more preferably 3 or 4.

[0056] Examples of organic group A include residues of m+n functionalized thiols. More specifically, examples of organic group A include residues obtained by removing the mercapto group from a sulfur-containing polythiol with three or more functionalities (hereinafter referred to as sulfur-containing polythiol residues with three or more functionalities).

[0057] A sulfur-containing polythiol with three or more functions is an organic compound that contains three or more mercapto groups in one molecule, and also contains one or more (preferably two or three) sulfur atoms in addition to the mercapto groups. Examples of sulfur-containing polythiols with three or more functions include sulfur-containing trithiol, sulfur-containing tetrathiol, sulfur-containing pentatiol, sulfur-containing hexatiol, and sulfur-containing octatiol.

[0058] Sulfur-containing trithiols are trifunctional thiols that contain a sulfur atom in addition to the mercapto group. Examples of 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 Examples include ]-6-[4-(6-mercaptomethylthio)-1,3-dithianylthio]-1,3-dithiane, tris(mercaptomethylthio)methane, tris(mercaptoethylthio)methane, 2,4,6-tris(mercaptomethylthio)-1,3,5-trithiacyclohexane, tris[(4-mercaptomethyl-2,5-dithiacyclohexyl-1-yl)methylthio]methane, 4-mercaptomethyl-2-(2,3-dimercaptopropylthio)-1,3-dithiacyclopentane, and 4-mercaptomethyl-2-(1,3-dimercapto-2-propylthio)-1,3-dithiacyclopentane.

[0059] Sulfur-containing tetrathiols are tetrafunctional thiols that contain a sulfur atom in addition to the mercapto group. Examples of 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, bis(2,3-dimercaptopropyl ester) thiodipropionate, bis(2,3-dimercaptopropyl ester) dithiodiglycolate, bis(2,3-dimercaptopropyl ester) thiodipropionate, bis(2,3-dimercaptopropyl ester) dithiodipropionate, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 1,1,5,5-tetrakis(mercaptomethylthio)- 3-Tiapentane, 1,1,6,6-Tetrakis(mercaptomethylthio)-3,4-Dithiahexane, 2,5-Bis(4,4-Bis(mercaptomethylthio)-2-thiabutyl)-1,4-Dithiane, 2,2-Bis(mercaptomethylthio)-1,3-Propanedithiol, 3,6-Bis(mercaptomethylthio)-1,9-Dimercapto-2,5,8-Tritianonane, 4-[3,5-Bis(mercaptomethylthio)-7-Mercapto-2,6-Dithiaheptylthio]-6-Mercaptomethylthio-1,3-Dithiane , 1,1-bis[4-(6-mercaptomethylthio)-1,3-dithianylthio]-1,3-bis(mercaptomethylthio)propane, 3-[2-(1,3-dithiethanyl)]methyl-7,9-bis(mercaptomethylthio)-1,11-dimercapto-2,4,6,10-tetrathiaundecane, 4-[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]-5-mercaptomethylthio-1,3-dithiolane, 2-[3,4-bis(mercaptomethylthio)-6-mercapto-2,Examples include 5-dithiahexylthio]mercaptomethylthiomethyl-1,3-dithiethane, 4-{1-[2-(1,3-dithietanyl)]-3-mercapto-2-thiapropylthio}-5-[1,2-bis(mercaptomethylthio)-4-mercapto-3-thiabutylthio]-1,3-dithiolane, 1,1,5,5-tetrakis(mercaptomethylthio)-2,4-dithiapentane, and 1,1,3,3-tetrakis(mercaptomethylthio)-2-thiapropane.

[0060] Sulfur-containing pentatiols are pentafunctional thiols that contain a sulfur atom in addition to the mercapto group. Examples of sulfur-containing pentatiols 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.

[0061] Sulfur-containing hexathiols are hexafunctional thiols that contain a sulfur atom in addition to the mercapto group. Examples of 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(mercapto Methylthio)-1,11-dimercapto-2,5,7,10-tetrathiaundecane, 4,6-bis[3,5-bis(mercaptomethylthio)-7-mercapto-2,6-dithiaheptylthio]-1,3-dithiane, 3-[2-(1,3-dithiethanyl)]methyl-7,9,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,4,6,10,12,16-hexathiaheptadecane, 4-[3,4,8,9-tetrakis(mercaptomethylthio)-11-mercapto-2,5,7,10 -Tetrathiaundecyl]-5-mercaptomethylthio-1,3-dithiolane, 4,5-bis[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]-1,3-dithiolane, 4-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiaoctyl]-5-mercaptomethylthio-1,3-dithiolane, 2-{bis[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio] Methyl-1,3-dithiethane, 2-[3,4,8,9-tetrakis(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathiaundecylthio]mercaptomethylthiomethyl-1,3-dithiethane, 2-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiaoctyl]mercaptomethylthiomethyl-1,3-dithiethane, Tris[4,4-bis(mercaptomethylthio)-1,3-dithiabutyl]methane, Tris[2,Examples include 2-bis(mercaptomethylthio)-2-thiapropyl]methane, tris[4,4-bis(mercaptomethylthio)-3-thiabutyl]methane, and 2,4,6-tris[3,3-bis(mercaptomethylthio)-2-thiapropyl]-1,3,5-trithiacyclohexane.

[0062] Sulfur-containing octatiols are octafunctional thiols that contain a sulfur atom in addition to the mercapto group. Examples of sulfur-containing octatiols 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, and tetrakis(2,2 Examples include bis(mercaptomethylthio)ethyl)methane, 3,4,8,9,13,14-hexakis(mercaptomethylthio)-1,16-dimercapto-2,5,7,10,12,15-hexatiahexadecane, 8-[bis(mercaptomethylthio)methyl]-3,4,12,13-tetrakis(mercaptomethylthio)-1,15-dimercapto-2,5,7,9,11,14-hexatiapentadecane, and tetrakis[3,3-bis(mercaptomethylthio)-2-thiapropyl]methane.

[0063] Preferably, sulfur-containing polythiol residues with three or more functions include sulfur-containing polythiol residues with three to six functions, more preferably sulfur-containing polythiol residues with three to four functions, and even more preferably sulfur-containing polythiol residues with three functions.

[0064] In other words, in formula (1), A is preferably a 3- to 6-functional sulfur-containing polythiol residue, more preferably a 3- to 4-functional sulfur-containing polythiol residue, and even more preferably a 3-functional sulfur-containing polythiol residue.

[0065] In other words, A is preferably a 3- to 6-valent organic group containing one or more (preferably two or three) sulfur atoms. More preferably A is a trivalent organic group containing one or more (preferably two or three) sulfur atoms, and a tetravalent organic group containing one or more (preferably two or three) sulfur atoms, and even more preferably a trivalent organic group containing sulfur atoms.

[0066] From the viewpoint of obtaining a good balance between refractive index and flexibility, preferably, A contains sulfur atoms in a predetermined proportion or higher. More specifically, in A, the ratio of the number of sulfur atoms to the total 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. Also, from the viewpoint of obtaining a good balance between refractive index and flexibility, the ratio of the number of sulfur atoms to the total 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 typical element atoms (excluding sulfur atoms and hydrogen atoms) is calculated by the following formula.

[0067] The percentage of sulfur atoms (%) = Number of sulfur atoms / [Number of sulfur atoms + Number of typical element atoms (excluding sulfur and hydrogen atoms)] × 100

[0068] A trivalent organic group (organic group A(m+n=3)) containing one or more sulfur atoms (preferably two or three, more preferably two) is preferably a residue obtained by removing the mercapto group from the above-mentioned sulfur-containing trithiol, and more preferably a residue obtained by removing the mercapto group from 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (GST) (GST residue).

[0069] The residue obtained by removing the mercapto group from 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (GST) (GST residue) is represented, for example, by the following formula (2).

[0070] [ka] (In equation (2), S has the same meaning as S in equation (1). If A in equation (1) is shown in equation (2), then m+n in equation (1) represents 3.)

[0071] If A in formula (1) above is a GST residue, a cured resin product can be obtained that possesses particularly excellent refractive index and curability, as well as particularly excellent flexibility.

[0072] A GST residue is an organic group consisting of two sulfur atoms and seven carbon atoms. In a GST residue, the ratio of sulfur atoms to the total number of typical element atoms (excluding sulfur and hydrogen atoms) is approximately 22% (2 / [2+7]×100).

[0073] As a tetravalent organic group (organic group A(m+n=4)) containing one or more sulfur atoms (preferably two or three, more preferably three), a suitable example is a residue obtained by removing the mercapto group from the above-mentioned sulfur-containing tetrathiol, and more preferably a residue obtained by removing the mercapto group from 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (FSH) (FSH residue).

[0074] The residue obtained by removing the mercapto group from 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (FSH) (FSH residue) is represented, for example, by the following formula (3).

[0075] [ka] (In equation (3), S has the same meaning as S in equation (1). If A in equation (1) is shown in equation (3), then m+n in equation (1) represents 4.)

[0076] If A in formula (1) above is an FSH residue, a resin cured product can be obtained that possesses particularly excellent refractive index and curability, as well as particularly excellent flexibility.

[0077] FSH residues are organic groups consisting of three sulfur atoms and ten carbon atoms. In FSH residues, the ratio of sulfur atoms to the total number of typical element atoms (excluding sulfur and hydrogen atoms) is approximately 23% (3 / [3+10]×100).

[0078] From the viewpoint of refractive index, hardening properties, and flexibility, the A in formula (1) is preferably the GST residue shown in formula (2) and the FSH residue shown in formula (3), and more preferably the GST residue.

[0079] (3) S in equation In the above formula (1), S represents a sulfur atom.

[0080] (4) X In formula (1) above, X represents a single bond or a carbonyl group.

[0081] When X represents a single bond, S and R in formula (1) above are directly bonded. That is, when X represents a single bond, the SXR group in formula (1) above represents an SR group.

[0082] When X represents a carbonyl group, in formula (1) above, S and R are indirectly bonded via the carbonyl group. That is, when X represents a carbonyl group, the SXR group in formula (1) above represents an S(C=O)R group.

[0083] The compound represented by formula (1) above comprises one or more SXR groups, depending on the values ​​of m and n. In other words, formula (1) may contain one X or multiple (two or more) X groups. When formula (1) contains multiple X groups, each X may be the same as or different from one another. Preferably, each X is the same as one another.

[0084] (5) R In formula (1) above, R represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or an aromatic aliphatic hydrocarbon group.

[0085] Examples of aliphatic hydrocarbon groups include aliphatic hydrocarbon groups having 1 to 20 carbon atoms. More specifically, examples of aliphatic hydrocarbon groups include linear aliphatic hydrocarbon groups having 1 to 20 carbon atoms and cyclic aliphatic hydrocarbon groups having 3 to 20 carbon atoms.

[0086] Examples of 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. Examples of linear saturated aliphatic hydrocarbon groups having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, 2-butyl group, 1-pentyl group, 2-pentyl group, 3-pentyl group, 2-methyl-1-butyl group, isopentyl group, tert-pentyl group, 3-methyl-2-butyl group, neopentyl group, n-hexyl group, 4-methyl Examples include tyl-2-pentyl group, 1-heptyl group, 3-heptyl group, 1-octyl group, 2-octyl group, 2-ethyl-1-hexyl group, 1,1-dimethyl-3,3-dimethylbutyl group, 1-nonyl group, 1-decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and eicosyl group. Examples of linear unsaturated aliphatic hydrocarbon groups having 1 to 20 carbon atoms include vinyl group and 2-propenyl group. These can be used individually or in combination of two or more.

[0087] Examples of cyclic aliphatic hydrocarbon groups having 3 to 20 carbon atoms include cyclic saturated aliphatic hydrocarbon groups 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 individually or in combination of two or more types.

[0088] Examples of aromatic hydrocarbon groups include aromatic hydrocarbon groups having 6 to 20 carbon atoms. Examples of aromatic hydrocarbon groups having 6 to 20 carbon atoms include phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,4,6-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 1-naphthyl group, and 2-naphthyl group. These can be used individually or in combination of two or more types.

[0089] Examples of aromatic aliphatic hydrocarbon groups include those having 7 to 20 carbon atoms. Examples of aromatic aliphatic hydrocarbon groups having 7 to 20 carbon atoms include benzyl group, 1-phenylethyl group, 2-phenylethyl group, 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 individually or in combination of two or more types.

[0090] Aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and aromatic aliphatic hydrocarbon groups may have substituents. Examples of substituents include halogeno groups, cyano groups, amino groups, carboxyl groups, sulfonyl groups, and alkoxy groups. These may be used individually or in combination of two or more. The number of substituents may be set as appropriate depending on the purpose and application. The substitution positions may be set as appropriate depending on the purpose and application.

[0091] The compound represented by formula (1) above comprises one or more SXR groups, depending on the values ​​of m and n. In other words, formula (1) may contain one R or multiple (two or more) R groups. When formula (1) contains multiple R groups, each R may be the same as or different from one another. Preferably, each R is the same as one another.

[0092] When R represents an aliphatic hydrocarbon group, preferably a linear aliphatic hydrocarbon group having 1 to 10 carbon atoms is included, more preferably a linear aliphatic hydrocarbon group having 1 to 4 carbon atoms is included, even more preferably a linear aliphatic hydrocarbon group having 1 to 2 carbon atoms is included, and particularly preferably a methyl group is included.

[0093] When R represents an aromatic hydrocarbon group, preferably it is 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.

[0094] When R represents an aromatic aliphatic hydrocarbon group, preferably it is 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 and a 2-phenylethyl group.

[0095] From the viewpoint of obtaining a cured product with a good balance of refractive index and flexibility, in formula (1) above, preferably, X represents a carboxyl group, and R represents a methyl group, a phenyl group, or a 2-phenylethyl group.

[0096] (6) R' In formula (1) above, R' represents a hydrogen atom or a methyl group. R' constitutes the thio(meth)acryloyl group in formula (1) above.

[0097] More specifically, when R' represents a hydrogen atom, formula (1) above includes a thioacryloyl group (-SC(=O)CH=CH2). Also, when R' represents a methyl group, formula (1) above includes a thiomethacryloyl group (-SC(=O)C(CH3)=CH2).

[0098] The compound represented by formula (1) above comprises one or more thio(meth)acryloyl groups, depending on the values ​​of m and n. In other words, formula (1) may contain one R' or may contain multiple (two or more) R' groups. When formula (1) contains multiple R' groups, each R' may be the same as or different from each other. Preferably, each R' is the same as each other.

[0099] (7) Specific examples Preferably, the compounds represented by formula (1) above include compounds in which the organic group A in formula (1) is a GST residue, and compounds in which A in formula (1) is an FSH residue. More preferably, the compounds represented by formula (1) above include compounds in which A in formula (1) is a GST residue.

[0100] Examples of compounds in which the organic group A in formula (1) is a GST residue include the compound shown in formula (1-1) below and the compound shown in formula (1-2) below.

[0101] [ka] (In equation (1-1), S, X, R, and R' have the same meaning as S, X, R, and R' in equation (1). In equation (1-1), the part enclosed by the dashed line represents the organic group A (m+n=3) in equation (1).)

[0102] In formula (1-1) above, of the three binding sites (m+n) of organic group A (GST residue) in formula (1), SXR groups are attached to two sites and a thio(meth)acryloyl group is attached to one site. In other words, the compound represented by formula (1-1) above is the compound in formula (1) above where m is 2 and n is 1. Hereinafter, the compound represented by formula (1-1) above may be referred to as a monothio(meth)acryloyl modified form (diSXR modified form) of GST.

[0103] The compound represented by formula (1-1) above (a monothio(meth)acryloyl modified form of GST) has one thio(meth)acryloyl group. Therefore, the compound represented by formula (1-1) above forms a linear structure by radical polymerization (described later).

[0104] Furthermore, the compound represented by formula (1-1) above (a monothio(meth)acryloyl modified form of GST) has two SXR groups. Therefore, using the compound represented by formula (1-1) above, it is possible to obtain a resin cured product that combines excellent refractive index and curability with excellent flexibility.

[0105] [ka] (In equation (1-2), S, X, R, and R' have the same meanings as S, X, R, and R' in equation (1). In equation (1-2), the portion enclosed by the dashed line represents the organic group A (m+n=3) in equation (1).)

[0106] In formula (1-2) above, of the three binding sites (m+n) of organic group A (GST residue) in formula (1), an SXR group is attached to one site and thio(meth)acryloyl groups are attached to the other two sites. In other words, the compound represented by formula (1-2) above is the compound in formula (1) above where m is 1 and n is 2. Hereinafter, the compound represented by formula (1-2) above may be referred to as a dithio(meth)acryloyl modified form of GST (monoSXR modified form).

[0107] The compound represented by formula (1-2) above (dithio(meth)acryloyl modified GST) has two thio(meth)acryloyl groups. Therefore, the compound represented by formula (1-2) above forms a two-dimensional crosslinked structure by radical polymerization (described later).

[0108] Furthermore, the compound represented by formula (1-2) above (dithio(meth)acryloyl modified GST) has one SXR group. Therefore, using the compound represented by formula (1-2) above, it is possible to obtain a resin cured product that combines excellent refractive index and curability with excellent flexibility.

[0109] The compounds represented by formula (1) above can be used individually or in combination of two or more.

[0110] The compound represented by formula (1) above is a novel compound having a specific structure. Using this compound, a resin cured product (described later) possessing both refractive index and flexibility can be obtained. Therefore, the compound represented by formula (1) above is preferably used as a polymerizable compound, as will be described in more detail later.

[0111] The method for producing the compound shown in formula (1) above will be described later.

[0112] 2. Polymerizable composition (1) Polymerizable compound A polymerizable composition is a raw material composition that can be radically polymerized. A polymerizable composition contains a radically polymerizable compound (hereinafter referred to as a polymerizable compound).

[0113] (a) Compound represented by formula (1) above Examples of polymerizable compounds include the compound represented by formula (1) above (partially thio(meth)acryloyl modified compound). In other words, the polymerizable composition contains the compound represented by formula (1) above (partially thio(meth)acryloyl modified compound) as a polymerizable compound. These can be used alone or in combination of two or more types.

[0114] Preferably, polymerizable compounds include those represented by formula (1) above, where organic group A is a GST residue. Also preferably, polymerizable compounds include those represented by formula (1) above, where organic group A is an FSH residue. From the viewpoint of refractive index and flexibility, more preferably, polymerizable compounds include those represented by formula (1) above, where organic group A is a GST residue, used alone.

[0115] More preferably, from the viewpoint of refractive index and flexibility, polymerizable compounds include the compound represented by formula (1-1) above (a modified monothio(meth)acryloyl of GST) and the compound represented by formula (1-2) above (a modified dithio(meth)acryloyl of GST). These can be used alone or in combination.

[0116] As a polymerizable compound, from the viewpoint of refractive index and flexibility, the above formula ( 1 Examples include polymerizable compounds in which n=1 in the above formula ( 1The polymerizable compound comprises n=1 in the given formula. More preferably, the polymerizable composition comprises a monothio(meth)acryloyl modified form of GST.

[0117] As a polymerizable compound, more preferably, from the viewpoint of refractive index and flexibility, the above formula ( 1 A polymerizable compound in which n=1 in the above formula ( 1 A polymerizable compound in which n=2 is used in combination with the above. More preferably, a monothio(meth)acryloyl modified form of GST and a dithio(meth)acryloyl modified form of GST are used in combination.

[0118] In other words, from the viewpoint of refractive index and flexibility, the polymerizable composition preferably contains both a monothio(meth)acryloyl modified form of GST and a dithio(meth)acryloyl modified form of GST as polymerizable compounds.

[0119] In polymerizable compositions, the content ratio (total amount) of the compound represented by formula (1) above (partially thio(meth)acryloyl modified compound) is set appropriately according to the purpose and application.

[0120] More specifically, the content (total mass) of the compound represented by formula (1) above is, from the viewpoint of flexibility, for example, 1% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 40% by mass or more, even more preferably 50% by mass or more, and particularly preferably 60% by mass or more, relative to the total amount of polymerizable composition. Also, the content (total moles) of the compound represented by formula (1) above is, from the viewpoint of flexibility, for example, 100% by mass or less, preferably 99% by mass or less, more preferably 95% by mass or less, even more preferably 90% by mass or less, even more preferably 85% by mass or less, and particularly preferably 80% by mass or less, relative to the total amount of polymerizable composition.

[0121] Furthermore, if the polymerizable composition contains both a monothio(meth)acryloyl modified form of GST and a dithio(meth)acryloyl modified form of GST as compounds represented by formula (1) above, the proportions of these compounds will be appropriately set according to the purpose and application.

[0122] For example, from the viewpoint of flexibility, the content ratio of the monothio(meth)acryloyl modified GST relative to the total moles of polymerizable compounds (compounds represented by formula (1) above, and other polymerizable compounds (described later)) is, for example, 0.1 mol% or more, preferably 1 mol% or more. Also, from the viewpoint of flexibility, the content ratio of the monothio(meth)acryloyl modified GST relative to the total moles of polymerizable compounds is, for example, 99 mol% or less, preferably 90 mol% or less.

[0123] Furthermore, from the viewpoint of flexibility, the content ratio of the dithio(meth)acryloyl modified GST relative to the total moles of the polymerizable compound is, for example, 0.1 mol% or more, preferably 1 mol% or more. Also, from the viewpoint of flexibility, the content ratio of the dithio(meth)acryloyl modified GST relative to the total moles of the polymerizable compound is, for example, 99 mol% or less, preferably 90 mol% or less.

[0124] Furthermore, for example, the amount of GST monothio(meth)acryloyl modified material relative to the total moles of GST monothio(meth)acryloyl modified material and GST dithio(meth)acryloyl modified material is, for example, 25 mol% or more, preferably 50 mol% or more, from the viewpoint of flexibility. Also, the amount of GST monothio(meth)acryloyl modified material relative to the total moles of GST monothio(meth)acryloyl modified material and GST dithio(meth)acryloyl modified material is usually less than 100 mol% from the viewpoint of curability.

[0125] Furthermore, from the viewpoint of curability, the amount of dithio(meth)acryloyl modified GST is usually greater than 0 mol% relative to the total moles of monothio(meth)acryloyl modified GST and dithio(meth)acryloyl modified GST. Also, from the viewpoint of flexibility, the amount of dithio(meth)acryloyl modified GST is, for example, 75 mol% or less, preferably 50 mol% or less, relative to the total moles of monothio(meth)acryloyl modified GST and dithio(meth)acryloyl modified GST.

[0126] Furthermore, from the viewpoint of curability, the molar amount of dithio(meth)acryloyl modified GST per 100 moles of monothio(meth)acryloyl modified GST is, for example, 10 moles or more, preferably 20 moles or more. Also, from the viewpoint of flexibility, the molar amount of dithio(meth)acryloyl modified GST per 100 moles of monothio(meth)acryloyl modified GST is, for example, 50 moles or less, preferably 40 moles or less.

[0127] Furthermore, in the total amount of the compound represented by formula (1) above, the average number of (meth)acryloyl groups exceeds, for example, 1.0, from the viewpoint of curability.

[0128] Furthermore, in the total amount of the compound represented by formula (1) above, the average number of (meth)acryloyl groups is, from the viewpoint of flexibility, for example, less than 1.5, preferably 1.4 or less, and more preferably 1.35 or less.

[0129] Furthermore, such polymerizable compositions contain the compound represented by formula (1) above. Therefore, using a polymerizable composition, it is possible to obtain a resin cured product that combines excellent refractive index and curability with excellent flexibility.

[0130] Furthermore, polymerizable compositions containing such partially thio(meth)acryloyl modified compounds can be obtained, for example, as reaction products (reaction product compositions) in the production of the compound represented by formula (1) above (described later).

[0131] (b) Other polymerizable compounds The polymerizable composition may, in addition to the compound represented by formula (1) above (partially thio(meth)acryloyl modified compound), optionally contain other polymerizable compounds.

[0132] Other polymerizable compounds include, for example, compounds in which all of the mercapto groups of a trifunctional or more sulfur-containing polythiol form thio(meth)acryloyl groups.

[0133] Hereinafter, such compounds may be referred to as fully thio(meth)acryloyl modified compounds.

[0134] In the complete thio(meth)acryloyl modified compound, the thio(meth)acryloyl group is bonded (added) to all (m+n) bonds of organic group A in formula (1) above.

[0135] Examples of completely thio(meth)acryloyl modified compounds include the compound shown in formula (7) below.

[0136] [ka] (In equation (7), A, S, R', m, and n have the same meanings as A, S, R', m, and n in equation (1).)

[0137] Preferably, compounds represented by formula (7) include compounds in which the organic group A in formula (7) is a GST residue, and compounds in which the organic group A in formula (7) is an FSH residue.

[0138] More preferably, the compound represented by formula (7) above 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).

[0139] [ka] (In equation (7-1), S and R' have the same meaning as S and R' in equation (1). In equation (7-1), the part enclosed by the dashed line represents the organic group A (m+n=3) in equation (1).)

[0140] In formula (7-1) above, thio(meth)acryloyl groups are attached to all three binding sites (m+n) of organic group A (GST residue) in formula (1) above.

[0141] In other words, the compound represented by formula (7-1) is the compound in formula (1) where m is 0 and n is 3. Hereinafter, the compound represented by formula (7-1) may be referred to as a trithio(meth)acryloyl modified form of GST.

[0142] Examples of trithio(meth)acryloyl modified forms of GST include 1,8-bis(meth)acryloylthio-(4-(meth)acryloylthiomethyl-3,6-dithiaoctane) (GST(M)A). From the viewpoint of refractive index and flexibility, 1,8-bisacryloylthio-(4-acryloylthiomethyl-3,6-dithiaoctane (GSTA) is preferred as a trithio(meth)acryloyl modified form of GST. Note that 1,8-bis(meth)acryloylthio-(4-(meth)acryloylthiomethyl-3,6-dithiaoctane) is synthesized, for example, based on the description in Japanese Patent Application Publication No. 4-29967.

[0143] Complete thio(meth)acryloyl modified compounds can be used alone or in combination of two or more types.

[0144] Complete thio(meth)acryloyl modified compounds have three or more (m+n) thio(meth)acryloyl groups. Therefore, complete thio(meth)acryloyl modified compounds form a three-dimensional crosslinked structure through radical polymerization (described later).

[0145] The method for obtaining the complete thio(meth)acryloyl modified compound is not particularly limited. For example, the complete thio(meth)acryloyl modified compound can be obtained as a by-product in the synthesis reaction of the compound represented by formula (1) above (described later). Alternatively, the complete thio(meth)acryloyl modified compound can be obtained, for example, in accordance with the method described in Japanese Patent Application Publication No. 4-29967.

[0146] Furthermore, polymerizable compositions containing a fully thio(meth)acryloyl modified compound can be obtained, for example, as a reaction product (reaction product composition) in the production of the compound represented by formula (1) above.

[0147] In polymerizable compositions, the content ratio of the fully modified thio(meth)acryloyl is appropriately set according to the purpose and application.

[0148] For example, the content ratio (total moles) of the complete thio(meth)acryloyl modified product relative to the total moles of the polymerizable compound is usually 0 mol% or more, preferably 0.1 mol% or more. Also, the content ratio (total amount) of the complete thio(meth)acryloyl modified product relative to the total moles of the polymerizable compound is, for example, 80 mol% or less, preferably 50 mol% or less, and more preferably 20 mol% or less.

[0149] Furthermore, the content ratio (total amount) of the compound represented by formula (7) (complete thio(meth)acryloyl modified) per 100 parts by mass of the compound represented by formula (1) (partial thio(meth)acryloyl modified) is usually 0 parts by mass or more, preferably 0.1 parts by mass or more. Also, the content ratio (total amount) of the compound represented by formula (7) (complete thio(meth)acryloyl modified) per 100 parts by mass of the compound represented by formula (1) (partial thio(meth)acryloyl modified) 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.

[0150] Furthermore, in the total amount of the compound represented by formula (1) above (partially thio(meth)acryloyl modified) and the compound represented by formula (7) above (completely thio(meth)acryloyl modified), the average number of (meth)acryloyl groups exceeds, for example, 1.0 from the viewpoint of curability.

[0151] Furthermore, in the total amount of the compound represented by formula (1) above (partially thio(meth)acryloyl modified) and the compound represented by formula (7) above (completely thio(meth)acryloyl modified), 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 can be obtained. Therefore, the cured resin can be suitably used, in particular, as an adhesive.

[0152] Other polymerizable compounds include, for example, monofunctional (meth)acrylates and / or polyfunctional (meth)acrylates. In other words, polymerizable compositions can include monofunctional (meth)acrylates and / or polyfunctional (meth)acrylates.

[0153] The polymerizable composition preferably contains monofunctional (meth)acrylate and / or polyfunctional (meth)acrylate in order to obtain the desired physical properties according to the application.

[0154] Examples of monofunctional (meth)acrylates include aromatic ring-containing mono(meth)acrylates and aromatic ring-free mono(meth)acrylates.

[0155] Examples of aromatic ring-containing mono(meth)acrylates 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, nonylphenoxyethyltetrahydrofurfuryl(meth)acrylate, and 1-naphthylmethyl(meth)acrylate. These can be used individually or in combination of two or more.

[0156] Examples of aromatic ring-free mono(meth)acrylates 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, methoxyethyl( Examples include meth)acrylate, butoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, glycidyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, diethylaminoethyl (meth)acrylate, caprolactone-modified tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and dicyclopentenyloxyethyl (meth)acrylate. These can be used alone or in combination of two or more types.

[0157] These monofunctional (meth)acrylates can be used individually or in combination of two or more types. Preferably, the monofunctional (meth)acrylates include mono(meth)acrylates containing aromatic rings used individually, and mono(meth)acrylates without aromatic rings used individually.

[0158] Furthermore, as monofunctional (meth)acrylates, from the viewpoint of refractive index and flexibility, aromatic ring-containing mono(meth)acrylates are preferred, more preferably (o,m or p-)phenoxybenzyl(meth)acrylate (POB-(M)A), even more preferably (o,m or p-)phenoxybenzylacrylate (POB-A), and from the viewpoint of flexibility, o-phenoxybenzylacrylate is particularly preferred.

[0159] Furthermore, as monofunctional (meth)acrylates, from the viewpoint of viscosity (low Tg), aromatic ring-free mono(meth)acrylates are preferred, more preferably 2-ethylhexyl (meth)acrylate (2EH(M)A), and even more preferably 2-ethylhexyl acrylate (2EHA).

[0160] In polymerizable compositions, the proportion of monofunctional (meth)acrylate is appropriately set according to the purpose and application.

[0161] For example, the content (total amount) of monofunctional (meth)acrylate relative to the total moles of polymerizable compound is, for example, 0 mol% or more, preferably 5 mol% or more. Also, the content (total amount) of monofunctional (meth)acrylate relative to the total moles of polymerizable compound is, for example, 80 mol% or less, preferably 50 mol% or less.

[0162] Furthermore, the content ratio (total amount) of monofunctional (meth)acrylate per 100 parts by mass of the compound represented by formula (1) above (partially thio(meth)acryloyl modified compound) is, for example, 0 parts by mass or more, preferably 5 parts by mass or more. Also, the content ratio (total amount) of monofunctional (meth)acrylate per 100 parts by mass of the compound represented by formula (1) above (partially thio(meth)acryloyl modified compound) is, for example, 500 parts by mass or less, preferably 200 parts by mass or less.

[0163] Examples of polyfunctional (meth)acrylates include difunctional (meth)acrylates and trifunctional (meth)acrylates.

[0164] Examples of difunctional (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, tricyclodecanedimethanol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and tris(2-hydroxyethyl)isocyanurate-di(meth)acrylate. These can be used individually or in combination of two or more types.

[0165] Examples of (meth)acrylates with three or more functionalities 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 individually or in combination of two or more types.

[0166] These polyfunctional (meth)acrylates can be used individually or in combination of two or more types.

[0167] In polymerizable compositions, the proportion of polyfunctional (meth)acrylate is appropriately set according to the purpose and application.

[0168] For example, the content (total amount) of polyfunctional (meth)acrylate relative to the total moles of polymerizable compound is, for example, 0 mol% or more, preferably 3 mol% or more. Also, the content (total amount) of polyfunctional (meth)acrylate relative to the total moles of polymerizable compound is, for example, 50 mol% or less, preferably 20 mol% or less.

[0169] Furthermore, the content ratio (total amount) of polyfunctional (meth)acrylate per 100 parts by mass of the compound represented by formula (1) above (partially thio(meth)acryloyl modified compound) is, for example, 0 parts by mass or more, preferably 3 parts by mass or more. Also, the content ratio (total amount) of polyfunctional (meth)acrylate per 100 parts by mass of the compound represented by formula (1) above (partially thio(meth)acryloyl modified compound) is, for example, 100 parts by mass or less, preferably 50 parts by mass or less.

[0170] Other polymerizable compounds include, for example, styrene, α-methylstyrene, vinyltoluene, vinylbiphenyl, and divinylbenzene. These can be used individually or in combination of two or more. The proportions of these compounds are set appropriately according to the purpose and application.

[0171] Other polymerizable compounds can be used alone or in combination of two or more. Preferred examples of other polymerizable compounds include fully thio(meth)acryloyl modified compounds and monofunctional (meth)acrylates.

[0172] For example, in the field of molded articles, as described later, from the viewpoint of curability and other polymerizable compounds, a completely thio(meth)acryloyl modified compound is preferred.

[0173] Furthermore, in the field of adhesives, as described later, other polymerizable compounds that are preferable from the viewpoint of refractive index and tackiness include monofunctional (meth)acrylates (excluding methyl methacrylate).

[0174] In polymerizable compositions, the content of other polymerizable compounds is appropriately set according to the purpose and application. For example, the content (total amount) of other polymerizable compounds relative to the total moles of polymerizable compounds is, for example, 0 mol% or more, preferably 5 mol% or more. Alternatively, the content (total amount) of other polymerizable compounds relative to the total moles of polymerizable compounds is, for example, 80 mol% or less, preferably 50 mol% or less.

[0175] Furthermore, the content ratio (total amount) of other polymerizable compounds relative to 100 parts by mass of the compound represented by formula (1) above (partially thio(meth)acryloyl modified compound) is, for example, 0 parts by mass or more, preferably 5 parts by mass or more. Also, the content ratio (total amount) of other polymerizable compounds relative to 100 parts by mass of the compound represented by formula (1) above (partially thio(meth)acryloyl modified compound) is, for example, 500 parts by mass or less, preferably 200 parts by mass or less.

[0176] (2) Additives Polymerizable compositions may optionally contain additives as components that do not undergo radical polymerization. Examples of additives include plasticizers, radical polymerization initiators, crosslinking agents, silane coupling agents, defoamers, leveling agents, antifungal agents, rust inhibitors, matting agents, flame retardants, thixotropes, 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 individually or in combination of two or more. The amount and timing of additive addition are determined appropriately according to the purpose and application.

[0177] Preferably, plasticizers are used as additives. That is, the polymerizable composition preferably contains a plasticizer.

[0178] Examples of plasticizers include compounds in which all of the mercapto groups of a trifunctional or more sulfur-containing polythiol form SXR groups.

[0179] Hereinafter, such compounds may be referred to as thio(meth)acryloyl unmodified compounds.

[0180] In the unmodified thio(meth)acryloyl, the thio(meth)acryloyl group does not bond (add) to any of the bonds of organic group A in formula (1) above, while the SXR group bonds (adds) to all (m+n) bonds of organic group A in formula (1) above.

[0181] Examples of unmodified thio(meth)acryloyl include the compound shown in formula (4) below.

[0182] [ka] (In equation (4), A, S, X, R, m, and n have the same meanings as A, S, X, R, m, and n in equation (1), respectively.)

[0183] Examples of compounds represented by formula (4) above include, preferably, compounds in which the organic group A in formula (4) is a GST residue, and compounds in which the organic group A in formula (4) is an FSH residue. More preferably, examples of compounds represented by formula (4) above include compounds 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).

[0184] [ka] (In equation (4-1), S, X, and R have the same meanings as S, X, and R in equation (1). In equation (4-1), the portion enclosed by the dashed line represents the organic group A (m+n=3) in equation (1).)

[0185] In formula (7-1) above, SXR groups are attached to all three bonding sites (m+n) of organic group A (GST residue) in formula (1) above. That is, the compound represented by formula (4-1) above is the compound in formula (1) above where m is 3 and n is 0. Hereinafter, the compound represented by formula (4-1) above may be referred to as the unmodified thio(meth)acryloyl of GST.

[0186] Examples of thio(meth)acryloyl undenatured forms of 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). Furthermore, examples of thio(meth)acryloyl undenatured forms of GST 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).

[0187] Unmodified thio(meth)acryloyl can be used alone or in combination with two or more other types.

[0188] Unmodified thio(meth)acryloyl has three or more (m+n) SXR groups. Therefore, unmodified thio(meth)acryloyl is used as a plasticizer that does not undergo radical polymerization.

[0189] There are no particular limitations on the method for obtaining the unmodified thio(meth)acryloyl. For example, the unmodified thio(meth)acryloyl can be obtained as a byproduct in the synthesis reaction of the compound represented by formula (1) above (described later).

[0190] Furthermore, polymerizable compositions containing unmodified thio(meth)acryloyl can be obtained, for example, as reaction products (reaction product compositions) in the production of the compound represented by formula (1) above.

[0191] In addition to the above-mentioned unmodified thio(meth)acryloyl, other known plasticizers can also be used. Examples of known plasticizers include benzoic acid esters, phthalate esters, terephthalate esters, isophthalate esters, adipic acid esters, sebacate acid esters, trimellitic acid esters, pyromellitic acid esters, phosphate esters, epoxy esters, glycol esters, and waxes. These can be used individually or in combination of two or more.

[0192] Preferably, the plasticizer is unmodified thio(meth)acryloyl. If the plasticizer contains unmodified thio(meth)acryloyl, the plasticizer can improve the flexibility of the cured resin product (described later) and suppress the decrease in the refractive index of the cured resin product (described later), or improve the refractive index.

[0193] In polymerizable compositions, the proportion of plasticizer (preferably thio(meth)acryloyl unmodified) is appropriately set according to the purpose and application.

[0194] For example, the content of the plasticizer (preferably unmodified thio(meth)acryloyl) relative to the total moles of the polymerizable compound is, for example, 0 mol% or more, preferably 5 mol% or more. Also, the content of the plasticizer (preferably unmodified thio(meth)acryloyl) relative to the total moles of the polymerizable compound is, for example, 80 mol% or less, preferably 50 mol% or less.

[0195] Furthermore, the content ratio of the plasticizer (preferably unmodified thio(meth)acryloyl) per 100 parts by mass of the total amount of the compound represented by formula (1) above (partially modified thio(meth)acryloyl) is, for example, 0 parts by mass or more, preferably 5 parts by mass or more. Also, the content ratio of the plasticizer (preferably unmodified thio(meth)acryloyl) per 100 parts by mass of the total amount of the compound represented by formula (1) above (partially modified thio(meth)acryloyl) is, for example, 500 parts by mass or less, preferably 50 parts by mass or less.

[0196] (3)Applications According to the above polymerizable composition (uncured resin), a cured resin product can be obtained that possesses excellent refractive index and curability, as well as excellent flexibility.

[0197] Therefore, the above polymerizable composition is suitably used in various industrial fields. For this reason, the above polymerizable composition (uncured resin) is suitably used as an optical polymerizable composition.

[0198] Applications of polymerizable compositions include, for example, adhesives. An adhesive is an uncured resin composition that, upon curing, forms a cured adhesive product (a cured resin product described later). The cured adhesive product adheres to the substrates. The substrates to which the adhesive can be applied are not particularly limited, but examples include paper, cloth and leather, resin sheets, rubber sheets, foams, metal foils, glass and wood.

[0199] Such adhesives include the polymerizable composition described above. In other words, the above adhesive yields a cured resin product with excellent refractive index and excellent flexibility. Therefore, the above adhesive is suitably used as an optical adhesive.

[0200] Furthermore, the applications of polymerizable compositions are not limited to adhesives.

[0201] Other applications of polymerizable compositions include, for example, coatings and paints, preferably optical coatings and optical paints.

[0202] Other applications of polymerizable compositions include molded article materials and adhesive materials, preferably optical molded article materials and optical adhesive materials.

[0203] 3. Method for producing compounds, and method for producing polymerizable compositions (1) Raw materials The compound represented by formula (1) above can be synthesized, for example, by the reaction of the above-mentioned trifunctional or more sulfur-containing polythiol with a first modifying agent for forming the SXR group in formula (1) and a second modifying agent for forming the thio(meth)acryloyl group in formula (1).

[0204] (a) Polythiol Examples of polythiols include the three or more sulfur-containing polythiols mentioned above. In other words, a polythiol is an m+n valency (where m+n is an integer of 3 or more) polythiol containing a sulfur atom.

[0205] More specifically, examples of polythiols include the above-mentioned sulfur-containing trithiol, sulfur-containing tetrathiol, sulfur-containing pentatiol, sulfur-containing hexatiol, and sulfur-containing octatiol. From the viewpoint of availability and reactivity, the above-mentioned sulfur-containing trithiol and sulfur-containing tetrathiol are preferred as polythiols.

[0206] As a sulfur-containing trithiol, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (GST) is more preferred from the viewpoint of availability and reactivity. 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (GST) is represented, for example, by the following formula (5).

[0207] [ka]

[0208] As a sulfur-containing tetrathiol, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (FSH) is more readily available and more reactive. 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (FSH) is represented, for example, by the following formula (6).

[0209] [ka]

[0210] Polythiols can be used alone or in combination of two or more types. Preferably, polythiols are used alone. Preferred polythiols include the polythiol represented by formula (5) above, and the polythiol represented by formula (6) above, used alone. In other words, the polythiol is more preferably represented by formula (5) or formula (6) above.

[0211] More preferably, from the viewpoint of availability and reactivity, the polythiol is a sulfur-containing trithiol, and particularly preferably, the polythiol represented by the above formula (5) (4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (GST)).

[0212] (b) First denaturing agent The first modifying agent is a compound that encapsulates the molecular ends of the above-mentioned polythiol and does not form a (meth)acryloyl group. In other words, the first modifying agent is a compound that modifies the mercapto group of the above-mentioned trifunctional or more sulfur-containing polythiol to an SXR group.

[0213] Examples of the first modifying agent include the compound shown in formula (8) below.

[0214] [ka] (In formula (8), X and R have the same meanings as X and R in formula (1). Y represents a halogen or hydroxyl group.)

[0215] In formula (8) above, X and R have the same meanings as X and R in formula (1). Y represents a halogen or a hydroxyl group. Examples of halogens include fluorine, chlorine, bromine, and iodine. Preferably, the halogens are chlorine and bromine.

[0216] In formula (8) above, when Y is a halogen and X is a single bond, halogenated hydrocarbons can be used as the first modifying agent. Examples include alkyl halides, aryl halides, and aralkyl halides. Examples of alkyl halides include methyl fluoride, methyl chloride, methyl bromide, methyl iodide, ethyl fluoride, ethyl chloride, ethyl bromide, and ethyl iodide. Examples of aryl halides include phenyl fluoride, phenyl chloride, phenyl bromide, and phenyl iodide. Examples of aralkyl halides include benzyl fluoride, benzyl chloride, benzyl bromide (benzyl bromide), and benzyl iodide. These can be used alone or in combination of two or more. Preferably, the first modifying agent is an aralkyl halide, and more preferably, benzyl bromide (benzyl bromide).

[0217] In formula (8) above, when Y is a halogen and X is a carbonyl group, a halogenated acyl can be used as the first modifying agent. Examples of halogenated acyls 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 can be used alone or in combination of two or more. Preferably, the first modifying agent is benzoyl chloride, phenylacetyl chloride (phenylacetyl chloride), and phenylpropionyl chloride (phenylpropionyl chloride).

[0218] In formula (8) above, when Y is a hydroxyl group and X is a carbonyl group, a carboxylic acid can be used as the first modifying agent. Examples of carboxylic acids include monocarboxylic acids and their anhydrides. Examples of monocarboxylic acids include aliphatic monocarboxylic acids, aromatic monocarboxylic acids, and aromatic aliphatic monocarboxylic acids. Examples of aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, caproic acid, octic acid, lauric acid, myristic acid, palmitic acid, stearic acid, 2-ethylhexanoic acid, cyclohexanecarboxylic acid, and cyclopentanecarboxylic acid. Examples of aromatic monocarboxylic acids include benzoic acid and toluic acid. An example of an aromatic aliphatic monocarboxylic acid is diphenylacetic acid. These can be used alone or in combination of two or more. Preferably, the first modifying agent is an aliphatic monocarboxylic acid and its anhydride, more preferably acetic acid and its anhydride, and even more preferably acetic anhydride.

[0219] (c) Second denaturing agent The second modifying agent is a compound that encapsulates the molecular ends of the above-mentioned polythiol and forms a (meth)acryloyl group. In other words, the second modifying agent is a compound that modifies the mercapto group of the above-mentioned trifunctional or more sulfur-containing polythiol to a thio(meth)acryloyl group.

[0220] Examples of secondary modifying agents include (meth)acrylate halides and (meth)acrylate anhydrides. Examples of (meth)acrylate halides include (meth)acrylate chloride, (meth)acrylate bromide, and (meth)acrylate iodide. Examples of (meth)acrylate anhydrides include acrylic anhydride and methacrylic anhydride. These can be used individually or in combination of two or more types.

[0221] Furthermore, as a second modifying agent, two or more compounds can be used in combination in a way that allows them to form a (meth)acryloyl group.

[0222] More specifically, the second denaturing agent may include, for example, (meth)acrylic acid and a dehydrating condensing agent. Examples of dehydrating condensing agents include imidazole-based condensing agents, triazine-based condensing agents, phosphonium-based condensing agents, uronium-based condensing agents, and halouronium-based condensing agents. These can be used alone or in combination of two or more.

[0223] Furthermore, the second modifying agent may include, for example, a propionic acid derivative and a basic compound. Examples of propionic acid derivatives include those described in Japanese Patent Publication No. 4-29967. More specifically, examples of propionic acid derivatives include β-chloropropionic acid, β-bromopropionic acid, β-hydroxypropionic acid toluenesulfonyl ester, β-hydroxypropionic acid benzenesulfonyl ester, β-hydroxypropionic acid methanesulfonyl ester, α-methyl-β-chloropropionic acid, α-methyl-β-bromopropionic acid, α-methyl-β-hydroxypropionic acid toluenesulfonyl ester, α-methyl-β-hydroxypropionic acid benzenesulfonyl ester, α-methyl-β-hydroxypropionic acid methanesulfonyl ester, and their acid halides. More specifically, acid halides include β-chloropropionate (3-chloropropionate), β-bromopropionate, α-methyl-β-chloropropionate, and α-methyl-β-bromopropionate. These can be used alone or in combination of two or more. Examples of bases include sodium hydroxide, potassium hydroxide, triethylamine, and pyridine. These can be used alone or in combination of two or more.

[0224] (2) Mixing ratio and reaction conditions In the synthesis of the compound shown in formula (1) above, first, a sulfur-containing polythiol with three or more functionalities, a first modifier, and a second modifier are mixed in appropriate proportions as reaction raw materials. Then, these reaction raw materials are reacted under appropriate conditions. The reaction method, reaction sequence, and reaction conditions are set appropriately according to the type of reaction raw materials.

[0225] More specifically, this method first involves preparing a sulfur-containing polythiol with three or more functions (a polythiol containing a sulfur atom with an m+n valency (where m+n is an integer of 3 or more)) (preparation step).

[0226] Next, in this method, a sulfur-containing polythiol with three or more functionalities is reacted with a first modifying agent and a second modifying agent (reaction step).

[0227] In the reaction process, the reaction order of the first and second denaturing agents is not particularly limited. 。 For example, a sulfur-containing polythiol with three or more functionalities may be reacted simultaneously with a first modifier and a second modifier. Alternatively, the sulfur-containing polythiol with three or more functionalities may be reacted first with the first modifier, and then the reaction products may be reacted with the second modifier. Alternatively, for example, the sulfur-containing polythiol with three or more functionalities may be reacted first with the second modifier, and then the reaction products may be reacted with the first modifier.

[0228] From the viewpoint of productivity and reactivity, it is preferable to first react a trifunctional or more sulfur-containing polythiol with a first modifying agent, and then react these reaction products with a second modifying agent.

[0229] In other words, preferably, a trifunctional or more sulfur-containing polythiol is first modified with a first modifying agent to add an SXR group. Then, these reaction products are modified with a second modifying agent to add a thio(meth)acryloyl group.

[0230] More specifically, in the reaction step, the above-mentioned trifunctional or more sulfur-containing polythiol and the above-mentioned first modifying agent are first reacted by an appropriate method (first reaction step).

[0231] The formulation, reaction method, and reaction conditions in the first reaction step are appropriately selected, for example, depending on the type of first denaturing agent.

[0232] Examples of reactions between a trifunctional or more sulfur-containing polythiol and a first modifying agent include nucleophilic substitution reactions, nucleophilic acylation reactions, cross-coupling reactions, and dehydration condensation reactions.

[0233] For example, when the first modifying agent contains a halogenated hydrocarbon, the trifunctional or more sulfur-containing polythiol and the first modifying agent undergo a nucleophilic substitution reaction in the presence of a known basic compound to produce the compound shown in formula (1) above. More specifically, the basic compound removes a proton from the trifunctional or more sulfur-containing polythiol, producing a nucleophile. Then, the nucleophile derived from the trifunctional or more sulfur-containing polythiol undergoes a nucleophilic substitution reaction with the halogenated hydrocarbon. Examples of basic compounds include metal alkylates and amine compounds. In such a reaction, the mixing ratio of the trifunctional or more sulfur-containing polythiol and the first modifying agent is adjusted based on the equivalent ratio of halogen atoms in the first modifying agent (halogenated hydrocarbon) to mercapto groups in the sulfur-containing polythiol.

[0234] The equivalent ratio of halogen atoms in the first modifying agent (halogenated hydrocarbon) to mercapto groups in the sulfur-containing polythiol (halogen atoms / mercapto groups) is, for example, 0.1 or more, preferably 0.3 or more. Furthermore, the equivalent ratio of halogen atoms in the first modifying agent (halogenated hydrocarbon) to mercapto groups in the sulfur-containing polythiol (halogen atoms / mercapto groups) is, for example, 0.9 or less, preferably 0.8 or less.

[0235] When the first modifying agent contains a halogenated hydrocarbon, the reaction conditions for the nucleophilic substitution reaction are appropriately selected depending on the type of sulfur-containing polythiol with three or more functions and the type of the first modifying agent. For example, the reaction temperature is, for example, -20°C or higher, preferably -10°C or higher. Also, the reaction temperature is, for example, 50°C or lower, preferably 30°C or lower. Also, the reaction time is, for example, 3 hours or more, preferably 6 hours or more. Also, the reaction time is, for example, 48 hours or less, preferably 24 hours or less. Furthermore, the sulfur-containing polythiol with three or more functions and the first modifier may be reacted without a solvent, or with a known solvent. The type and amount of solvent added are set as appropriate. Furthermore, the sulfur-containing polythiol with three or more functions and the first modifier may be reacted without a catalyst, or with a known catalyst. The type and amount of catalyst added are set as appropriate.

[0236] Furthermore, for example, if the first modifying agent contains an acyl halogenate, the trifunctional or more sulfur-containing polythiol and the first modifying agent undergo a nucleophilic acylation reaction in the presence of the basic compound described above to produce the compound shown in formula (1). More specifically, the basic compound removes a proton from the trifunctional or more sulfur-containing polythiol, producing a nucleophile. Then, the nucleophile derived from the trifunctional or more sulfur-containing polythiol and the acyl halogenate undergo a nucleophilic acylation reaction. In such a reaction, the mixing ratio of the trifunctional or more sulfur-containing polythiol and the first modifying agent is adjusted based on the equivalent ratio of halogen atoms in the first modifying agent (acyl halogenate) to mercapto groups in the sulfur-containing polythiol.

[0237] The equivalent ratio of halogen atoms in the first modifying agent (acyl halide) to the mercapto groups in the sulfur-containing polythiol (halogen atoms / mercapto groups) is, for example, 0.1 or more, preferably 0.3 or more. Furthermore, the equivalent ratio of halogen atoms in the first modifying agent (acyl halide) to the mercapto groups in the sulfur-containing polythiol (halogen atoms / mercapto groups) is, for example, 0.9 or less, preferably 0.8 or less.

[0238] When the first modifying agent contains an acyl halogenate, the reaction conditions for the nucleophilic acylation reaction are appropriately selected depending on the type of sulfur-containing polythiol with three or more functions and the type of the first modifying agent. For example, the reaction temperature is, for example, -20°C or higher, preferably -10°C or higher. Alternatively, 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. Alternatively, the reaction time is, for example, 48 hours or less, preferably 24 hours or less. The sulfur-containing polythiol with three or more functions and the first modifying agent may react without a solvent or with a known solvent. The type and amount of solvent added are set appropriately. The sulfur-containing polythiol with three or more functions and the first modifying agent may react without a catalyst or with a known catalyst. The type and amount of catalyst added are set appropriately.

[0239] Furthermore, for example, if the first modifying agent contains a carboxylic acid, the trifunctional or more sulfur-containing polythiol and the first modifying agent (carboxylic acid) undergo a dehydration condensation reaction in the presence of the basic compound to produce the compound shown in formula (1) above. In such a reaction, the mixing ratio of the trifunctional or more sulfur-containing polythiol and the first modifying agent is adjusted based on the equivalent ratio of carboxyl groups in the first modifying agent (carboxylic acid) to mercapto groups in the sulfur-containing polythiol. The equivalent ratio of carboxyl groups in the first modifying agent (carboxylic acid) to mercapto groups in the sulfur-containing polythiol (carboxyl group / mercapto group) is, for example, 0.1 or more, preferably 0.5 or more. Also, the equivalent ratio of carboxyl groups in the first modifying agent (carboxylic acid) to mercapto groups in the sulfur-containing polythiol (carboxyl group / mercapto group) is, for example, 0.9 or less, preferably 0.8 or less.

[0240] When the first modifying agent contains a carboxylic acid, the reaction conditions for the dehydration condensation reaction are appropriately selected depending on the type of sulfur-containing polythiol with three or more functions and the type of the first modifying agent. For example, the reaction temperature is, for example, -20°C or higher, preferably -10°C or higher. Alternatively, 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. Alternatively, the reaction time is, for example, 48 hours or less, preferably 24 hours or less. The sulfur-containing polythiol with three or more functions and the first modifying agent may react without a solvent or with a known solvent. The type and amount of solvent added are set appropriately. The sulfur-containing polythiol with three or more functions and the first modifying agent may react without a catalyst or with a known catalyst. The type and amount of catalyst added are set appropriately.

[0241] As described above, in the first reaction step, at least a portion of the mercapto groups (SH groups) of the polythiol are modified by the first modifying agent, forming SXR groups. The remaining mercapto groups (SH groups) of the polythiol (hereinafter referred to as the remaining mercapto groups) remain unmodified. This yields the primary reaction product. The primary reaction product is the reaction product from the first reaction step.

[0242] In this method, after the first reaction step described above, the reaction product from the first reaction step (primary reaction product) is reacted with the second denaturing agent described above by an appropriate method (second reaction step).

[0243] The formulation, reaction method, and reaction conditions in the second reaction step are appropriately selected, for example, depending on the type of second denaturing agent.

[0244] For example, when the second modifying agent contains (meth)acrylic acid halide, a condensation reaction occurs between the residual mercapto groups of the primary reaction product and the halogen atoms of the (meth)acrylic acid halide. As a result, thio(meth)acryloyl groups are formed. In such a reaction, the blending ratio of the second modifying agent is adjusted based on the equivalent ratio of halogen atoms in the second modifying agent ((meth)acrylic acid halide) to the residual mercapto groups of the primary reaction product.

[0245] The equivalent ratio of halogen atoms in the second modifying agent ((meth)acrylic acid halide) to the residual mercapto groups of the primary reaction product (halogen atoms / residual mercapto groups) is, for example, 0.8 or more, preferably 0.9 or more. Further, the equivalent ratio of halogen atoms in the second modifying agent ((meth)acrylic acid halide) to the residual mercapto groups of the primary reaction product (halogen atoms / residual mercapto groups) is, for example, 1.5 or less, preferably 1.3 or less.

[0246] When the second modifying agent contains (meth)acrylic acid halide, the reaction conditions are appropriately selected according to the type of the trifunctional or higher sulfur-containing polythiol, the type of the first modifying agent, and the type of the second modifying agent. Further, the primary reaction product and the second modifying agent may be reacted in the absence of a solvent, or may be reacted in a known solvent. The type and addition amount of the solvent are appropriately set. Further, the primary reaction product and the second modifying agent may be reacted in the absence of a catalyst, or may be reacted in the presence of a known catalyst. The type and addition amount of the catalyst are appropriately set.

[0247] For example, when the second modifying agent contains (meth)acrylic anhydride, a condensation reaction between the residual mercapto groups of the primary reaction product and the (meth)acrylic anhydride proceeds by a known method. As a result, thio(meth)acryloyl groups are formed. In such a reaction, the blending ratio of the second modifying agent is adjusted based on the equivalent ratio of the second modifying agent ((meth)acrylic anhydride) to the residual mercapto groups of the primary reaction product.

[0248] The equivalent ratio of the second modifier ((meth)acrylic anhydride) to the residual mercapto groups in the primary reaction product ((meth)acrylic anhydride / residual mercapto groups) is, for example, 0.8 or more, preferably 0.9 or more. Further, the equivalent ratio of the second modifier ((meth)acrylic anhydride) to the residual mercapto groups in the primary reaction product ((meth)acrylic anhydride / residual mercapto groups) is, for example, 1.5 or less, preferably 1.3 or less.

[0249] When the second modifier contains (meth)acrylic anhydride, the reaction conditions are appropriately selected according to the type of trifunctional or higher functional sulfur-containing polythiol, the type of the first modifier, and the type of the second modifier. In addition, the primary reaction product and the second modifier may be reacted in the absence of a solvent, or may be reacted in a known solvent. The type and addition amount of the solvent are appropriately set. Further, the primary reaction product and the second modifier may be reacted in the absence of a catalyst, or may be reacted in the presence of a known catalyst. The type and addition amount of the catalyst are appropriately set.

[0250] For example, when the second modifier contains (meth)acrylic anhydride, the residual mercapto groups of the primary reaction product and (meth)acrylic anhydride undergo a condensation reaction by a known method. In such a reaction, the blending ratio of the second modifier is adjusted based on the equivalent ratio of the second modifier ((meth)acrylic anhydride) to the residual mercapto groups in the primary reaction product.

[0251] The equivalent ratio of the second modifier ((meth)acrylic anhydride) to the residual mercapto groups in the primary reaction product ((meth)acrylic anhydride / residual mercapto groups) is, for example, 0.8 or more, preferably 0.9 or more. Further, the equivalent ratio of the second modifier ((meth)acrylic anhydride) to the residual mercapto groups in the primary reaction product ((meth)acrylic anhydride / residual mercapto groups) is, for example, 1.5 or less, preferably 1.3 or less.

[0252] When the second modifying agent contains (meth)acrylic anhydride, the reaction conditions are appropriately selected depending on the type of trifunctional or higher sulfur-containing polythiol, the type of first modifying agent, and the type of second modifying agent. The primary reaction product and the second modifying agent may react without a solvent or with a known solvent. The type and amount of solvent added are set appropriately. The primary reaction product and the second modifying agent may react without a catalyst or with a known catalyst. The type and amount of catalyst added are set appropriately.

[0253] Furthermore, if the second modifying agent contains (meth)acrylic acid and a dehydrating condensing agent, the remaining mercapto groups of the primary reaction product and (meth)acrylic acid undergo a condensation reaction in the presence of the dehydrating condensing agent. This forms a thio(meth)acryloyl group. In such a reaction, the proportion of the second modifying agent is adjusted based on the equivalent ratio of (meth)acrylic acid in the second modifying agent to the remaining mercapto groups of the primary reaction product.

[0254] The equivalent ratio of (meth)acrylic acid in the second modifying agent to the remaining mercapto groups in the primary reaction product ((meth)acrylic acid / remaining mercapto groups) is, for example, 0.8 or higher, preferably 0.9 or higher. Furthermore, the equivalent ratio of (meth)acrylic acid in the second modifying agent to the remaining mercapto groups in the primary reaction product ((meth)acrylic acid / remaining mercapto groups) is, for example, 1.5 or lower, preferably 1.3 or lower.

[0255] When the second modifying agent contains (meth)acrylic acid and a dehydrating condensation agent, the reaction conditions are appropriately selected depending on the type of trifunctional or higher sulfur-containing polythiol, the type of first modifying agent, and the type of second modifying agent. The primary reaction product and the second modifying agent may react without a solvent or with a known solvent. The type and amount of solvent added are set appropriately. The primary reaction product and the second modifying agent may react without a catalyst or with a known catalyst. The type and amount of catalyst added are set appropriately.

[0256] Furthermore, if the second modifying agent 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 Japanese Patent Publication No. 4-29967. More specifically, first, the remaining mercapto groups of the primary reaction product and the propionic acid derivative undergo a condensation reaction. Next, the halogens of these reaction products (condensates) are treated (eliminated) with the base compound, forming ethylenically unsaturated bonds. This forms a thio(meth)acryloyl group. In such a reaction, the blending ratio of the second modifying agent is adjusted based on the equivalent ratio of the propionic acid derivative in the second modifying agent to the remaining mercapto groups of the primary reaction product.

[0257] The equivalent ratio of the propionic acid derivative in the second modifying agent to the remaining mercapto groups in the primary reaction product (propionic acid derivative / remaining mercapto groups) is, for example, 0.8 or higher, preferably 0.9 or higher. Furthermore, the equivalent ratio of the propionic acid derivative in the second modifying agent to the remaining mercapto groups in the primary reaction product (propionic acid derivative / remaining mercapto groups) is, for example, 1.5 or lower, preferably 1.3 or lower.

[0258] When the second modifying agent contains a propionic acid derivative and a basic compound, the reaction conditions are appropriately selected depending on the type of trifunctional or higher sulfur-containing polythiol, the type of first modifying agent, and the type of second modifying agent. The primary reaction product and the second modifying agent may react without a solvent or with a known solvent. The type and amount of solvent added are set appropriately. The primary reaction product and the second modifying agent may react without a catalyst or with a known catalyst. The type and amount of catalyst added are set appropriately.

[0259] As described above, in the second reaction step, the remaining mercapto groups of the primary reaction product are modified, and thio(meth)acryloyl groups are formed. This yields the secondary reaction product, which is the reaction product of the second reaction step.

[0260] In the method described above, some of the mercapto groups of the trifunctional or more sulfur-containing polythiols are modified by the first denaturing agent. As a result, an SXR group is attached to the residue (organic group A) of the trifunctional or more sulfur-containing polythiol.

[0261] Furthermore, in the above method, the remainder of the mercapto groups of the trifunctional or more sulfur-containing polythiol is modified by the second denaturing agent. As a result, a thio(meth)acryloyl group is bonded to the residue (organic group A) of the trifunctional or more sulfur-containing polythiol.

[0262] As a result, the compound represented by formula (1) above (a partially thio(meth)acryloyl modified compound) is formed by the method described above.

[0263] In other words, the reaction product of a trifunctional or more sulfur-containing polythiol, a first modifier, and a second modifier contains the compound represented by formula (1) above (a partially thio(meth)acryloyl modified compound). That is, the reaction product of a trifunctional or more sulfur-containing polythiol, a first modifier, and a second modifier is a polymerizable composition.

[0264] The content of the compound represented by formula (1) (partially thio(meth)acryloyl modified compound) in the reaction product (polymerizable composition) is, for example, within the range described above. Furthermore, if necessary, the reaction product can be purified by appropriate methods to adjust the content of the compound represented by formula (1) (partially thio(meth)acryloyl modified compound) to within the range described above.

[0265] Furthermore, in the above reaction, a fully modified thio(meth)acryloyl compound may be formed as a by-product. In such cases, the reaction product (polymerizable composition) contains the fully modified thio(meth)acryloyl compound.

[0266] The content ratio of the fully thio(meth)acryloyl modified product in the reaction product (polymerizable composition) falls within the above range, for example. If necessary, the reaction product can be purified by an appropriate method to adjust the content ratio of the fully thio(meth)acryloyl modified product to the above range.

[0267] In addition, in the above reaction, an unmodified thio(meth)acryloyl product may be formed as a by-product in some cases. In such cases, the above reaction product (polymerizable composition) contains the unmodified thio(meth)acryloyl product as a plasticizer.

[0268] The content ratio of the unmodified thio(meth)acryloyl product in the reaction product (polymerizable composition) falls within the above range, for example. If necessary, the reaction product can be purified by an appropriate method to adjust the content ratio of the unmodified thio(meth)acryloyl product to the above range.

[0269] It should be noted that the first modifier, the second modifier, and the method of reacting these are not limited to the above. For example, an ene-thiol reaction can be mentioned as the reaction between a sulfur-containing polythiol having three or more functional groups and the first modifier. Also, the first strange modifier includes, for example, compounds capable of undergoing an ene-thiol reaction with the above-described sulfur-containing polythiol having three or more functional groups. Examples of such compounds include vinyl compounds. Examples of the vinyl compounds include styrene, methylstyrene and butylstyrene. These can be used alone or in combination of two or more kinds.

[0270] When a vinyl compound is used as the first modifier, the sulfur-containing polythiol having three or more functional groups and the first modifier (vinyl compound) undergo an ene-thiol reaction in the presence of a known radical initiator, thereby modifying the mercapto groups of the sulfur-containing polythiol having three or more functional groups into SXR groups where X represents a single bond and R represents a hydrocarbon group derived from the vinyl compound.

[0271] 4. Cured Resin The resin cured product is formed by curing the polymerizable composition described above by a known method. In other words, the resin cured product includes, and preferably consists of, the cured polymerizable composition described above.

[0272] More specifically, to obtain a cured resin product, for example, a polymerizable composition of the desired shape is irradiated with active energy rays and / or heated.

[0273] Examples of active energy rays include ultraviolet rays and electron beams. The wavelength of the active energy rays is set appropriately according to the purpose and application. The integrated light intensity is, for example, 0.1 mJ / cm². 2 That concludes the explanation. Furthermore, the integrated light intensity is, for example, 5000 mJ / cm². 2 Preferably, 3000 mJ / cm² 2 The following applies: Illuminance is, for example, 0.01 mW / cm². 2 That's all. Also, the illuminance is, for example, 500 mW / cm². 2 Preferably, 300 mW / cm² 2 The following applies:

[0274] The heating conditions are set appropriately according to the purpose and application. For example, the heating temperature is 40°C or higher, preferably 50°C or higher. Alternatively, the heating temperature is 200°C or lower, preferably 100°C or lower. The heating time is 1 minute or more, preferably 5 minutes or more. Alternatively, the heating time is 10 hours or less, preferably 5 hours or less.

[0275] This allows the polymerizable composition to be subjected to radical polymerization (photo-radical polymerization and / or thermal radical polymerization). In other words, the polymerizable composition can be cured by active energy rays and / or heat. As a result, a cured resin product (cured product of the polymerizable composition) is obtained.

[0276] Furthermore, the method for obtaining the cured resin product is not limited to the above. For example, the polymerizable composition described above can be used to prepare a two-component curable resin composition. More specifically, the polymerizable composition described above can be reacted with a hydroxyl group-containing (meth)acrylate to prepare an acrylic polyol. Then, the acrylic polyol (main component) can be reacted with a known curing agent (e.g., polyisocyanate) to cure it. As a result, the cured resin product described above can be obtained.

[0277] The above-mentioned cured resin product contains the cured product of the above-mentioned polymerizable composition. The above-mentioned polymerizable composition contains the above-mentioned compound. Therefore, the above-mentioned cured resin product possesses both excellent refractive index and excellent flexibility.

[0278] More specifically, the refractive index of the cured resin is relatively high. The refractive index of the cured resin is, for example, 1.45 or higher, preferably 1.50 or higher, more preferably 1.55 or higher, even more preferably 1.60 or higher, and particularly preferably 1.61 or higher. Alternatively, the refractive index of the cured resin is, for example, 1.80 or lower, preferably 1.70 or lower. The refractive index is measured according to the examples described later.

[0279] The tensile storage modulus (E') of the cured resin at 25°C is relatively low. For example, the tensile storage modulus (E') of the cured resin at 25°C is 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. Alternatively, the tensile storage modulus (E') of the cured resin at 25°C is 1 MPa or more. The tensile storage modulus (E') is measured according to the examples described later.

[0280] The above-mentioned cured resin products (cured products of polymerizable compositions) are suitably used in various industrial fields. Examples of applications for cured resin products include molded articles (resin molded products) and adhesives. Adhesives are a preferred application for cured resin products.

[0281] Molded articles (resin molded articles) are obtained by curing a polymerizable composition to any shape. The shape of the molded article (resin molded article) is not particularly limited. Examples of molded articles include lenses, films, sheets, and boards, with lenses and films being preferred.

[0282] The adhesive is a cured polymerizable composition. The adhesive has a relatively low glass transition temperature (below 0°C) and is tacky. The substrate to which the adhesive can be applied is not particularly limited, but examples include paper, cloth and leather, resin sheets, rubber sheets, foams, metal foils, glass and wood.

[0283] Furthermore, the above-mentioned cured resin products, molded products, films, and adhesives possess both excellent refractive index and excellent flexibility.

[0284] Therefore, the above-mentioned cured resins, molded articles, films, and adhesives are suitably used in the field of optics. More specifically, the cured resins are suitably used as cured resins for optical applications. Examples of fields in which the cured resins are used include optical transparent adhesives, coatings for optical elements, adhesives for thin-film glass films, protective films for thin-film glass films, polarizing films for liquid crystal displays, and polarizing films for organic EL displays. The molded articles are suitably used as optical components (e.g., optical lenses and optical fibers). The films are suitably used as optical films. The adhesives are suitably used as optical adhesives.

[0285] Furthermore, the resin compound described above contains a sulfur atom. Therefore, the cured resin, molded article, film and adhesive described above have excellent adhesion to metal substrates. Accordingly, the cured resin, molded article, film and adhesive are suitably used, for example, in the fields of construction materials, electronic components, semiconductors, member sealing, automotive components, aerospace components, and sporting goods. Examples of construction materials include barrier materials, roofing materials, solar panel materials, battery packaging materials, window materials, outdoor flooring materials, lighting protection materials, automotive members, signboards, and stickers. Examples of electronic components include electronic material members and laminates for electric / electronic circuits; more specific examples include flexible copper-clad laminates, coverlays, bonding sheets, copper foil with resin, multilayer printed wiring boards, capacitors, underfill materials, interchip fills for 3D-LSI, insulating sheets, heat dissipation substrates, and metal foil adhesives for heat dissipation films. Note that the above fields are merely examples, and the application is not limited thereto.

Examples

[0286] Specific numerical values such as blending ratios (content ratios), physical property values, and parameters used in the following description can be substituted with the upper limit values (values defined as "not more than" or "less than") or lower limit values (values defined as "not less than" or "more than") of the corresponding descriptions such as blending ratios (content ratios), physical property values, and parameters described in the above "Description of Embodiments" section. Unless otherwise specified in the following description, "parts" and "%" are based on mass.

[0287] <A. Synthesis of Compounds> Example A1 (1) First reaction step 48.0 g (184.3 mmol) of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (trifunctional sulfur-containing polythiol (GST)) was charged into a four-necked flask equipped with a stirrer, a thermometer, a nitrogen introduction line and a dropping funnel. Next, 200 mL of dichloromethane was added to the flask to dissolve GST in dichloromethane.

[0288] Next, 41.0 g of triethylamine (base catalyst, 405.4 mmol) was slowly added to the flask while stirring.

[0289] Next, the solution in the flask was cooled in an ice bath. Then, while maintaining the temperature inside the flask below 10°C, 51.8 g of benzoyl chloride (first denaturing agent, 368.5 mmol) was added dropwise to the flask.

[0290] After the dropwise addition was complete, the ice bath was removed and the temperature inside the flask was allowed to return to room temperature. The reaction product in the flask was then stirred overnight. This allowed the benzoyl group (XR in formula (1)) derived from benzoyl chloride to form.

[0291] Subsequently, 300 mL of water and 200 mL of dichloromethane were added to the reaction product in the flask. The organic phase was then separated by liquid-liquid extraction. Next, the organic phase was washed with dilute hydrochloric acid. Then, the organic phase was washed with saturated sodium bicarbonate aqueous solution. Finally, the solvent in the organic phase was removed by distillation using an evaporator. This yielded the crude product.

[0292] The crude product was diluted with 100 mL of dichloromethane to obtain a diluted solution. The diluted solution was passed through 100 mL of silica gel. The diluted solution was then eluted using 300 mL of dichloromethane. The eluted diluted solution was then concentrated using an evaporator. This yielded 83.4 g of the primary reaction product. 。 The primary reaction product was a partially benzoylated GST.

[0293] In the above reaction, 2 / 3 equivalents of the mercapto groups (trifunctional) of GST were benzoylated.

[0294] (2) Second reaction step 30.0 g of the primary reaction product was placed in a four-necked flask equipped with a stirrer, thermometer, nitrogen introduction line, and dropping funnel. Next, 50 mL of dichloromethane was added to the flask to dilute the primary reaction product with dichloromethane.

[0295] Next, the diluted solution in the flask was cooled in an ice bath. Then, while maintaining the temperature inside the flask below 40°C, 9.77 g of 3-chloropropionyl chloride (second denaturing agent, 77.0 mmol) was added dropwise to the flask.

[0296] Next, the reaction product in the flask was stirred at room temperature for 48 hours. Then, 100 mL of pure water was added to the flask. After that, the organic phase was separated by liquid-liquid extraction. The organic phase was then washed twice with 100 mL of saturated sodium bicarbonate aqueous solution. Finally, the solvent in the organic phase was removed by distillation using an evaporator.

[0297] Next, the reaction product was placed in a four-necked flask equipped with a thermometer and a dropping funnel. 30 mg of 4-methoxyphenol (polymerization inhibitor) was then added to the flask. The contents of the flask were then stirred at room temperature to dissolve the 4-methoxyphenol.

[0298] Next, the diluted solution in the flask was cooled in an ice bath. Then, while maintaining the temperature inside the flask below 40°C, 8.44 g (83.4 mmol) of triethylamine (second denaturing agent, base) was added dropwise to the flask. Next, the reaction product in the flask was stirred at room temperature for 1 hour. This treated the reaction product with the base, forming an acryloyl group derived from 3-chloropropionyl chloride.

[0299] Subsequently, 1M hydrochloric acid (300 mL) was added to the reaction product in the flask. The organic phase was then separated by liquid-liquid extraction.

[0300] Next, the organic phase was passed through silica gel (30 mL). 30 mg of 4-methoxyphenol (polymerization inhibitor) was added to the organic phase. Finally, the organic phase was concentrated under reduced pressure.

[0301] This yielded 32.1 g of a colorless and transparent secondary reaction product (hereinafter referred to as Bz2.0-GSTA). The secondary reaction products were benzoyl and acrylic compounds of GST.

[0302] In the above reaction, one-third of the mercapto groups (trifunctional) of GST were acrylicated.

[0303] The secondary reaction product was analyzed by high-performance liquid chromatography (HPLC). The reaction product was a polymerizable composition containing the following components in the following proportions.

[0304] GST trithio(meth)acryloyl modified compound 1.6 mol% (LC%) Dithio(meth)acryloyl modified form of GST 15.2 mol% (LC%) Monothio(meth)acryloyl modified form of GST: 41.7 mol% (LC%) GST thio(meth)acryloyl undenatured 41.5 mol% (LC%)

[0305] The dithio(meth)acryloyl modified form of GST and the monothio(meth)acryloyl modified form of GST are the compounds shown in formula (1) above. The trithio(meth)acryloyl modified form of GST is the compound shown in formula (7) above. The thio(meth)acryloyl unmodified form of GST is the compound shown in formula (4) above.

[0306] The average number of (meth)acryloyl groups in the combined trithio(meth)acryloyl variant of GST, the dithio(meth)acryloyl variant of GST, and the monothio(meth)acryloyl variant of GST was 1.31.

[0307] Example A2 (1) First reaction step 48.0 g (184.3 mmol) of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (trifunctional sulfur-containing polythiol (GST)) was placed in a four-necked flask equipped with a stirrer, thermometer, nitrogen introduction line, and dropping funnel. Next, 200 mL of dichloromethane was added to the flask to dissolve the GST in the dichloromethane.

[0308] Next, 41.0 g of triethylamine (base catalyst, 405.4 mmol) was slowly added to the flask while stirring.

[0309] Next, the solution in the flask was cooled in an ice bath. Then, while maintaining the temperature inside the flask below 10°C, 25.9 g of benzoyl chloride (first denaturing agent, 184.3 mmol) was added dropwise to the flask.

[0310] After the dropwise addition was complete, the ice bath was removed and the temperature inside the flask was allowed to return to room temperature. The reaction product in the flask was then stirred overnight. This allowed the benzoyl group (XR in formula (1)) derived from benzoyl chloride to form.

[0311] Subsequently, 300 mL of water and 200 mL of dichloromethane were added to the reaction product in the flask. The organic phase was then separated by liquid-liquid extraction. Next, the organic phase was washed with dilute hydrochloric acid. Then, the organic phase was washed with saturated sodium bicarbonate aqueous solution. Finally, the solvent in the organic phase was removed by distillation using an evaporator. This yielded the crude product.

[0312] The crude product was diluted with 100 mL of dichloromethane to obtain a diluted solution. The diluted solution was passed through 100 mL of silica gel. The diluted solution was then eluted using 300 mL of dichloromethane. Subsequently, the eluted diluted solution was concentrated using an evaporator. This yielded 63.2 g of the primary reaction product. The primary reaction product was a partially benzoylated GST.

[0313] In the above reaction, one-third of the mercapto groups (trifunctional) of GST were benzoylated.

[0314] (2) Second reaction step 30.0 g of the primary reaction product was placed in a four-necked flask equipped with a stirrer, thermometer, nitrogen introduction line, and dropping funnel. Next, 50 mL of dichloromethane was added to the flask to dilute the primary reaction product with dichloromethane.

[0315] Next, the diluted solution in the flask was cooled in an ice bath. Then, while maintaining the temperature inside the flask below 40°C, 25.2 g of 3-chloropropionyl chloride (second denaturing agent, 199 mmol) was added dropwise to the flask.

[0316] Next, the reaction product in the flask was stirred at room temperature for 48 hours. Then, 100 mL of pure water was added to the flask. After that, the organic phase was separated by liquid-liquid extraction. The organic phase was then washed twice with 100 mL of saturated sodium bicarbonate aqueous solution. Finally, the solvent in the organic phase was removed by distillation using an evaporator.

[0317] Next, the reaction product was placed in a four-necked flask equipped with a thermometer and a dropping funnel. 30 mg of 4-methoxyphenol (polymerization inhibitor) was then added to the flask. The contents of the flask were then stirred at room temperature to dissolve the 4-methoxyphenol.

[0318] Next, the diluted solution in the flask was cooled in an ice bath. Then, while maintaining the temperature inside the flask below 40°C, 21.8 g (215 mmol) of triethylamine (second denaturing agent, base) was added dropwise to the flask. Next, the reaction product in the flask was stirred at room temperature for 1 hour. This treated the reaction product with base, forming an acryloyl group derived from 3-chloropropionyl chloride.

[0319] Subsequently, 1M hydrochloric acid (300 mL) was added to the reaction product in the flask. The organic phase was then separated by liquid-liquid extraction.

[0320] Next, the organic phase was passed through silica gel (30 mL). 30 mg of 4-methoxyphenol (polymerization inhibitor) was added to the organic phase. Finally, the organic phase was concentrated under reduced pressure.

[0321] This yielded 36.8 g of a colorless and transparent secondary reaction product (hereinafter referred to as Bz2.0-GSTA). The secondary reaction products were benzoyl and acrylic compounds of GST.

[0322] In the above reaction, 2 / 3 equivalents of the mercapto groups (trifunctional) of GST were acrylicated.

[0323] The secondary reaction product was analyzed by high-performance liquid chromatography (HPLC). The reaction product was a polymerizable composition containing the following components in the following proportions.

[0324] GST trithio(meth)acryloyl variant 40.5 mol% (LC%) Dithio(meth)acryloyl modified form of GST: 41.2 mol% (LC%) Monothio(meth)acryloyl modified form of GST 11.5 mol% (LC%) GST thio(meth)acryloyl undenatured 6.8 mol% (LC%)

[0325] The dithio(meth)acryloyl modified form of GST and the monothio(meth)acryloyl modified form of GST are the compounds shown in formula (1) above. The trithio(meth)acryloyl modified form of GST is the compound shown in formula (7) above. The thio(meth)acryloyl unmodified form of GST is the compound shown in formula (4) above.

[0326] The average number of (meth)acryloyl groups in the combined trithio(meth)acryloyl variant of GST, the dithio(meth)acryloyl variant of GST, and the monothio(meth)acryloyl variant of GST was 2.31.

[0327] Example A3 (1) First reaction step 20.0 g (76.8 mmol) of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (trifunctional sulfur-containing polythiol (GST)) was placed in a four-necked flask equipped with a stirrer, thermometer, nitrogen introduction line, and dropping funnel. Then, 100 mL of toluene was added to the flask to dissolve the GST in toluene.

[0328] Next, 23.3 g of triethylamine (base catalyst, 230.3 mmol) was slowly added to the flask while stirring.

[0329] Next, the solution in the flask was cooled in an ice bath. Then, while maintaining the temperature inside the flask below 10°C, 15.7 g of acetic anhydride (first denaturing agent, 153.5 mmol) was added dropwise to the flask.

[0330] After the dropwise addition was complete, the ice bath was removed and the temperature inside the flask was allowed to return to room temperature. The reaction product in the flask was then stirred overnight. This allowed the acetyl group (XR in formula (1)) derived from acetic anhydride to form.

[0331] Subsequently, 300 mL of water and 200 mL of toluene were added to the reaction product in the flask. The organic phase was then separated by liquid-liquid extraction. Next, the organic phase was washed with dilute hydrochloric acid. Then, the organic phase was washed with saturated sodium bicarbonate aqueous solution. Finally, the solvent in the organic phase was removed by distillation using an evaporator. This yielded the crude product.

[0332] The crude product was diluted with 100 mL of toluene to obtain a diluted solution. The diluted solution was passed through 20 mL of silica gel. The diluted solution was then eluted using 300 mL of toluene. The eluted diluted solution was then concentrated using an evaporator. This yielded 26.0 g of the primary reaction product. The primary reaction product was a partially acetylated GST.

[0333] In the above reaction, 2 / 3 equivalents of the mercapto groups (trifunctional) of GST were acetylated.

[0334] (2) Second reaction step 20.0 g of the primary reaction product was placed in a four-necked flask equipped with a stirrer, thermometer, nitrogen introduction line, and dropping funnel. Next, 100 mL of dichloromethane was added to the flask to dilute the primary reaction product with dichloromethane.

[0335] Next, the diluted solution in the flask was cooled in an ice bath. Then, while maintaining the temperature inside the flask below 40°C, 14.7 g of 3-chloropropionyl chloride (second denaturing agent, 116.0 mmol) was added dropwise to the flask.

[0336] Next, the reaction product in the flask was stirred at room temperature for 48 hours. Then, 100 mL of pure water was added to the flask. After that, the organic phase was separated by liquid-liquid extraction. The organic phase was then washed twice with 100 mL of saturated sodium bicarbonate aqueous solution. Finally, the solvent in the organic phase was removed by distillation using an evaporator.

[0337] Next, the reaction product was placed in a four-necked flask equipped with a thermometer and a dropping funnel. 23 mg of 4-methoxyphenol (polymerization inhibitor) was then added to the flask. The contents of the flask were then stirred at room temperature to dissolve the 4-methoxyphenol.

[0338] Next, the diluted solution in the flask was cooled in an ice bath. Then, while maintaining the temperature in the flask below 40°C, 7.63 g (75.4 mmol) of triethylamine (second denaturing agent, base) was added dropwise to the flask. Next, the reaction product in the flask was stirred at room temperature for 1 hour. This treated the reaction product with base, forming an acryloyl group derived from 3-chloropropionyl chloride.

[0339] Subsequently, 1M hydrochloric acid (300 mL) was added to the reaction product in the flask. The organic phase was then separated by liquid-liquid extraction.

[0340] Next, the organic phase was passed through silica gel (30 mL). 23 mg of 4-methoxyphenol (polymerization inhibitor) was added to the organic phase. Finally, the organic phase was concentrated under reduced pressure.

[0341] This yielded 22.5 g of a colorless, transparent secondary reaction product (hereinafter referred to as Ac2.0-GSTA). The secondary reaction products were acetylated and acrylicated GST.

[0342] In the above reaction, one-third of the mercapto groups (trifunctional) of GST were acrylicated.

[0343] The secondary reaction product was analyzed by high-performance liquid chromatography (HPLC). The reaction product was a polymerizable composition containing the following components in the following proportions.

[0344] GST trithio(meth)acryloyl modified compound 5.4 mol% (LC%) Dithio(meth)acryloyl modified form of GST: 31.9 mol% (LC%) Monothio(meth)acryloyl modified form of GST: 48.0 mol% (LC%) GST thio(meth)acryloyl undenatured 14.6 mol% (LC%)

[0345] The dithio(meth)acryloyl modified form of GST and the monothio(meth)acryloyl modified form of GST are the compounds shown in formula (1) above. The trithio(meth)acryloyl modified form of GST is the compound shown in formula (7) above. The thio(meth)acryloyl unmodified form of GST is the compound shown in formula (4) above.

[0346] The average number of (meth)acryloyl groups, calculated from the LC%, for the combined trithio(meth)acryloyl variant of GST, the dithio(meth)acryloyl variant of GST, and the monothio(meth)acryloyl variant of GST was 1.28.

[0347] Example A4 (1) First reaction step 19.1 g (73.2 mmol) of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (trifunctional sulfur-containing polythiol (GST)) was placed in a four-necked flask equipped with a stirrer, thermometer, nitrogen introduction line, and dropping funnel. Then, 100 mL of toluene was added to the flask to dissolve the GST in toluene.

[0348] Next, 15.2 g of triethylamine (base catalyst, 150.0 mmol) was slowly added to the flask while stirring.

[0349] Next, the solution in the flask was cooled in an ice bath. Then, while maintaining the temperature inside the flask below 10°C, 24.7 g of 3-phenylpropionyl chloride (first denaturing agent, 146.3 mmol) was added dropwise to the flask.

[0350] After the dropwise addition was complete, the ice bath was removed and the temperature inside the flask was returned to room temperature. The reaction product in the flask was also stirred overnight. This allowed the formation of the 3-phenylpropionyl group (XR in formula (1)) derived from 3-phenylpropionyl chloride.

[0351] Subsequently, 300 mL of water and 200 mL of toluene were added to the reaction product in the flask. The organic phase was then separated by liquid-liquid extraction. Next, the organic phase was washed with dilute hydrochloric acid. Then, the organic phase was washed with saturated sodium bicarbonate aqueous solution. Finally, the solvent in the organic phase was removed by distillation using an evaporator. This yielded the crude product.

[0352] The crude product was diluted with 150 mL of toluene to obtain a diluted solution. The diluted solution was passed through 30 mL of activated alumina (basic, 300 mesh). The diluted solution was then eluted using 100 mL of toluene. The eluted diluted solution was then concentrated using an evaporator. This yielded 37.4 g of the primary reaction product. The primary reaction product was a partially 3-phenylpropionylated form of GST.

[0353] In the above reaction, 2 / 3 equivalents of the mercapto groups (trifunctional) of GST were 3-phenylpropionylated.

[0354] (2) Second reaction step 20.0 g of the primary reaction product was placed in a four-necked flask equipped with a stirrer, thermometer, nitrogen introduction line, and dropping funnel. Next, 100 mL of dichloromethane was added to the flask to dilute the primary reaction product with dichloromethane.

[0355] Next, the diluted solution in the flask was cooled in an ice bath. Then, while maintaining the temperature inside the flask below 40°C, 9.68 g of 3-chloropropionyl chloride (second denaturing agent, 76.2 mmol) was added dropwise to the flask.

[0356] Next, the reaction product in the flask was stirred at room temperature for 48 hours. Then, 100 mL of pure water was added to the flask. After that, the organic phase was separated by liquid-liquid extraction. The organic phase was then washed twice with 100 mL of saturated sodium bicarbonate aqueous solution. Finally, the solvent in the organic phase was removed by distillation using an evaporator.

[0357] Next, the reaction product was placed in a four-necked flask equipped with a thermometer and a dropping funnel. 22 mg of 4-methoxyphenol (polymerization inhibitor) was then added to the flask. The contents of the flask were then stirred at room temperature to dissolve the 4-methoxyphenol.

[0358] Next, the diluted solution in the flask was cooled in an ice bath. Then, while maintaining the temperature in the flask below 40°C, 5.01 g (49.5 mmol) of triethylamine (second denaturing agent, base) was added dropwise to the flask. Next, the reaction product in the flask was stirred at room temperature for 1 hour. This treated the reaction product with base, forming acryloyl groups derived from 3-chloropropionyl chloride.

[0359] Subsequently, 1M hydrochloric acid (300 mL) was added to the reaction product in the flask. The organic phase was then separated by liquid-liquid extraction.

[0360] Next, the organic phase was passed through silica gel (30 mL). 22 mg of 4-methoxyphenol (polymerization inhibitor) was added to the organic phase. Finally, the organic phase was concentrated under reduced pressure.

[0361] This yielded 21.2 g of a colorless and transparent secondary reaction product (hereinafter referred to as PP2.0-GSTA). The secondary reaction products were 3-phenylpropionyl and acrylic compounds of GST.

[0362] In the above reaction, one-third of the mercapto groups (trifunctional) of GST were acrylicated.

[0363] The secondary reaction product was analyzed by high-performance liquid chromatography (HPLC). The reaction product was a polymerizable composition containing the following components in the following proportions.

[0364] GST trithio(meth)acryloyl modified compound 6.1 mol% (LC%) Dithio(meth)acryloyl modified form of GST: 22.6 mol% (LC%) Monothio(meth)acryloyl modified form of GST: 37.0 mol% (LC%) GST thio(meth)acryloyl undenatured 34.3 mol% (LC%)

[0365] The dithio(meth)acryloyl modified form of GST and the monothio(meth)acryloyl modified form of GST are the compounds shown in formula (1) above. The trithio(meth)acryloyl modified form of GST is the compound shown in formula (7) above. The thio(meth)acryloyl unmodified form of GST is the compound shown in formula (4) above.

[0366] In the total of trithio(meth)acryloyl modified GST, dithio(meth)acryloyl modified GST and monothio(meth)acryloyl modified GST, the average number of (meth)acryloyl groups determined from LC% was 1.01.

[0367] <B. Molded Article (Cured Resin)> Examples B1 to B2 and Comparative Examples B1 to B2 (1) Polymerizable Composition Raw materials (total 100 parts by mass) were prepared according to the formulation shown in Table 1. Then, 3 parts by mass of Omnirad 184 (1-hydroxycyclohexyl phenyl ketone, manufactured by IGM RESINS) as a radical polymerization initiator was blended with 100 parts by mass of the raw materials. Thus, a liquid polymerizable composition was prepared.

[0368] (2) Cured Resin The polymerizable composition was encapsulated in a silicone mold having a predetermined size of 50 mm × 50 mm × 0.5 mm.

[0369] An electrodeless light source (H bulb) was used to irradiate the polymerizable composition with an active energy ray (wavelength: 365 nm, illuminance: 100 mW / cm 2 , integrated light quantity: 1000 mJ / cm 2 ). Further, the polymerizable composition was peeled off from the glass substrate and heated at 80°C for 30 minutes under a nitrogen atmosphere. Thus, the polymerizable composition was cured by the active energy ray and heat. As a result, a cured resin (molded article) was obtained.

[0370] <C. Adhesive (Cured Resin)> Examples C1 to C12 and Comparative Example C1 (1) Polymerizable Composition Raw materials (total 100 parts by mass) were prepared according to the formulation shown in Table 2. Then, 3 parts by mass of Omnirad 184 (1-hydroxycyclohexyl phenyl ketone, manufactured by IGM RESINS) as a radical polymerization initiator was blended with 100 parts by mass of the raw materials. Thus, a liquid polymerizable composition was prepared.

[0371] (2) Cured resin A pair of glass substrates (Eagle-XG, manufactured by Corning) were surface-treated with a release agent (Novec 1720, manufactured by 3M). The polymerizable composition was sandwiched between the glass substrates in a mold formed of a silicone sheet having a thickness of 250 μm.

[0372] Using an electrodeless light source (H bulb), the polymerizable composition was irradiated with an active energy ray having a wavelength of 365 nm and an illuminance of 100 mW / cm 2 and an integrated light quantity of 1000 mJ / cm 2 ). Thereafter, the polymerizable composition was peeled from the glass substrate and heated at 80° C. for 30 minutes under a nitrogen atmosphere. Thereby, the polymerizable composition was cured by active energy rays and heat. As a result, a cured resin (pressure-sensitive adhesive film) was obtained.

[0373] <D. Evaluation Method> (1) Refractive index and Abbe number The refractive index (nd) of d-line (wavelength: 587.6 nm) of the cured resin was measured at room temperature (20° C.) using an Abbe refractometer (DR-M4, manufactured by Atago Co., Ltd.).

[0374] Further, the refractive index (nC) of C-line (wavelength: 656.3 nm) of the cured resin was measured at room temperature (20° C.) using an Abbe refractometer (DR-M4, manufactured by Atago Co., Ltd.).

[0375] Further, the refractive index (nF) of F-line (wavelength: 486.1 nm) of the cured resin was measured at room temperature (20° C.) using an Abbe refractometer (DR-M4, manufactured by Atago Co., Ltd.).

[0376] Then, the Abbe number of the cured resin was calculated according to the following formula. Abbe number = (nd-1) / (nF-nC)

[0377] (2) Glass transition temperature (Tg) and storage elastic modulus (E') The solid viscoelasticity of the cured resin was measured under the following conditions. Apparatus: RSA-G2 (manufactured by TA Instruments) Deformation mode: Tension Temperature range: -50℃ to 100℃ Temperature increase: 3°C / min Frequency: 1Hz Environment: N2 atmosphere

[0378] Then, from the viscoelasticity measurement results, the glass transition temperature (Tg) and the storage modulus at 25°C (E'(25°C)) of the cured resin were determined. The temperature at which the value of tanδ showed a maximum was measured as the glass transition temperature (Tg).

[0379] [Table 1]

[0380] [Table 2]

[0381] Details of the abbreviations in the table are as follows. POB-A;o-Phenoxybenzylacrylate, manufactured by Kyoeisha Chemical Co., Ltd. 2EHA; 2-Ethylhexyl acrylate, manufactured by Toagosei Co., Ltd. GSTA; 1,8-bisacryloylthio-(4-acryloylthiomethyl-3,6-dithiaoctane) prepared in accordance with Example 3 of Japanese Patent Publication No. 4-29967

[0382] The above invention is provided as an illustrative embodiment of the present invention, but this is merely illustrative and should not be interpreted restrictively. Modifications of the present invention that are obvious to those skilled in the art are included in the claims described below. [Industrial applicability]

[0383] The compounds, polymerizable compositions, adhesives, cured resins, molded articles, films, tacks, and methods for producing the compounds of the present invention are particularly suitable for use in the field of optics.

Claims

1. As shown in equation (1) below, In equation (1), A is, A compound represented by the following formula (2) or formula (3). Formula (1); 【Chemistry 1】 (In 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 a fragrant aliphatic hydrocarbon group. R' represents a hydrogen atom or a methyl group. If the formula contains multiple X's, each X may be the same or different from the others. Similarly, if the formula contains multiple R's, each R' may be the same or different from the others.) Formula (2); 【Chemistry 2】 (In equation (2), S has the same meaning as S in equation (1). If A in equation (1) is shown in equation (2), then m + n in equation (1) represents 3.) Formula (3); 【Transformation 3】 (In equation (3), S has the same meaning as S in equation (1). When A in equation (1) is shown in equation (3), then m + n in equation (1) represents 4.)

2. In formula (1), X represents a carbonyl group, The compound according to claim 1, wherein R represents a methyl group, a phenyl group, or a 2-phenylethyl group.

3. A polymerizable composition comprising the compound described in claim 1.

4. The polymerizable composition according to claim 3, comprising the compound in formula (1) where n = 1.

5. Furthermore, it contains other polymerizable compounds, The polymerizable composition according to claim 3, wherein the other polymerizable compounds include a compound represented by the following formula (7). Formula (7); 【Chemistry 4】 (In equation (7), A, S, R', m, and n have the same meanings as A, S, R', m, and n in equation (1).)

6. The polymerizable composition according to claim 5, wherein the average number of (meth)acryloyl groups in the total amount of the compound represented by formula (1) and the compound represented by formula (7) is 1.4 or less.

7. Furthermore, it contains other polymerizable compounds, The polymerizable composition according to claim 3, wherein the other polymerizable compounds include monofunctional (meth)acrylates and / or polyfunctional (meth)acrylates.

8. Furthermore, it contains plasticizers, The polymerizable composition according to claim 3, wherein the plasticizer comprises a compound represented by the following formula (4). Formula (4); 【Transformation 5】 (In equation (4), A, S, X, R, m, and n have the same meanings as A, S, X, R, m, and n in equation (1), respectively.)

9. An adhesive comprising the polymerizable composition described in claim 3.

10. The adhesive according to claim 9, which is an optical adhesive.

11. A resin cured product comprising a cured product of the polymerizable composition described in claim 3.

12. The refractive index is 1.60 or higher. The resin cured product according to claim 11, wherein the tensile storage modulus is 10 MPa or less.

13. A molded article comprising the resin cured product described in claim 11.

14. A molded article according to claim 13, which is an optical component.

15. A film comprising the resin cured product described in claim 11.

16. The film according to claim 15, which is an optical film.

17. An adhesive comprising the resin cured product described in claim 11.

18. The adhesive according to claim 17, which is an optical adhesive.

19. A method for producing the compound described in claim 1, A preparation step to prepare a polythiol with an m+n valency (where m+n is an integer of 3 or more) containing a sulfur atom, The aforementioned polythiol, A first modifying agent that encapsulates the molecular ends of the polythiol and does not form a (meth)acryloyl group, A reaction step in which the molecular ends of the polythiol are encapsulated and reacted with a second modifying agent to form a (meth)acryloyl group, Equipped with, A method for producing a compound in which the polythiol is represented by the following formula (5) or the following formula (6). Formula (5); 【Transformation 6】 Formula (6); 【Transformation 7】

20. The reaction step described above is A first reaction step involves reacting the polythiol with the first modifying agent, A second reaction step is performed after the first reaction step, in which the reaction product from the first reaction step is reacted with the second denaturing agent. A method for producing the compound according to claim 19, comprising:

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