Compound, additive, plasticizer, curable composition, adhesive, cured product, and tackifier

Abstract

A compound according to the present invention is represented by general formula (1). (In formula (1), A represents an n-valent organic group that includes a sulfur atom. S represents a sulfur atom. X1 represents a single bond or a carbonyl group. R1 represents an alkylene group. Y represents an aryloxy group or an arylalkyloxy group. X2 represents a single bond or a carbonyl group. R2 represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or an aromatic aliphatic hydrocarbon group. X1, R1, Y, X2, and R2 may each be the same or different from each other. n represents an integer of 3 or more. m represents an integer of at least 1 and no more than n.)

Description

Compounds, additives, plasticizers, curable compositions, adhesives, cured products, and pressure-sensitive adhesives

[0001] The present invention relates to a compound, an additive, a plasticizer, a curable composition, an adhesive, a cured product, and a pressure-sensitive adhesive.

[0002] In various optical fields, optical resins are used as adhesives and pressure-sensitive adhesives. Optical resins have a relatively high refractive index. Depending on the application, optical resins may be required to be flexible. Therefore, adding a plasticizer to optical resins is being considered.

[0003] Known examples of plasticizers include dioctyl phthalate (DOP, bis(2-ethylhexyl) phthalate) (see, for example, Patent Document 1).

[0004] JP 2015-105329 A

[0005] When the above-mentioned plasticizer is added to an optical resin, the crystallinity of the optical resin is reduced and the flexibility is improved. However, the reduction in the crystallinity of the optical resin may reduce the refractive index of the optical resin. Furthermore, for example, if the refractive index of the optical resin is not reduced by the plasticizer, the crystallinity of the optical resin may not be reduced sufficiently, and the flexibility may not be improved.

[0006] Therefore, there is a demand for plasticizers that can improve flexibility without lowering the refractive index. Furthermore, depending on the application, optical resins are required to have excellent weather resistance.

[0007] The present invention relates to a compound, an additive, a plasticizer, a curable composition, an adhesive, a cured product, and a pressure-sensitive adhesive for obtaining a cured product that has a refractive index, flexibility, and weather resistance.

[0008] The present invention [1] includes a compound represented by the following general formula (1): General formula (1);

[0009]

[0010] In formula (1), A represents an n-valent organic group containing a sulfur atom. S represents a sulfur atom. X １ represents a single bond or a carbonyl group. １represents an alkylene group; Y represents an aryloxy group or an arylalkyloxy group; X ２ represents a single bond or a carbonyl group. ２ represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or an araliphatic hydrocarbon group. １ , R １ , Y, X ２ and R ２ may be the same or different from each other. n represents an integer of 3 or more. m represents an integer of 1 or more and n or less.

[0011] The present invention [2] includes the compound according to the above [1], wherein in the above formula (1), A has a molecular weight of 50 or more and 9,000 or less.

[0012] The present invention [3] includes the compound according to the above [1] or [2], wherein A represents an organic group containing a sulfur atom and a typical element atom (excluding sulfur and hydrogen atoms), and the ratio of the number of sulfur atoms to the total number of sulfur atoms and the typical element atoms (excluding sulfur and hydrogen atoms) in A exceeds 20%.

[0013] The present invention [4] includes the compound according to any one of the above [1] to [3], wherein in formula (1), A is a residue (GST residue) obtained by removing the mercapto group from 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (GST).

[0014] The present invention [5] includes the compound according to any one of the above [1] to [3], wherein in formula (1), A is a residue (FSH residue) obtained by removing a mercapto group from 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (FSH).

[0015] The present invention [6] is a compound represented by the formula (1), wherein X １ represents a carbonyl group, and R １ represents an alkylene group having 1 to 2 carbon atoms, and Y represents a phenoxy group.

[0016] The present invention [7] includes the compound according to any one of the above [1] to [6], wherein m=n in the above formula (1).

[0017] The present invention [8] includes an additive containing the compound according to any one of the above [1] to [7].

[0018] The present invention [9] includes a plasticizer containing the compound according to any one of the above [1] to [7].

[0019] The present invention

[10] includes a curable composition containing the plasticizer described in the above [9] and a curable compound.

[0020] The present invention

[11] further comprises at least one additive selected from the group consisting of an ultraviolet absorber, a light stabilizer, and an antioxidant, and the ratio of the additive to 1 part by mass of the curable composition is 10 × 10 －６ Mass part or more 10,000×10 －６ The curable composition according to the above

[10] is contained in an amount of not more than parts by mass.

[0021] The present invention

[12] includes an adhesive containing the curable composition according to the above

[10] or

[11] .

[0022] The present invention

[13] includes a cured product containing the plasticizer described in [9] above and a cured resin.

[0023] The present invention

[14] includes the cured product according to the above

[13] , which has a refractive index of 1.60 or more and a tensile storage modulus at 25°C of 100 MPa or less.

[0024] The present invention

[15] further comprises at least one additive selected from the group consisting of an ultraviolet absorber, a light stabilizer, and an antioxidant, and the ratio of the additive to 1 part by mass of the cured product is 10 × 10 －６ Mass part or more 10,000×10 －６ The cured product according to

[13] or

[14] is contained in an amount of not more than parts by mass.

[0025] The present invention

[16] includes the cured product according to any one of the above

[13] to

[15] , wherein the cured resin includes a reaction product of a base agent containing an acrylic polyol and a curing agent containing a polyisocyanate.

[0026] The present invention

[15] includes the cured product according to any one of the above

[11] to

[13] , wherein the cured resin includes a cured acrylic resin.

[0027] The present invention

[16] includes a pressure-sensitive adhesive comprising the cured product according to any one of the above

[11] to

[15] .

[0028] The compound, additive, plasticizer, curable composition, and adhesive of the present invention can provide a cured product that has a refractive index, flexibility, and weather resistance.

[0029] The cured product and adhesive of the present invention contain the above compound and therefore have a refractive index, flexibility, and weather resistance.

[0030] 1. Compound (1) Structure of Compound The compound of the present invention is represented by the following general formula (1): General formula (1);

[0031]

[0032] In formula (1), A represents an n-valent organic group containing a sulfur atom. S represents a sulfur atom. X １ represents a single bond or a carbonyl group. １ represents an alkylene group; Y represents an aryloxy group or an arylalkyloxy group; X ２ represents a single bond or a carbonyl group. ２ represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or an araliphatic hydrocarbon group. １ , R １ , Y, X ２ and R ２ may be the same or different from each other. n represents an integer of 3 or more. m represents an integer of 1 or more and n or less.

[0033] (2) A and n in Formula In the above formula (1), A represents an n-valent organic group containing a sulfur atom. Preferably, A represents an organic group containing a sulfur atom and a main element atom (excluding sulfur and hydrogen atoms).

[0034] In the typical element atoms (excluding sulfur and hydrogen atoms), typical elements (excluding sulfur and hydrogen) refer to elements with atomic numbers of 2 to 15, elements with atomic numbers of 17 to 20, elements with atomic numbers of 31 to 38, elements with atomic numbers of 49 to 56, and elements with atomic numbers of 81 to 88. Preferred typical elements (excluding sulfur and hydrogen) include elements with atomic numbers of 2 to 15, more preferably elements with atomic numbers of 6 to 9, and more specifically, carbon, nitrogen, oxygen, and fluorine. These may be used alone or in combination of two or more types.

[0035] More preferably, the typical element (excluding sulfur and hydrogen) is carbon or oxygen, and particularly preferably carbon. From the viewpoint of achieving a good balance between refractive index and flexibility, A more preferably represents an organic group containing a sulfur atom and a carbon atom, and even more preferably represents an organic group consisting of a sulfur atom and a carbon atom.

[0036] In the above formula (1), the molecular weight of A is, for example, 50 or more, preferably 60 or more, more preferably 100 or more, and even more preferably 130 or more. In addition, in the above formula (1), the molecular weight of A is, for example, 9000 or less, preferably 4000 or less, and more preferably 500 or less. That is, in the above formula (1), the molecular weight of A is, for example, 50 or more and 9000 or less, preferably 60 or more and 4000 or less, more preferably 100 or more and 500 or less, and even more preferably 130 or more and 500 or less.

[0037] The molecular weight of A can be calculated, for example, from the molecular weight of the compound represented by the above formula (1) by the following formula: (SX １ R １ Y)m and the molecular weight of (SX ２ R ２)n and the molecular weight of n. The method for measuring the molecular weight of the compound represented by the formula (1) is not particularly limited. For example, when the compound represented by the formula (1) is a monomer, the molecular weight of the compound represented by the formula (1) is calculated from the molecular skeleton and the number of atoms. When multiple compounds represented by the formula (1) are used in combination, the molecular weight of the compound represented by the formula (1) is calculated as the average molecular weight of each compound (the same applies below). Furthermore, when the compound represented by the formula (1) is a polymer, the molecular weight of the compound represented by the formula (1) can be measured as a polystyrene-equivalent molecular weight by gel permeation chromatogram (GPC) (the same applies below).

[0038] n is the valence of A. n represents an integer of 3 or more. n preferably represents an integer of 3 or more and 8 or less. n more preferably represents an integer of 3 or more and 6 or less. n is even more preferably 3 or 4.

[0039] Examples of n-valent A include residues of n-functional thiols. In other words, A is a residue obtained by removing a mercapto group from an n-functional thiol. More specifically, A includes residues obtained by removing a mercapto group from a trifunctional or higher sulfur-containing polythiol (hereinafter referred to as a trifunctional or higher sulfur-containing polythiol residue).

[0040] A tri- or higher functional sulfur-containing polythiol is an organic compound containing three or more mercapto groups in one molecule and one or more (preferably two or three) sulfur atoms other than the mercapto groups. Examples of tri- or higher functional sulfur-containing polythiols include sulfur-containing trithiol, sulfur-containing tetrathiol, sulfur-containing pentathiol, sulfur-containing hexathiol, and sulfur-containing octathiol.

[0041] The sulfur-containing trithiol is a trifunctional thiol containing a sulfur atom in addition to a 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, 4,6-bis[4-(6-mercaptomethylthio)-1,3-dithianylthio] ]-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.

[0042] The sulfur-containing tetrathiol is a tetrafunctional thiol containing a sulfur atom in addition to a 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, thiodipropionic acid bis(2,3-dimercaptopropyl ester), dithiodiglycolic acid bis(2,3-dimercaptopropyl ester), thiodipropionic acid bis(2,3-dimercaptopropyl ester), dithiodipropionic acid bis(2,3-dimercaptopropyl ester), 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 1,1,5,5-tetrakis(mercaptomethylthio)- 3-Thiapentane, 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-trithianonane, 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-dithietanyl)]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-2,5-dithiahexylthio]mercaptomethylthiomethyl-1,3-dithietane, 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.

[0043] The sulfur-containing pentathiol is a pentafunctional thiol containing a sulfur atom in addition to a mercapto group. Examples of sulfur-containing pentathiols include 1-[4-(6-mercaptomethylthio)-1,3-dithianylthio]-3-[2,2-bis(mercaptomethylthio)ethyl]-7,9-bis(mercaptomethylthio)-2,4,6,10-tetrathiaundecane and bis[4,4-bis(mercaptomethylthio)-1,3-dithiabutyl]-(mercaptomethylthio)methane.

[0044] The sulfur-containing hexathiol is a hexafunctional thiol containing a sulfur atom in addition to a 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(mercaptomethylthio). 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-dithietanyl)]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-dithietane, 2-[3,4,8,9-tetrakis(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathiaundecylthio]mercaptomethylthiomethyl-1,3-dithietane, 2-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiaoctyl]mercaptomethylthiomethyl-1,3-dithietane, tris[4,4-bis(mercaptomethylthio)-1,3-dithiabutyl]methane, tris[2,2-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.

[0045] The sulfur-containing octathiol is an octafunctional thiol containing a sulfur atom in addition to a mercapto group. Examples of sulfur-containing octathiols include tetrakis(4,4-bis(mercaptomethylthio)-2-thiabutyl)methane, 3,5,9,11,15,17-hexakis(mercaptomethylthio)-1,19-dimercapto-2,6,8,12,14,18-hexathianonadecane, 9-(2,2-bis(mercaptomethylthio)ethyl)-3,5,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane, tetrakis(2,2 -bis(mercaptomethylthio)ethyl)methane, 3,4,8,9,13,14-hexakis(mercaptomethylthio)-1,16-dimercapto-2,5,7,10,12,15-hexathiahexadecane, 8-[bis(mercaptomethylthio)methyl]-3,4,12,13-tetrakis(mercaptomethylthio)-1,15-dimercapto-2,5,7,9,11,14-hexathiapentadecane, and tetrakis[3,3-bis(mercaptomethylthio)-2-thiapropyl]methane.

[0046] The tri- or higher functional sulfur-containing polythiol residue is preferably a tri- to hexa-functional sulfur-containing polythiol residue, more preferably a tri- or tetra-functional sulfur-containing polythiol residue, and even more preferably a tri-functional sulfur-containing polythiol residue.

[0047] That is, in the general formula (1), A is preferably a trifunctional to hexafunctional sulfur-containing polythiol residue, more preferably a trifunctional to tetrafunctional sulfur-containing polythiol residue, and even more preferably a trifunctional sulfur-containing polythiol residue.

[0048] In other words, A is preferably a trivalent to hexavalent organic group containing one or more (preferably two or three) sulfur atoms. A is more preferably a trivalent organic group containing one or more (preferably two or three) sulfur atoms, or a tetravalent organic group containing one or more (preferably two or three) sulfur atoms, and even more preferably a trivalent organic group containing a sulfur atom.

[0049] From the viewpoint of achieving a good balance between refractive index and flexibility, A preferably contains sulfur atoms at a predetermined ratio or more. More specifically, in A, the ratio of the number of sulfur atoms to the total number of sulfur atoms and the number of typical element atoms (excluding sulfur atoms and hydrogen atoms) is, for example, more than 20%, preferably 21% or more, more preferably 22% or more. Furthermore, from the viewpoint of achieving a good balance between refractive index and flexibility, the ratio of the number of sulfur atoms to the total number of sulfur atoms and the number of typical element atoms (excluding sulfur atoms and hydrogen atoms) is, for example, 80% or less, preferably 50% or less, more preferably 30% or less, and even more preferably 25% or less. The ratio of the number of sulfur atoms to the total number of sulfur atoms and the number of typical element atoms (excluding sulfur atoms and hydrogen atoms) is calculated by the following formula:

[0050] Percentage of number of sulfur atoms (%) = number of sulfur atoms / [number of sulfur atoms + number of main group atoms (excluding sulfur atoms and hydrogen atoms)] × 100

[0051] The trivalent organic group (organic group A (n=3)) containing one or more sulfur atoms (preferably two or three, more preferably two) is preferably a residue obtained by removing a mercapto group from the above-mentioned sulfur-containing trithiol, more preferably a residue obtained by removing a mercapto group from 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (GST) (GST residue).

[0052] That is, A in the above formula (1) is more preferably a residue (GST residue) obtained by removing a mercapto group from 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (GST). The residue (GST residue) obtained by removing a mercapto group from 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (GST) is represented, for example, by the following general formula (2): General formula (2);

[0053] (In formula (2), the wavy line represents SX in formula (1) １ R １ Y group or SX ２ R ２ indicates the bonding position relative to the group.)

[0054] When A in the above formula (1) is a GST residue, a cured product having both an especially excellent refractive index and especially excellent flexibility can be obtained.

[0055] The GST residue is an organic group consisting of two sulfur atoms and seven carbon atoms. In the GST residue, the ratio of the number of sulfur atoms to the total number of sulfur atoms and main group atoms (excluding sulfur and hydrogen atoms) is approximately 22% (2 / [2+7]×100).

[0056] The tetravalent organic group (organic group A (n=4)) containing one or more sulfur atoms (preferably two or three, more preferably three) is preferably a residue obtained by removing a mercapto group from the above-mentioned sulfur-containing tetrathiol, more preferably a residue obtained by removing a mercapto group from 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (FSH) (FSH residue).

[0057] That is, A in the above formula (1) is more preferably a residue (FSH residue) obtained by removing a mercapto group from 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (FSH). The residue (FSH residue) obtained by removing a mercapto group from 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (FSH) is represented, for example, by the following general formula (3): General formula (3);

[0058] (In formula (3), the wavy line represents SX in formula (1) １ R １ Y group or SX ２ R ２ indicates the bonding position relative to the group.)

[0059] When A in the above formula (1) is an FSH residue, a cured product having both an especially excellent refractive index and especially excellent flexibility can be obtained.

[0060] The FSH residue is an organic group consisting of three sulfur atoms and ten carbon atoms. In the FSH residue, the ratio of the number of sulfur atoms to the total number of sulfur atoms and main group atoms (excluding sulfur and hydrogen atoms) is approximately 23% (3 / [3+10]×100).

[0061] From the viewpoint of refractive index and flexibility, A in the above formula (1) is preferably a GST residue or an FSH residue, more preferably a GST residue.

[0062] (3) S in Formula In the above formula (1), S represents a sulfur atom.

[0063] (4) X in the formula １ In the above formula (1), X １ represents a single bond or a carbonyl group.

[0064] For example, X １ represents a single bond, in the above formula (1), S and R １ is directly bonded. That is, X １ When represents a single bond, SX in the above formula (1) １ R １ The Y group is SR １ represents the Y group.

[0065] X １ represents a carbonyl group, S and R １ In other words, when X represents a carbonyl group, SX in the above formula (1) １ R １ The Y group is S(C=O)R １represents a Y group. In other words, the above compound is a thioester (—SC(═O)—) compound.

[0066] X １ Preferably, SX in the above formula (1) represents a carbonyl group. １ R １ The Y group is preferably S(C=O)R １ represents the Y group.

[0067] The compound of the formula (1) may contain a plurality of SX １ R １ In such a case, each SX １ R １ Each X contained in the Y group １ may be the same as or different from each other. Preferably, in the above formula (1), each SX １ R １ Each X contained in the Y group １ are identical to each other.

[0068] (5) R in the formula １ In the above formula (1), R １ represents an alkylene group. Examples of the alkylene group include alkylene groups having 1 to 10 carbon atoms, and preferably alkylene groups having 1 to 4 carbon atoms. Examples of the alkylene group having 1 to 4 carbon atoms include methylene (-CH ２ -), methylmethylene (-CH(CH ３ )-), dimethylmethylene (-C(CH ３ ) ２ -), ethylene (-CH ２ CH ２ -), trimethylene (-CH ２ CH ２ CH ２ -), and tetramethylene (-CH ２ CH ２ CH ２ CH ２ These may be used alone or in combination of two or more. The alkylene group is preferably an alkylene group having 1 to 2 carbon atoms.

[0069] That is, R １represents preferably an alkylene group having 1 to 2 carbon atoms. The alkylene group having 1 to 2 carbon atoms is preferably methylene (—CH ２ -) and methylmethylene (-CH(CH ３ )-), and more preferably methylene (—CH ２ -) are listed.

[0070] The compound of the formula (1) may contain a plurality of SX １ R １ In such a case, each SX １ R １ Each R contained in the Y group １ may be the same as or different from each other. Preferably, in the above formula (1), each SX １ R １ Each R contained in the Y group １ are identical to each other.

[0071] (6) Y in Formula In the above formula (1), Y represents an aryloxy group or an arylalkyloxy group.

[0072] The aryloxy group is R １ The aryloxy group is a substituent having an oxygen atom (O) directly bonded to the above group and an aromatic ring bonded to the oxygen atom (—O-aromatic ring). Examples of the aryloxy group include aryloxy groups having 6 to 20 carbon atoms, and more specifically, phenoxy groups (—O—C ６ H ５ ), and naphthyloxy group (—O—C １０ H ７ The arylalkyloxy group is R １ The arylalkyloxy group is a substituent having an oxygen atom (O) directly bonded to the oxygen atom, an alkylene group bonded to the oxygen atom, and an aromatic ring bonded to the alkylene group (-O-alkylene group-aromatic ring). Examples of the arylalkyloxy group include arylalkyloxy groups having 7 to 20 carbon atoms, and more specifically, a benzyloxy group (-O-CH ２ -C ６ H ５These may be used alone or in combination of two or more. An aryloxy group is preferred, and a phenoxy group is more preferred.

[0073] That is, in the above formula (1), Y preferably represents an aryloxy group, and more preferably represents a phenoxy group.

[0074] The compound of the formula (1) may contain a plurality of SX １ R １ In such a case, each SX １ R １ Each Y contained in the Y group may be the same as or different from each other. Preferably, in the above formula (1), each SX １ R １ Each Y in the Y group is the same as each other.

[0075] (7) m in formula In the above formula, m represents an integer of 1 or more and n or less. As described above, n is the valence of A. That is, m is 1 or more and the valence of A or less. m preferably represents an integer of 3 or more and 6 or less. m more preferably represents 3 or 4.

[0076] Furthermore, m particularly preferably represents the valence of A. That is, particularly preferably, m and n are the same (m=n). In other words, particularly preferably, all bonds of A are connected to SX １ R １ Y group is bonded, and SX ２ R ２ In addition, m may be less than the valence of A. That is, only some of the bonds of A are bonded to SX. １ R １ In such a case, the remaining bond to the part may be SX ２ R ２ The group is bonded.

[0077] (8) X in the formula ２ In the above formula (1), X ２ represents a single bond or a carbonyl group.

[0078] X ２represents a single bond, in the above formula (1), S and R ２ is directly bonded. That is, X ２ When represents a single bond, SX in the above formula (1) ２ R ２ The group represents an SR group.

[0079] X ２ represents a carbonyl group, S and R ２ is indirectly bonded via a carbonyl group. ２ represents a carbonyl group, the SXR group in the above formula (1) is S(C=O)R ２ The group is shown.

[0080] The compound of the formula (1) may contain a plurality of SX ２ R ２ In such a case, each SX ２ R ２ Each X contained in the group ２ may be the same as or different from each other. Preferably, in the above formula (1), each SX ２ R ２ Each X contained in the group ２ are identical to each other.

[0081] (9) R in the formula ２ In the above formula (1), R ２ represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or an araliphatic hydrocarbon group.

[0082] Examples of the aliphatic hydrocarbon group include aliphatic hydrocarbon groups having 1 to 20 carbon atoms. More specific examples of the aliphatic hydrocarbon group include linear aliphatic hydrocarbon groups having 1 to 20 carbon atoms and cyclic aliphatic hydrocarbon groups having 3 to 20 carbon atoms.

[0083] Examples of the linear aliphatic hydrocarbon group having 1 to 20 carbon atoms include a linear saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms and a linear unsaturated aliphatic hydrocarbon group having 1 to 20 carbon atoms. Examples of the linear saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a 2-butyl group, a 1-pentyl group, a 2-pentyl group, a 3-pentyl group, a 2-methyl-1-butyl group, an isopentyl group, a tert-pentyl group, a 3-methyl-2-butyl group, a neopentyl group, an n-hexyl group, a 4-methyl-2-butyl group, a 5-methyl-1-butyl group, a 6-methyl-2-butyl group, a 7-methyl-2-butyl group, a 8-methyl-2-butyl group, a 9-methyl-2-butyl group, a 10-methyl-2-butyl group, a 20-methyl-2-butyl group, a 21-methyl-2-butyl group, a 22-methyl-2-butyl group, a 23-methyl-2-butyl group, a 24-methyl-2-butyl group, a 25-methyl-2-butyl group, a 26-methyl-2-butyl group, a 27-methyl-2-butyl group, a 28-methyl-2-butyl group, a 29-methyl-2-butyl group, a 30-methyl-2-butyl group, a 31-methyl-2-butyl group, a 32-methyl-2-butyl group, a 33-methyl-2-butyl group, a 34-methyl-2-butyl group, a 35-methyl-2-butyl group, a 36-methyl-2-butyl group, a 37-methyl-2-butyl group, a 38-methyl-2-butyl Examples of the linear unsaturated aliphatic hydrocarbon group having 1 to 20 carbon atoms include vinyl and 2-propenyl groups. These may be used alone or in combination of two or more.

[0084] Examples of cyclic aliphatic hydrocarbon groups having 3 to 20 carbon atoms include saturated cyclic aliphatic hydrocarbon groups having 3 to 20 carbon atoms and unsaturated cyclic aliphatic hydrocarbon groups having 3 to 20 carbon atoms. Examples of saturated cyclic aliphatic hydrocarbon groups having 3 to 20 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl groups. Examples of unsaturated cyclic aliphatic hydrocarbon groups having 3 to 20 carbon atoms include cyclopentenyl and cyclohexenyl groups. These can be used alone or in combination of two or more types.

[0085] 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, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl, 2,3,4-trimethylphenyl, 3,4,5-trimethylphenyl, 2,4,6-trimethylphenyl, 2,3,4,5-tetramethylphenyl, 2,3,4,6-tetramethylphenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 1-naphthyl, and 2-naphthyl groups. These groups can be used alone or in combination of two or more.

[0086] Examples of aromatic aliphatic hydrocarbon groups include aromatic aliphatic hydrocarbon groups having 7 to 20 carbon atoms. Examples of aromatic aliphatic hydrocarbon groups having 7 to 20 carbon atoms include benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylpropyl, 2-phenylpropyl, 3-phenylpropyl, o-methylbenzyl, m-methylbenzyl, p-methylbenzyl, o-ethylbenzyl, m-ethylbenzyl, p-ethylbenzyl, o-isopropylbenzyl, m-isopropylbenzyl, p-isopropylbenzyl, 2,3,4-trimethylbenzyl, 3,4,5-trimethylbenzyl, and 2,4,6-trimethylbenzyl. These can be used alone or in combination of two or more types.

[0087] The aliphatic hydrocarbon group, aromatic hydrocarbon group, and aromatic aliphatic hydrocarbon group may have a substituent. Examples of the substituent include a halogeno group, a cyano group, an amino group, a carboxy group, a sulfonyl group, and an alkoxy group (an alkoxy group not containing an aromatic ring). These may be used alone or in combination of two or more types. The number of substituents is appropriately determined depending on the purpose and application. The substitution position is appropriately determined depending on the purpose and application.

[0088] The compound of the formula (1) may contain a plurality of SX ２ R ２ In such a case, each SX２ R ２ R contained in the group ２ may be the same as or different from each other. Preferably, one selected from the group consisting of an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and an araliphatic hydrocarbon group is used alone. That is, preferably, in the above formula (1), each SX ２ R ２ R contained in the group ２ are identical to each other.

[0089] R ２ represents an aliphatic hydrocarbon group, preferably a linear aliphatic hydrocarbon group having 1 to 10 carbon atoms, more preferably a linear aliphatic hydrocarbon group having 1 to 4 carbon atoms, even more preferably a linear aliphatic hydrocarbon group having 1 or 2 carbon atoms, and particularly preferably a methyl group.

[0090] R ２ When represents an aromatic hydrocarbon group, it is preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 8 carbon atoms, and even more preferably a phenyl group.

[0091] R ２ When represents an aromatic aliphatic hydrocarbon group, preferably, an aromatic aliphatic hydrocarbon group having 7 to 15 carbon atoms is used, more preferably, an aromatic aliphatic hydrocarbon group having 7 to 10 carbon atoms is used, and even more preferably, a benzyl group or a 2-phenylethyl group is used.

[0092] From the viewpoint of achieving both refractive index and weather resistance, R ２ preferably represents an aromatic hydrocarbon group or an araliphatic hydrocarbon group.

[0093] (10) Combination In the above formula (1), n ​​and m may be the same as each other (n=m), or m may be smaller than n (n>m). １ , R １ , Y, X ２ and R ２ may be the same or different from each other. １ , R１ , Y, X ２ and R ２ are selected appropriately depending on the purpose and application.

[0094] Preferably, n=m. That is, in the above formula (1), preferably, the compound represented by the above formula (1) is a compound represented by the above formula (1) having a plurality of SX １ R １ Y group, SX ２ R ２ In such a case, a plurality of SX １ R １ In Y, each X １ are preferably the same as each other, and more preferably represent a carbonyl group. １ R １ In Y, each R １ are preferably the same as each other, and more preferably represent an alkylene group having 1 to 2 carbon atoms. １ R １ In Y, each Y is preferably the same as another, and more preferably represents a phenoxy group.

[0095] From the viewpoint of achieving both refractive index and weather resistance, it is particularly preferable that n=m and X １ represents a carbonyl group, and R １ represents an alkylene group having 1 to 2 carbon atoms, and Y represents a phenoxy group.

[0096] (11) Uses The above compound is a novel compound and has a specific structure represented by the above formula (1). Uses of such a compound will be described in detail later, but include, for example, additives. That is, the additive preferably contains the above compound. More specifically, examples of additives include plasticizers and refractive index adjusters, and preferably plasticizers. That is, the plasticizer preferably contains the above compound. In other words, the above compound is preferably used as a plasticizer. The above compound can be used to obtain a cured product (described below) that has a refractive index, flexibility, and weather resistance.

[0097] 2. Method for Producing the Compound The method for producing the compound is not limited to the above. For example, when n=m in the formula (1), a polythiol corresponding to A in the formula (1) and a SX １ R １ The compound can be prepared by reacting it with a modifying agent corresponding to the Y group.

[0098] In addition, when n<m in the above formula (1), a polythiol corresponding to A in the above formula (1) and SX in the above formula (1) １ R １ A modifying agent corresponding to the Y group and SX of the above formula (1) ２ R ２ The above compound can be prepared by reacting the hydroxyl group with a modifying agent corresponding to the hydroxyl group.

[0099] Examples of such reaction methods include nucleophilic substitution reactions, nucleophilic acylation reactions, cross-coupling reactions, and dehydration condensation reactions. The modifier is appropriately selected depending on the reaction method. For example, a halogenated hydrocarbon can be used as a modifier in nucleophilic substitution reactions. Furthermore, an acyl halide can be used as a modifier in nucleophilic acylation reactions. Furthermore, a carboxylic acid can be used as a modifier in cross-coupling reactions and dehydration condensation reactions.

[0100] The modifier and reaction method are not limited to those described above. For example, an ene-thiol reaction can be used as a reaction method. Furthermore, for example, a compound capable of undergoing an ene-thiol reaction with the above-mentioned tri- or higher functional sulfur-containing polythiol can be used as a modifier. Such compounds include, for example, vinyl compounds. Examples of vinyl compounds include styrene, methylstyrene, and butylstyrene. These can be used alone or in combination of two or more types.

[0101] In addition, in the above formula (1), n=m, and X １represents a carbonyl group, the compound represented by the above formula (1) (thioester compound) can be produced, for example, by reacting (A) a carboxylic acid, (B) a halide of toluenesulfonic acid, (C) a first tertiary amine compound, (D) a second tertiary amine compound, and (E) a thiol.

[0102] Each of the components (A) to (E) will be described in detail below.

[0103] [(A) Carboxylic Acid] Examples of (A) carboxylic acids include carboxylic acids having an aryloxy group and / or an arylalkyloxy group, and preferably carboxylic acids having an aryloxy group. More specific examples of carboxylic acids having an aryloxy group include phenoxyacetic acid, 3-phenoxypropionic acid, and 2-phenoxypropionic acid. These can be used alone or in combination of two or more. Preferred examples of (A) carboxylic acids include phenoxyacetic acid and 2-phenoxypropionic acid.

[0104] [(B) Halide of Toluenesulfonic Acid] (B) Halide of toluenesulfonic acid can be obtained by halogenating toluenesulfonic acid by a known method. Examples of toluenesulfonic acids include p-toluenesulfonic acid, m-toluenesulfonic acid, and o-toluenesulfonic acid. These can be used alone or in combination of two or more. Preferably, toluenesulfonic acid is p-toluenesulfonic acid. Examples of halogens include fluorine, chlorine, bromine, and iodine. These can be used alone or in combination of two or more. Preferably, halogen is chlorine.

[0105] (B) toluenesulfonic acid halides include, for example, p-toluenesulfonic acid fluoride, p-toluenesulfonic acid chloride, m-toluenesulfonic acid fluoride, and m-toluenesulfonic acid chloride. These can be used alone or in combination of two or more. As the toluenesulfonic acid halide, p-toluenesulfonic acid chloride is preferred.

[0106] [(C) to (D) Tertiary Amine Compounds] The tertiary amine compounds are organic compounds having one or more tertiary amino groups per molecule. As described above, the raw material components contain the first tertiary amine compound (C) and the second tertiary amine compound (D).

[0107] [(C) First Tertiary Amine Compound] (C) First tertiary amine compound is a tertiary amine compound having an acid dissociation constant (pKa1) of the conjugate acid of a predetermined value or more.

[0108] More specifically, the acid dissociation constant (pKa1) of the conjugate acid of the first tertiary amine compound (C) is not particularly limited, but is, for example, 7.8 or more, preferably 8.0 or more, more preferably 9.0 or more, even more preferably 10.0 or more, and particularly preferably 10.5 or more. Also, the acid dissociation constant (pKa1) of the conjugate acid of the first tertiary amine compound (C) is, for example, 13.0 or less, preferably 12.0 or less, more preferably 11.5 or less, and even more preferably 11.0 or less.

[0109] The acid dissociation constant of the conjugate acid of the first tertiary amine compound (C) can be determined by neutralization titration. When two or more tertiary amine compounds are used in combination, the acid dissociation constant of the conjugate acid of the first tertiary amine compound (C) is the average value of the acid dissociation constants of the conjugate acids of the respective tertiary amine compounds.

[0110] The first tertiary amine compound (C) is only required to have an acid dissociation constant (pKa1) of the conjugate acid of a predetermined value or more, and the molecular structure of the first tertiary amine compound (C) is not particularly limited.

[0111] For example, in the first tertiary amine compound (C), the number of tertiary amino groups is not particularly limited and may be singular (one) or plural (two or more). In addition, the first tertiary amine compound (C) may or may not have a ring structure. Examples of the ring structure include an aromatic ring, an alicyclic ring, and a heterocyclic ring.

[0112] More specific examples of the (C) first tertiary amine compound include triethylamine (TEA, conjugate acid pKa 10.7), N-ethyldiisopropylamine (DIPEA, conjugate acid pKa 11.4), triethylenediamine (TEDA, conjugate acid pKa 8.7), N-methylmorpholine (NMM, conjugate acid pKa 7.8), 4-dimethylaminopyridine (DMAP, conjugate acid pKa 9.9), and diazabicyclononene (DBN, conjugate acid pKa 13.5). These can be used alone or in combination of two or more.

[0113] From the viewpoint of yellowing resistance, the first tertiary amine compound (C) is preferably a tertiary amine that does not contain an aromatic ring structure in the molecule (aromatic ring structure-free amine). That is, the first tertiary amine compound (C) preferably contains an amine that does not contain an aromatic ring structure. The first tertiary amine compound (C) more preferably consists of an amine that does not contain an aromatic ring structure.

[0114] Among the above-mentioned (C) first tertiary amine compounds, examples of amines not containing an aromatic ring structure include triethylamine (TEA, pKa of conjugate acid 10.7), N-ethyldiisopropylamine (DIPEA, pKa of conjugate acid 11.4), triethylenediamine (TEDA, pKa of conjugate acid 8.7), and N-methylmorpholine (NMM, pKa of conjugate acid 7.8). These can be used alone or in combination of two or more.

[0115] From the viewpoint of yellowing resistance, the first tertiary amine compound (C) is more preferably a tertiary amine that does not contain a ring structure (aromatic ring, alicyclic ring, or heterocyclic ring) in the molecule (a ring-structure-free amine). That is, the first tertiary amine compound (C) more preferably contains an amine that does not contain a ring structure. The first tertiary amine compound (C) is particularly preferably composed of an amine that does not contain a ring structure.

[0116] Among the above-mentioned (C) first tertiary amine compounds, examples of amines not containing a ring structure include triethylamine (TEA, pKa of conjugate acid 10.7), N-ethyldiisopropylamine (DIPEA, pKa of conjugate acid 11.4), and triethylenediamine (TEDA, pKa of conjugate acid 8.7). These can be used alone or in combination of two or more.

[0117] The first tertiary amine compound (C) is preferably a tertiary amine having one tertiary amino group per molecule. That is, the first tertiary amine compound (C) preferably contains a tertiary monoamine. More preferably, the first tertiary amine compound (C) consists of a tertiary monoamine.

[0118] Among the above-mentioned (C) first tertiary amine compounds, examples of tertiary monoamines include triethylamine (TEA, pKa of conjugate acid 10.7), N-ethyldiisopropylamine (DIPEA, pKa of conjugate acid 11.4), and N-methylmorpholine (NMM, pKa of conjugate acid 7.8). These can be used alone or in combination of two or more.

[0119] From the viewpoint of low cost, triethylamine (TEA, pKa of conjugate acid: 10.7) is particularly preferable as the first tertiary amine compound.

[0120] [(D) Second Tertiary Amine Compound] (D) The second tertiary amine compound is a tertiary amine compound having a predetermined molecular structure.

[0121] More specifically, the second tertiary amine compound (D) has two or more tertiary amino groups and one or more ring structures per molecule. Hereinafter, such an amine compound may be referred to as a "ring structure-containing polyfunctional tertiary amine."

[0122] The second tertiary amine compound (D) contains a ring-structure-containing amine having two or more tertiary amino groups in one molecule. The second tertiary amine compound (D) preferably consists of a ring-structure-containing amine having two or more tertiary amino groups in one molecule.

[0123] The second tertiary amine compound (D) may have any molecular structure as long as it has the above-described structure, and the acid dissociation constant (pKa2) of the conjugate acid of the second tertiary amine compound (D) is not particularly limited.

[0124] For example, the acid dissociation constant (pKa2) of the conjugate acid of the (D) second tertiary amine compound may be smaller than the acid dissociation constant (pKa1) of the conjugate acid of the (C) first tertiary amine compound, or may be larger than the acid dissociation constant (pKa1) of the conjugate acid of the (C) first tertiary amine compound, or may be the same as the acid dissociation constant (pKa1) of the conjugate acid of the (C) first tertiary amine compound.

[0125] The acid dissociation constant (pKa2) of the conjugate acid of the second tertiary amine compound (D) is not particularly limited, but is, for example, 5.0 or more, preferably 6.0 or more, and more preferably 7.0 or more. The acid dissociation constant (pKa2) of the conjugate acid of the second tertiary amine compound (D) is, for example, 13.0 or less, preferably 11.0 or less, more preferably 9.0 or less, even more preferably less than 7.8, and particularly preferably 7.5 or less.

[0126] The acid dissociation constant of the conjugate acid of the second tertiary amine compound (D) can be determined by neutralization titration. When two or more types of tertiary amine compounds are used in combination, the acid dissociation constant of the conjugate acid of the second tertiary amine compound (D) is the average value of the acid dissociation constants of the conjugate acids of the respective tertiary amine compounds.

[0127] More specific examples of the second tertiary amine compound (D) include N-methylimidazole (NMIMZ, pKa of conjugate acid 7.1), 4-dimethylaminopyridine (DMAP, pKa of conjugate acid 9.9), and diazabicyclononene (DBN, pKa of conjugate acid 13.5). These can be used alone or in combination of two or more.

[0128] From the viewpoint of reaction efficiency, the second tertiary amine compound (D) is preferably a compound having a resonance structure, more specifically, N-methylimidazole (NMIMZ, pKa of the conjugate acid is 7.1), 4-dimethylaminopyridine (DMAP, pKa of the conjugate acid is 9.9), and diazabicyclononene (DBN, pKa of the conjugate acid is 13.5). In other words, the second tertiary amine compound (D) preferably contains at least one selected from the group consisting of N-methylimidazole, 4-dimethylaminopyridine, and diazabicyclononene. The second tertiary amine compound (D) more preferably consists of at least one selected from the group consisting of N-methylimidazole, 4-dimethylaminopyridine, and diazabicyclononene. From the viewpoint of cost efficiency, the second tertiary amine compound is particularly preferably N-methylimidazole (NMIMZ, pKa of the conjugate acid is 7.1).

[0129] Furthermore, the acid dissociation constant (pKa2) of the conjugate acid of the second tertiary amine compound (D) is not particularly limited, but preferably, the acid dissociation constant (pKa1) of the conjugate acid of the first tertiary amine compound (C) is larger than the acid dissociation constant (pKa2) of the conjugate acid of the second tertiary amine compound (D).

[0130] That is, the combination of the (C) first tertiary amine compound and the (D) second tertiary amine compound is selected so that the acid dissociation constant (pKa1) of the conjugate acid of the (C) first tertiary amine compound is greater than the acid dissociation constant (pKa2) of the conjugate acid of the (D) second tertiary amine compound. If the acid dissociation constant (pKa1) of the conjugate acid of the (C) first tertiary amine compound is greater than the acid dissociation constant (pKa2) of the conjugate acid of the (D) second tertiary amine compound, the hydrochloric acid by-produced when the first intermediate product (described below) is produced and the (C) first tertiary amine compound will produce a more stable amine hydrochloride. This can promote the production of the first intermediate product (described below). As a result, the compound (thioester compound) can be obtained in a higher yield.

[0131] For example, when triethylamine (TEA, pKa of the conjugate acid is 10.7) is selected as the (C) first tertiary amine compound, preferred examples of the (D) second tertiary amine compound include N-methylimidazole (NMIMZ, pKa of the conjugate acid is 7.1) and 4-dimethylaminopyridine (DMAP, pKa of the conjugate acid is 9.9).

[0132] Furthermore, for example, when N-methylimidazole (NMIMZ, pKa of conjugate acid 7.1) is selected as the (D) second tertiary amine compound, preferred examples of the (C) first tertiary amine compound include triethylamine (TEA, pKa of conjugate acid 10.7), N-ethyldiisopropylamine (DIPEA, pKa of conjugate acid 11.4), triethylenediamine (TEDA, pKa of conjugate acid 8.7), and N-methylmorpholine (NMM, pKa of conjugate acid 7.8).

[0133] In such a case, from the viewpoint of reaction efficiency, the difference between the acid dissociation constant (pKa1) of the conjugate acid of the first tertiary amine compound (C) and the acid dissociation constant (pKa2) of the conjugate acid of the second tertiary amine compound (D) is, for example, 0 or more, preferably 1.0 or more, and more preferably 3.0 or more. Furthermore, from the viewpoint of suppressing side reactions, the difference between the acid dissociation constant (pKa1) of the conjugate acid of the first tertiary amine compound (C) and the acid dissociation constant (pKa2) of the conjugate acid of the second tertiary amine compound (D) is, for example, 5.0 or less, preferably 4.0 or less.

[0134] The first tertiary amine compound (C) and the second tertiary amine compound (D) may be the same type of tertiary amine compound, or may be different types of tertiary amine compounds.

[0135] That is, when a tertiary amine compound has an acid dissociation constant (pKa) of the conjugate acid equal to or greater than the above-mentioned predetermined value and does not have the above-mentioned predetermined structure (ring structure-containing polyfunctional tertiary amine), the tertiary amine compound can be used as (C) the first tertiary amine compound, but cannot be used as (D) the second tertiary amine compound.

[0136] Furthermore, when a tertiary amine compound does not have an acid dissociation constant (pKa) of the conjugate acid equal to or greater than the above-mentioned predetermined value and has the above-mentioned predetermined structure (ring structure-containing-polyfunctional-tertiary amine), the tertiary amine compound cannot be used as (C) the first tertiary amine compound, but can be used as (D) the second tertiary amine compound.

[0137] When such a tertiary amine compound is used, (C) the first tertiary amine compound and (D) the second tertiary amine compound are different types of tertiary amine compounds.

[0138] On the other hand, when a tertiary amine compound has an acid dissociation constant (pKa) of the conjugate acid equal to or greater than the above-mentioned predetermined value and has the above-mentioned predetermined structure (ring structure-containing polyfunctional tertiary amine), the tertiary amine compound can be used as (C) the first tertiary amine compound and can also be used as (D) the second tertiary amine compound.

[0139] When such a tertiary amine compound is used, (C) the first tertiary amine compound and (D) the second tertiary amine compound may be the same type of tertiary amine compound.

[0140] From the viewpoint of low cost and reaction efficiency, the first tertiary amine compound (C) and the second tertiary amine compound (D) are preferably different types of tertiary amine compounds.

[0141] [(E) Thiol] Examples of the (E) thiol include the above-mentioned tri- or higher functional sulfur-containing polythiols. More preferred examples of the (E) thiol include 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (GST) and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (FSH).

[0142] In other words, the (E) thiol preferably contains at least one selected from the group consisting of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (GST) and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (FSH). More preferably, the (E) thiol consists of at least one selected from the group consisting of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (GST) and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (FSH).

[0143] (2) Reaction Step In the production of the above compound (thioester compound), the above raw material components are reacted to generate the above compound (thioester compound) (reaction step).

[0144] The reactions in the reaction step include a first reaction, a second reaction, and a third reaction. The first reaction, the second reaction, and the third reaction may be carried out sequentially or simultaneously.

[0145] An embodiment in which the first reaction, the second reaction, and the third reaction are carried out in sequence will be described in detail below.

[0146] [First Reaction] The first reaction is a reaction in which (A) a carboxylic acid and (B) a halide of toluenesulfonic acid are reacted in the presence of (C) a first tertiary amine compound to obtain a first intermediate product.

[0147] More specifically, in the first reaction, for example, first, the carboxylic acid (A) is dissolved in a solvent to prepare a solution of the carboxylic acid (A). The solvent is not particularly limited, and a known organic solvent can be used. The blending ratio of the solvent is not particularly limited, and is appropriately set depending on the purpose and application.

[0148] Next, in the first reaction, the (A) carboxylic acid solution and the (C) first tertiary amine compound are mixed together, and the mixing ratio of the (A) carboxylic acid solution to the (C) first tertiary amine compound is adjusted based on the equivalent ratio of the (C) first tertiary amine compound to the carboxy groups of the (A) carboxylic acid (first tertiary amine compound / carboxy groups).

[0149] More specifically, from the viewpoint of reaction efficiency, the amount of the first tertiary amine compound (C) relative to the carboxy group of the carboxylic acid (A) is 1.0 equivalent or more, preferably 1.05 equivalents or more, more preferably 1.1 equivalents or more. Also, from the viewpoint of cost reduction, the amount of the first tertiary amine compound (C) relative to the carboxy group of the carboxylic acid (A) is less than 2.0 equivalents, preferably 1.5 equivalents or less, more preferably 1.3 equivalents or less.

[0150] By the above mixing, the (A) carboxylic acid solution and the (C) first tertiary amine compound are allowed to coexist in an unreacted state. The mixing conditions are not particularly limited. For example, the mixing temperature is, for example, -50°C or higher. The mixing temperature is, for example, 20°C or lower, preferably 10°C or lower, and more preferably 5°C or lower.

[0151] By the above mixing, a mixture containing (A) a solution of a carboxylic acid and (C) a first tertiary amine compound is obtained.

[0152] Next, in the first reaction, the mixture is mixed with (B) a halide of toluenesulfonic acid, and the mixing ratio of the mixture to (B) a halide of toluenesulfonic acid is adjusted based on the equivalent ratio of (B) a halide of toluenesulfonic acid to the carboxy group of (A) a carboxylic acid (first tertiary amine compound / carboxy group).

[0153] More specifically, from the viewpoint of reaction efficiency, the amount of the halide of toluenesulfonic acid (B) relative to the carboxy group of the carboxylic acid (A) is 1.0 equivalent or more, preferably 1.05 equivalents or more, more preferably 1.1 equivalents or more. Also, from the viewpoint of cost efficiency, the amount of the halide of toluenesulfonic acid (B) relative to the carboxy group of the carboxylic acid (A) is less than 2.0 equivalents, preferably 1.5 equivalents or less, more preferably 1.3 equivalents or less.

[0154] By the above mixing, (A) the carboxylic acid and (B) the toluenesulfonic acid halide are reacted in the presence of (C) the first tertiary amine compound. The reaction conditions are not particularly limited. For example, the reaction temperature is, for example, -50°C or higher. The reaction temperature is, for example, 20°C or lower, preferably 10°C or lower, and more preferably 5°C or lower. The reaction time is, for example, 5 minutes or longer, preferably 30 minutes or longer. The reaction time is, for example, 6 hours or shorter, preferably 3 hours or shorter.

[0155] In the first reaction, a first intermediate product is obtained. More specifically, in the first reaction, toluenesulfonic acid (Ts) is added to the carboxy group (—COOH) of the carboxylic acid (A) in the presence of a first tertiary amino compound (Base1) (C) as a base, to form a first adduct (—COO-Ts). As a result, in the first reaction, the first adduct (—COO-Ts) is obtained as the first intermediate product.

[0156] [Second Reaction] The second reaction is a reaction in which the first intermediate product is reacted with (D) a second tertiary amine compound to obtain a second intermediate product.

[0157] More specifically, in the second reaction, for example, the first intermediate product and (D) the second tertiary amine compound are mixed together, and the mixing ratio of the first intermediate product and (D) the second tertiary amine compound is adjusted based on the equivalent ratio (second tertiary amine compound / carboxy group) of the (D) second tertiary amine compound to the carboxy group of the (A) carboxylic acid (the (A) carboxylic acid used in the first reaction).

[0158] More specifically, from the viewpoint of reaction efficiency, the amount of the second tertiary amine compound (D) relative to the carboxy group of the carboxylic acid (A) is 1.0 equivalent or more, preferably 1.05 equivalents or more, more preferably 1.1 equivalents or more. Also, from the viewpoint of yellowing resistance, the amount of the second tertiary amine compound (D) relative to the carboxy group of the carboxylic acid (A) is less than 2.0 equivalents, preferably 1.5 equivalents or less, more preferably 1.3 equivalents or less.

[0159] From the viewpoint of reaction efficiency, the total amount of the first tertiary amine compound (C) and the second tertiary amine compound (D) relative to the carboxy group of the carboxylic acid (A) is 2.0 equivalents or more, preferably 2.1 equivalents or more, and more preferably 2.2 equivalents or more. From the viewpoints of cost reduction and yellowing resistance, the total amount of the first tertiary amine compound (C) and the second tertiary amine compound (D) relative to the carboxy group of the carboxylic acid (A) is less than 3.0 equivalents, preferably 2.8 equivalents or less, more preferably 2.5 equivalents or less, and even more preferably 2.3 equivalents or less.

[0160] By the above mixing, the first intermediate product and (D) the second tertiary amine compound are reacted. The reaction conditions are not particularly limited. For example, the reaction temperature is, for example, -50°C or higher. The reaction temperature is, for example, 20°C or lower, preferably 10°C or lower, and more preferably 5°C or lower. The reaction time is, for example, 5 minutes or longer, preferably 30 minutes or longer. The reaction time is, for example, 6 hours or shorter, preferably 3 hours or shorter.

[0161] In the second reaction, a second intermediate product is obtained. More specifically, in the above reaction, a substitution reaction occurs between the first adduct (-COO-Ts) as the first intermediate product and the second tertiary amine compound (Base2) (D). As a result, the second tertiary amine compound (Base2) (D) adds to the carbonyl group (-CO-) of the carboxylic acid (A), forming a second adduct (-CO-Base2). As a result, in the second reaction, the second adduct (-CO-Base2) is obtained as the second intermediate product.

[0162] [Third Reaction] The third reaction is a reaction in which the second intermediate product is reacted with (E) a thiol to obtain the compound (thioester compound).

[0163] More specifically, in the third reaction, for example, the second intermediate product and (E) thiol are mixed. The mixing ratio of the second intermediate product and (E) thiol is not particularly limited, but is adjusted, for example, based on the equivalent ratio (carboxy group / mercapto group) of the carboxy group of the (A) carboxylic acid (the (A) carboxylic acid used in the first reaction) to the mercapto group of the (E) thiol.

[0164] More specifically, from the viewpoint of reaction efficiency, the amount of carboxy groups in the (A) carboxylic acid (the (A) carboxylic acid used in the first reaction) relative to the mercapto groups in the (E) thiol is 1.0 equivalent or more, preferably 1.05 equivalents or more, and more preferably 1.1 equivalents or more. Also, from the viewpoint of yellowing resistance, the amount of carboxy groups in the (A) carboxylic acid (the (A) carboxylic acid used in the first reaction) relative to the mercapto groups in the (E) thiol is less than 2.0 equivalents, preferably 1.5 equivalents or less, and more preferably 1.3 equivalents or less.

[0165] By the above mixing, the second intermediate product and the (E) thiol are reacted. The reaction conditions are not particularly limited. For example, the reaction temperature is, for example, -50°C or higher. The reaction temperature is, for example, 20°C or lower, preferably 10°C or lower, and more preferably 5°C or lower. The reaction time is, for example, 5 minutes or longer, preferably 30 minutes or longer. The reaction time is, for example, 6 hours or shorter, preferably 3 hours or shorter.

[0166] In the third reaction, a reaction product containing the above-mentioned compound (thioester compound) is obtained. More specifically, in the third reaction, the second adduct (-CO-Base2) as the second intermediate product undergoes a substitution reaction with the (E) thiol. As a result, the thioalkoxy group (-SR) of the (E) thiol adds to the carbonyl group (-CO-) of the (A) carboxylic acid, forming a third adduct (-CO-S-R). As a result, in the third reaction, the above-mentioned compound (thioester compound) having a thioester structure (-CO-S-) is obtained.

[0167] As described above, the compound (thioester compound) is obtained by reacting raw material components including (A) a carboxylic acid, (B) a halide of toluenesulfonic acid, (C) a first tertiary amine compound, (D) a second tertiary amine compound, and (E) a thiol in a reaction step.

[0168] [Purification] The above compound (thioester compound) is purified by a known method as necessary (purification step). The purification method is not particularly limited, and examples thereof include washing, dehydration, impurity adsorption, liquid-liquid extraction, distillation, and recrystallization. These methods may be used alone or in combination of two or more.

[0169] [Reaction Order] The reaction order in the reaction step is not particularly limited. For example, as described above, the raw material components may be sequentially subjected to the first reaction and the second reaction, and after the first reaction and the second reaction are completed, the raw material components may be subjected to the third reaction.

[0170] More specifically, the raw material components may be subjected to the first reaction before the start of the second reaction and before the start of the third reaction (first reaction step). Alternatively, the raw material components may be subjected to the second reaction after the completion of the first reaction and before the start of the third reaction (second reaction step). Alternatively, the raw material components may be subjected to the third reaction after the completion of the first reaction and after the completion of the second reaction (third reaction step).

[0171] Furthermore, for example, the raw material components may be subjected to the first reaction and the second reaction simultaneously (batch reaction step), and after the first reaction and the second reaction are completed, the raw material components may be subjected to the third reaction.

[0172] In such a case, for example, the (A) carboxylic acid, (C) the first tertiary amine compound, and (D) the second tertiary amine compound are first mixed in the above-mentioned ratio and under the above-mentioned conditions to obtain a lump mixture containing the (A) carboxylic acid, (C) the first tertiary amine compound, and (D) the second tertiary amine compound.

[0173] Next, in this method, the lump mixture is mixed with (B) a halide of toluenesulfonic acid in the ratio and under the conditions described above.

[0174] As a result, in the presence of the first tertiary amine compound (C), the carboxylic acid (A) and the halide of toluenesulfonic acid (B) react (first reaction) to produce a first intermediate product. As the first reaction progresses, the first intermediate product reacts with the second tertiary amine compound (D) to produce a second intermediate product (second reaction). In other words, the raw material components are simultaneously subjected to the first reaction and the second reaction.

[0175] Then, in this method, the second intermediate product and the (E) thiol are mixed in the above-mentioned ratio and under the above-mentioned conditions, whereby the second intermediate product and the (E) thiol react with each other (third reaction) to produce the above-mentioned compound (thioester compound).

[0176] That is, as described above, even when the raw material components are subjected to the first and second reactions simultaneously and then subjected to the third reaction, the above compound (thioester compound) is produced.

[0177] The order of the reactions in the reaction steps is not limited to the above. For example, the first reaction may be carried out first to obtain a first intermediate product, and then (D) the second tertiary amine compound and (E) the thiol may be added to the first intermediate product simultaneously. In this case, the second reaction proceeds while the third reaction proceeds, producing the compound (thioester compound).

[0178] That is, the above compound (thioester compound) is also produced when the raw material components are subjected to the first reaction and then simultaneously subjected to the second and third reactions.

[0179] Furthermore, for example, (A) a carboxylic acid, (B) a halide of toluenesulfonic acid, (C) a first tertiary amine compound, (D) a second tertiary amine compound, and (E) a thiol can be mixed all at once. In such a case, the first reaction proceeds while the second reaction proceeds, producing a second intermediate product. Furthermore, the second reaction proceeds while the third reaction proceeds, producing the compound (thioester compound).

[0180] That is, even when the raw material components are simultaneously subjected to the first reaction, the second reaction, and the third reaction, the above-mentioned compound (thioester compound) is produced.

[0181] From the viewpoint of reaction efficiency, the raw material components are preferably first subjected to the first reaction and the second reaction, sequentially or simultaneously, and then subjected to the third reaction after the completion of the first and second reactions. From the viewpoint of reaction efficiency, the raw material components are more preferably subjected to the first reaction, the second reaction, and the third reaction, sequentially. That is, the raw material components are more preferably first subjected to the first reaction before the initiation of the second reaction and before the initiation of the third reaction, subjected to the second reaction after the completion of the first reaction and before the initiation of the third reaction, and subjected to the third reaction after the completion of the first reaction and after the completion of the second reaction. This allows the above compound (thioester compound) to be obtained in a relatively short time and with an excellent yield.

[0182] 3. Curable Composition (1) Main Component The curable composition contains a plasticizer and a curable compound as main components. The main component is a component whose content relative to the total is equal to or greater than a predetermined value. The content ratio of the main component relative to the total is, for example, 90% by mass or more. In other words, the total solid content of the plasticizer and the curable compound is 90% by mass or more relative to the total solid content of the curable composition.

[0183] The curable compound is an uncured compound that is cured by a known method to produce a cured resin (described below). The plasticizer is an additive that improves the flexibility of the cured resin (described below). The plasticizer and the curable compound are described in detail below.

[0184] (2) Plasticizer The plasticizer contains a compound represented by the above formula (1), and preferably consists of a compound represented by the above formula (1).

[0185] When the plasticizer contains a compound represented by the above formula (1), the plasticizer can improve the flexibility of the cured product (described later) and can suppress a decrease in the refractive index of the cured product (described later) or can improve the refractive index.

[0186] (3) Curable Compound The curable compound is not particularly limited, and examples thereof include resin raw materials capable of producing a cured resin (described below).

[0187] As described below, examples of the cured resin include cured polyurethane resin, cured polyolefin resin, cured polyamine resin, cured amide resin, cured urea resin, cured phenolic resin, cured epoxy resin, cured acrylic resin, cured melamine resin, and cured alkyd resin. These may be used alone or in combination of two or more.

[0188] As the curable resin (described later), preferably, a curable polyurethane resin or a curable acrylic resin is used, and the curable compound is selected depending on the type of the curable resin (described later).

[0189] For example, when a cured polyurethane resin is used as the curable resin, the curable compound may be, for example, a polyurethane resin raw material, or when a cured acrylic resin is used as the curable resin, the curable compound may be, for example, an acrylic resin raw material.

[0190] The polyurethane resin raw material and the acrylic resin raw material will be described in detail below.

[0191] (3-1) Polyurethane Resin Raw Material The polyurethane resin raw material is an uncured (unreacted) resin composition for producing a cured polyurethane resin (described later). The polyurethane resin raw material includes, for example, a polyisocyanate and a polyol.

[0192] (3-2) Polyisocyanate Polyisocyanate has multiple isocyanate groups in one molecule. Examples of polyisocyanate include polyisocyanate monomers and polyisocyanate derivatives.

[0193] Examples of polyisocyanate monomers include aliphatic polyisocyanates, aromatic polyisocyanates, and araliphatic polyisocyanates.

[0194] Examples of aliphatic polyisocyanates include ethylene diisocyanate, trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and 2,6-diisocyanate methyl caproate. These can be used alone or in combination of two or more.

[0195] The aliphatic polyisocyanate monomer also includes an alicyclic polyisocyanate monomer. Examples of the alicyclic polyisocyanate monomer include 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, methylenebis(cyclohexyl isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, norbornane diisocyanate, and bis(isocyanatomethyl)cyclohexane. These can be used alone or in combination of two or more types.

[0196] Examples of aromatic polyisocyanates include tolylene diisocyanate, phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane diisocyanate, 4,4'-toluidine diisocyanate, and 4,4'-diphenyl ether diisocyanate. These can be used alone or in combination of two or more.

[0197] Examples of aromatic aliphatic polyisocyanates include xylylene diisocyanate, tetramethylxylylene diisocyanate, and ω,ω'-diisocyanate-1,4-diethylbenzene. These can be used alone or in combination of two or more.

[0198] The polyisocyanate derivative is derived from the polyisocyanate monomer described above. Examples of the polyisocyanate derivative include isocyanurate-modified products, iminooxadiazinedione-modified products, triol adducts, allophanate-modified products, biuret-modified products, urea-modified products, oxadiazinetrione-modified products, carbodiimide-modified products, uretdione-modified products, and uretonimine-modified products. These can be used alone or in combination of two or more types. A preferred example of the polyisocyanate derivative is an isocyanurate-modified product.

[0199] The polyisocyanate may be used alone or in combination of two or more kinds. The polyisocyanate preferably contains a polyisocyanate derivative, and more preferably consists of a polyisocyanate derivative.

[0200] As the polyisocyanate derivative, from the viewpoint of improving the refractive index and transparency, a polyisocyanate derivative derived from an araliphatic polyisocyanate (araliphatic polyisocyanate derivative) is preferably used.

[0201] As the aromatic aliphatic polyisocyanate derivative, a derivative of xylylene diisocyanate is more preferred, and a triol adduct of xylylene diisocyanate is even more preferred.

[0202] The polyisocyanate has an average number of isocyanate groups of, for example, 2 or more, or preferably 2.5 or more. The polyisocyanate has an average number of isocyanate groups of, for example, 4 or less, or preferably 3.5 or less.

[0203] The polyisocyanate has an isocyanate group content (NCO%) of, for example, 5% by mass or more, or preferably 7% by mass or more, and for example, 30% by mass or less, or preferably 25% by mass or less.

[0204] (3-3) Polyols Polyols include, for example, macropolyols. Macropolyols have two or more hydroxyl groups per molecule. Macropolyols are relatively high molecular weight organic compounds. The number average molecular weight of macropolyols is, for example, 400 or more and, for example, 20,000 or less. The number average molecular weight can be calculated by a known method from the hydroxyl group equivalent weight and the average number of hydroxyl groups. The number average molecular weight can also be measured as a polystyrene-equivalent molecular weight by gel permeation chromatography (the same applies below).

[0205] Examples of macropolyols include polyether polyols, polyester polyols, polycarbonate polyols, polyurethane polyols, epoxy polyols, vegetable oil polyols, polyolefin polyols, acrylic polyols, and vinyl monomer-modified polyols. These macropolyols can be used alone or in combination of two or more.

[0206] The number average molecular weight of the macropolyol is, for example, more than 400, preferably 500 or more, more preferably 1000 or more. The number average molecular weight of the macropolyol is, for example, 20,000 or less, preferably 15,000 or less, more preferably 10,000 or less, and even more preferably 5,000 or less.

[0207] The hydroxyl value of the macropolyol is, for example, 5 mg KOH / g or more, preferably 10 mg KOH / g or more, more preferably 15 mg KOH / g or more, and even more preferably 20 mg KOH / g or more. The hydroxyl value of the macropolyol is, for example, 500 mg KOH / g or less, preferably 300 mg KOH / g or less, more preferably 200 mg KOH / g or less, even more preferably 100 mg KOH / g or less, and particularly preferably 50 mg KOH / g or less. The hydroxyl value is measured in accordance with the description of JIS K 1557-1 (2007) (hereinafter the same).

[0208] As the macropolyol, preferably, an acrylic polyol is used.

[0209] The acrylic polyol may be, for example, a copolymer of an acrylic raw material component, which may contain, for example, a hydroxyl group-containing (meth)acrylate and a copolymerizable vinyl monomer.

[0210] The term "(meth)acrylate" refers to an acrylate and / or a methacrylate, and the term "copolymerizable vinyl monomer" refers to a vinyl monomer that can be polymerized with the hydroxyl group-containing (meth)acrylate.

[0211] The hydroxyl group-containing (meth)acrylate contains a hydroxyl group and an alkyl group. Examples of the alkyl group include alkyl groups having 1 to 4 carbon atoms. Specific examples of the hydroxyalkyl (meth)acrylate include 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and 2,2-dihydroxymethylbutyl (meth)acrylate. These may be used alone or in combination of two or more. Preferred examples of the hydroxyl group-containing (meth)acrylate include hydroxyalkyl (meth)acrylate, more preferably 2-hydroxyethyl (meth)acrylate, and even more preferably 2-hydroxyethyl methacrylate.

[0212] Examples of copolymerizable vinyl monomers include alkyl(meth)acrylates. Alkyl(meth)acrylates do not contain hydroxyl groups but contain an alkyl group. Examples of alkyl groups include alkyl groups having 1 to 4 carbon atoms and alkyl groups having 5 to 8 carbon atoms. Examples of alkyl(meth)acrylates having an alkyl group having 1 to 4 carbon atoms include methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, isopropyl(meth)acrylate, butyl(meth)acrylate, isobutyl(meth)acrylate, s-butyl(meth)acrylate, and t-butyl(meth)acrylate. Examples of alkyl(meth)acrylates having an alkyl group having 5 to 8 carbon atoms include pentyl(meth)acrylate, isopentyl(meth)acrylate, hexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, and cyclohexyl(meth)acrylate. These can be used alone or in combination of two or more.

[0213] Furthermore, examples of copolymerizable vinyl monomers include aromatic ring-containing vinyl monomers. Examples of aromatic ring-containing vinyl monomers include aromatic ring-containing (meth)acrylates. Aromatic ring-containing (meth)acrylates contain an aromatic ring. Examples of aromatic rings include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. More specific examples of aromatic ring-containing (meth)acrylates include benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, m-phenoxybenzyl (meth)acrylate, and 1-naphthylmethyl (meth)acrylate. These can be used alone or in combination of two or more. Preferred examples of aromatic ring-containing (meth)acrylates include m-phenoxybenzyl (meth)acrylate and naphthylmethyl (meth)acrylate, and more preferred examples include m-phenoxybenzyl acrylate and naphthylmethyl acrylate. In addition to the above, examples of aromatic ring-containing vinyl monomers include styrene, α-methylstyrene, vinyltoluene, vinylbiphenyl, and divinylbenzene. These can be used alone or in combination of two or more. Preferred examples of aromatic ring-containing vinyl monomers include aromatic ring-containing (meth)acrylates.

[0214] Furthermore, examples of copolymerizable vinyl monomers include vinyl monomers containing functional groups (excluding hydroxyl groups). Examples of vinyl monomers containing functional groups (excluding hydroxyl groups) include carboxyl group-containing vinyl monomers, glycidyl group-containing vinyl monomers, amino group-containing vinyl monomers, cyano group-containing vinyl monomers, acetoacetoxy group-containing vinyl monomers, sulfonic acid group-containing vinyl monomers, and phosphate group-containing vinyl monomers. Examples of carboxyl group-containing vinyl monomers include acrylic acid. Examples of glycidyl group-containing vinyl monomers include glycidyl (meth)acrylate. Examples of amino group-containing vinyl monomers include 2-aminoethyl (meth)acrylate. Examples of cyano group-containing vinyl monomers include (meth)acrylonitrile. Examples of acetoacetoxy group-containing vinyl monomers include acetoacetoxyethyl (meth)acrylate. Examples of sulfonic acid group-containing vinyl monomers include allyl sulfonic acid and its salts. Examples of phosphate group-containing vinyl monomers include 2-methacryloyloxyethyl acid phosphate. These may be used alone or in combination of two or more. As the vinyl monomer containing a functional group (excluding a hydroxyl group), preferably, a vinyl monomer containing a carboxyl group is used, and more preferably, acrylic acid is used.

[0215] Examples of copolymerizable vinyl monomers include alicyclic group-containing vinyl monomers and (meth)acryloyl group-containing rubbers. Examples of alicyclic group-containing vinyl monomers include dicyclopentenyloxyethyl (meth)acrylate. Examples of (meth)acryloyl group-containing rubbers include (meth)acryloyl group-containing isoprene rubber. Furthermore, examples of copolymerizable vinyl monomers include, in addition to the above, vinyl esters, N-substituted unsaturated carboxylic acid amides, heterocyclic vinyl compounds, vinylidene halides, α-olefins, dienes, and crosslinkable vinyl monomers. Examples of crosslinkable vinyl monomers include polyfunctional (meth)acrylates, more specifically, bifunctional (meth)acrylates, trifunctional (meth)acrylates, and tetrafunctional or higher (meth)acrylates. Examples of bifunctional (meth)acrylates include ethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, and oligoethylene glycol di(meth)acrylate. Examples of trifunctional (meth)acrylates include trimethylolpropane tri(meth)acrylate. Examples of tetrafunctional or higher functional (meth)acrylates include pentaerythritol tetra(meth)acrylate. These may be used alone or in combination of two or more.

[0216] These copolymerizable vinyl monomers may be used alone or in combination of two or more.

[0217] The copolymerizable vinyl monomer is preferably an aromatic ring-containing vinyl monomer. If the copolymerizable vinyl monomer contains an aromatic ring-containing vinyl monomer, the acrylic polyol contains an aromatic ring. In other words, the acrylic polyol is preferably an aromatic ring-containing acrylic polyol. The aromatic ring-containing acrylic polyol can provide a cured product (described below) having an excellent refractive index and excellent flexibility.

[0218] Furthermore, as the copolymerizable vinyl monomer, a carboxy group-containing vinyl monomer is preferably used. If the acrylic polyol contains a carboxy group-containing vinyl monomer, the acrylic polyol contains a carboxy group. In other words, the acrylic polyol is preferably a carboxy group-containing acrylic polyol. The carboxy group-containing acrylic polyol can provide a cured product (described later) having an excellent refractive index and excellent flexibility.

[0219] The blending ratio of the hydroxyl group-containing (meth)acrylate and the copolymerizable vinyl monomer is appropriately set depending on the purpose and application. For example, the hydroxyl group-containing (meth)acrylate is, for example, 1 part by mass or more, preferably 3 parts by mass or more, per 100 parts by mass of the total of the hydroxyl group-containing (meth)acrylate and the copolymerizable vinyl monomer. Furthermore, the hydroxyl group-containing (meth)acrylate is, for example, 30 parts by mass or less, preferably 10 parts by mass or less, per 100 parts by mass of the total of the hydroxyl group-containing (meth)acrylate and the copolymerizable vinyl monomer.

[0220] The total amount of the copolymerizable vinyl monomer is, for example, 70 parts by mass or more, preferably 90 parts by mass or more, relative to 100 parts by mass of the total amount of the hydroxyl group-containing (meth)acrylate and the copolymerizable vinyl monomer. The total amount of the copolymerizable vinyl monomer is, for example, 99 parts by mass or less, preferably 97 parts by mass or less, relative to 100 parts by mass of the total amount of the hydroxyl group-containing (meth)acrylate and the copolymerizable vinyl monomer.

[0221] More specifically, when an aromatic ring-containing vinyl monomer is used, the amount of the aromatic ring-containing vinyl monomer is, for example, 70 parts by mass or more, preferably 90 parts by mass or more, per 100 parts by mass of the total amount of the hydroxyl group-containing (meth)acrylate and the copolymerizable vinyl monomer, and the amount of the aromatic ring-containing vinyl monomer is, for example, 99 parts by mass or less, preferably 97 parts by mass or less, per 100 parts by mass of the total amount of the hydroxyl group-containing (meth)acrylate and the copolymerizable vinyl monomer.

[0222] When a carboxyl group-containing vinyl monomer is used, the content of the carboxyl group-containing vinyl monomer is appropriately set so that the total of the acid value and hydroxyl value of the acrylic polyol (carboxyl group-containing acrylic polyol) falls within the range described below.

[0223] For example, the amount of the carboxyl group-containing vinyl monomer is, for example, 1 part by mass or more, preferably 5 parts by mass or more, per 100 parts by mass of the total amount of the hydroxyl group-containing (meth)acrylate and the copolymerizable vinyl monomer, and the amount of the carboxyl group-containing vinyl monomer is, for example, 99 parts by mass or less, preferably 97 parts by mass or less, per 100 parts by mass of the total amount of the hydroxyl group-containing (meth)acrylate and the copolymerizable vinyl monomer.

[0224] The method for producing the acrylic polyol is not particularly limited. For example, the above-mentioned acrylic raw material components are copolymerized in the presence of a known organic solvent. Examples of the organic solvent include toluene. The blending ratio and blending timing of the organic solvent are appropriately set depending on the purpose and application.

[0225] In the production of acrylic polyol, a known polymerization initiator is used as necessary. Examples of the polymerization initiator include known radical polymerization initiators (described below), more preferably azo compounds (described below) and peroxides (described below), even more preferably peroxides (described below), and particularly preferably t-butylperoxy-2-ethylhexanoate. The blending ratio and blending timing of the polymerization initiator are appropriately set depending on the purpose and application.

[0226] The polymerization conditions for the acrylic raw material components are appropriately set depending on the purpose and application. For example, the polymerization temperature is, for example, 50°C or higher, preferably 70°C or higher. The polymerization temperature is, for example, 150°C or lower, preferably 130°C or lower. The polymerization time is, for example, 30 minutes or longer, preferably 1 hour or longer. The polymerization time is, for example, 12 hours or shorter, preferably 6 hours or shorter.

[0227] For example, when an organic solvent is used in the above polymerization method, a solution and / or dispersion of the acrylic polyol is obtained as the reaction product liquid.

[0228] The solids concentration of the acrylic polyol solution and / or dispersion can be adjusted by a known method. For example, an organic solvent can be added to the reaction product liquid as needed. Alternatively, a portion of the organic solvent can be removed from the reaction product liquid.

[0229] The solids concentration of the acrylic polyol solution and / or dispersion is, for example, 30% by mass or more, preferably 40% by mass or more, and for example, 60% by mass or less, preferably 50% by mass or less.

[0230] The number average molecular weight of the acrylic polyol is, for example, more than 400, preferably 500 or more, and more preferably 1000 or more. The number average molecular weight of the acrylic polyol is, for example, 20000 or less, preferably 15000 or less, more preferably 10000 or less, and even more preferably 5000 or less.

[0231] The hydroxyl value of the acrylic polyol is, for example, 1 mgKOH / g or more, preferably 3 mgKOH / g or more. The hydroxyl value of the acrylic polyol is, for example, 500 mgKOH / g or less, preferably 300 mgKOH / g or less. The hydroxyl value is measured in accordance with the description of JIS K 1557-1 (2007) (the same applies hereinafter).

[0232] When the acrylic polyol does not contain a carboxyl group-containing acrylic polyol, the hydroxyl value of the acrylic polyol is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, even more preferably 15 mgKOH / g or more, and particularly preferably 20 mgKOH / g or more. The hydroxyl value of the acrylic polyol is preferably 200 mgKOH / g or less, more preferably 100 mgKOH / g or less, and particularly preferably 50 mgKOH / g or less.

[0233] Furthermore, when the acrylic polyol contains a carboxy group-containing acrylic polyol, the total acid value and hydroxyl value of the acrylic polyol (carboxy group-containing acrylic polyol) is preferably 1 mgKOH / g or more, more preferably 3 mgKOH / g or more. Furthermore, the total acid value and hydroxyl value of the acrylic polyol (carboxy group-containing acrylic polyol) is preferably 20 mgKOH / g or less, more preferably 10 mgKOH / g or less. The total acid value and hydroxyl value are measured in accordance with the description of JIS K 1557-5 (2007) (the same applies hereinafter).

[0234] When the acrylic polyol contains a carboxyl group-containing acrylic polyol, the acid value of the acrylic polyol (carboxyl group-containing acrylic polyol) is, for example, 1 mgKOH / g or more, preferably 3 mgKOH / g or more. The acid value of the acrylic polyol (carboxyl group-containing acrylic polyol) is, for example, 20 mgKOH / g or less, preferably 10 mgKOH / g or less. The acid value is measured in accordance with the description of JIS K 1557-5 (2007) (the same applies hereinafter).

[0235] The polyol may include a low molecular weight polyol in addition to the macropolyol. The low molecular weight polyol has two or more hydroxyl groups in one molecule. The low molecular weight polyol is a relatively low molecular weight organic compound. The molecular weight of the low molecular weight polyol is, for example, 40 or more, for example, 400 or less.

[0236] Examples of low-molecular-weight polyols include dihydric alcohols, trihydric alcohols, and tetrahydric or higher alcohols. Examples of dihydric alcohols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, and dipropylene glycol. Examples of trihydric alcohols include glycerin and trimethylolpropane. Examples of tetrahydric or higher alcohols include pentaerythritol and diglycerin. Examples of low-molecular-weight polyols include polymers obtained by addition polymerization of alkylene (C2-C3) oxides with dihydric to tetrahydric alcohols to obtain a number-average molecular weight of less than 400. These can be used alone or in combination of two or more types. Examples of low-molecular-weight polyols include preferably dihydric alcohols and trihydric alcohols, and more preferably dihydric alcohols.

[0237] The polyols can be used alone or in combination of two or more. As the polyol, preferably, a macropolyol is used alone, and more preferably, an acrylic polyol is used alone.

[0238] (3-4) Form of polyurethane resin raw material Examples of the form of polyurethane resin raw material include one-component curing polyurethane resin and two-component curing polyurethane resin. A preferred form of polyurethane resin raw material is two-component curing polyurethane resin. A two-component curing polyurethane resin comprises an independent curing agent and a base agent.

[0239] In the two-component curing polyurethane resin, the curing agent includes, for example, the above-mentioned polyisocyanate. In the two-component curing polyurethane resin, the base agent includes, for example, the above-mentioned polyol. The curing agent and base agent are blended at the time of use to form a urethane cured product (cured resin described below). In the base agent, the polyol may be diluted with a known organic solvent. In the curing agent, the polyisocyanate may be diluted with a known organic solvent.

[0240] The two-component curing polyurethane resin preferably contains a base resin containing the above-mentioned acrylic polyol and a curing agent containing the above-mentioned polyisocyanate, thereby producing a cured product (described below) that has an excellent refractive index, flexibility, and weather resistance.

[0241] The polyisocyanate and polyol undergo a urethane reaction by a known method to produce a cured polyurethane resin. In the urethane reaction, the blending ratio of the polyisocyanate and the polyol is adjusted, for example, based on the equivalent ratio (OH / NCO) of the hydroxyl groups in the polyol to the isocyanate groups in the polyisocyanate. The equivalent ratio (OH / NCO) of the hydroxyl groups in the polyol to the isocyanate groups in the polyisocyanate is, for example, 0.5 or more, preferably 0.8 or more, and more preferably 0.95 or more. Furthermore, the equivalent ratio (OH / NCO) of the hydroxyl groups in the polyol to the isocyanate groups in the polyisocyanate is, for example, 2.0 or less, preferably 1.5 or less, and more preferably 1.1 or less.

[0242] When the polyol contains the carboxyl group-containing acrylic polyol, the blending ratio of the polyisocyanate and the polyol is adjusted, for example, based on the equivalent ratio (OH+COOH / NCO) of the total amount of hydroxyl groups and carboxyl groups in the polyol to the isocyanate groups in the polyisocyanate. The equivalent ratio (OH+COOH / NCO) of the total amount of hydroxyl groups and carboxyl groups in the polyol to the isocyanate groups in the polyisocyanate is, for example, 0.5 or more, preferably 0.8 or more, and more preferably 0.95 or more. The equivalent ratio (OH+COOH / NCO) of the total amount of hydroxyl groups and carboxyl groups in the polyol to the isocyanate groups in the polyisocyanate is, for example, 2.0 or less, preferably 1.5 or less, and more preferably 1.1 or less.

[0243] (3-5) Acrylic Resin Raw Material The acrylic resin raw material is a curable compound for producing a cured acrylic resin (described later). The acrylic resin raw material contains, for example, a monomer component and a polymerization initiator.

[0244] (3-6) Monomer Component The monomer component contains, for example, a radically polymerizable monomer. The radically polymerizable monomer is a monomer that can generate a cured acrylic resin by radical polymerization.

[0245] Examples of radical polymerizable monomers include the monomers described above as raw materials for acrylic polyols. More specifically, examples of radical polymerizable monomers include the alkyl (meth)acrylates, hydroxyl group-containing (meth)acrylates, aromatic ring-containing vinyl monomers, carboxy group-containing vinyl monomers, glycidyl group-containing vinyl monomers, amino group-containing vinyl monomers, cyano group-containing vinyl monomers, acetoacetoxy group-containing vinyl monomers, sulfonic acid group-containing vinyl monomers, phosphoric acid group-containing vinyl monomers, alicyclic group-containing vinyl monomers, (meth)acryloyl group-containing rubbers, vinyl esters, N-substituted unsaturated carboxylic acid amides, heterocyclic vinyl compounds, vinylidene halide compounds, α-olefins, dienes, and crosslinkable vinyl monomers. These can be used alone or in combination of two or more.

[0246] As the radical polymerizable monomer, preferably, an alicyclic group-containing vinyl monomer and a (meth)acryloyl group-containing rubber are used, and more preferably, dicyclopentenyloxyethyl (meth)acrylate and a (meth)acryloyl group-containing isoprene rubber are used.

[0247] (3-7) Polymerization Initiator Examples of the polymerization initiator include known radical polymerization initiators, such as active energy ray radical polymerization initiators and thermal radical polymerization initiators.

[0248] Examples of active energy ray radical polymerization initiators include photoradical polymerization initiators. Examples of photoradical polymerization initiators include alkylphenone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, oxime ester-based photopolymerization initiators, carbazolephenone-based photopolymerization initiators, acridine-based photopolymerization initiators, triazine-based photopolymerization initiators, and benzoyl-based photopolymerization initiators. These can be used alone or in combination of two or more.

[0249] Examples of thermal radical polymerization initiators include azo compounds and peroxides. Examples of azo compounds include azoisobutyronitrile and dimethylazoisobutyrate. Examples of peroxides include benzoyl peroxide, ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxy ester, t-butylperoxy-2-ethylhexanoate, and peroxydicarbonate. These can be used alone or in combination of two or more.

[0250] The active energy ray radical polymerization initiator may also function as a thermal radical polymerization initiator, and the thermal radical polymerization initiator may also function as an active energy ray radical polymerization initiator.

[0251] The radical polymerization initiator may be commercially available. Examples of commercially available radical polymerization initiators include the Omnirad series manufactured by IGM Resins B.V. and the Percure series manufactured by NOF Corporation. These may be used alone or in combination of two or more types.

[0252] The polymerization initiator is preferably an active energy ray radical polymerization initiator, more preferably a photopolymerization initiator. The blending ratio and blending timing of the polymerization initiator are appropriately set depending on the purpose and application.

[0253] (3-8) Formulation of Acrylic Resin Raw Material The acrylic resin raw material may be, for example, a mixture containing the radical polymerizable monomer and the polymerization initiator. The acrylic resin raw material may also contain a known organic solvent. Preferably, the acrylic resin raw material does not contain an organic solvent and is composed of the radical polymerizable monomer and the polymerization initiator.

[0254] (4) Form of Curable Composition The curable composition contains, for example, a plasticizer and a curable compound as described above. Preferably, the curable composition contains a plasticizer and a polyurethane resin raw material and / or an acrylic resin raw material as the curable compound. More preferably, the curable composition contains a plasticizer and a polyurethane resin raw material, or a plasticizer and an acrylic resin raw material.

[0255] The blending ratio of the plasticizer and the curable compound is not particularly limited and is appropriately set depending on the purpose and application. For example, the plasticizer is, for example, 1 part by mass (phr) or more, preferably 5 parts by mass (phr) or more, per 100 parts by mass of the solid content of the curable compound. Furthermore, the plasticizer is, for example, 70 parts by mass (phr) or less, preferably 50 parts by mass (phr) or less, per 100 parts by mass of the solid content of the curable compound.

[0256] The content of the plasticizer is, for example, 1% by mass or more, preferably 3% by mass or more, based on the total amount (solid content) of the plasticizer and the curable compound, and is, for example, 50% by mass or less, preferably 35% by mass or less, based on the total amount (solid content) of the plasticizer and the curable compound.

[0257] The content of the curable compound is, for example, 50% by mass or more, preferably 65% ​​by mass or more, based on the total amount (solid content) of the plasticizer and the curable compound, and is, for example, 99% by mass or less, preferably 97% by mass or less, based on the total amount (solid content) of the plasticizer and the curable compound.

[0258] The form in which the plasticizer is contained is not particularly limited. For example, when the curable compound is a two-component curing polyurethane resin, the plasticizer may be added to the curing agent (polyisocyanate) of the two-component curing polyurethane resin. Alternatively, the plasticizer may be added to the base agent (polyol) of the two-component curing polyurethane resin. Alternatively, the plasticizer may be added to both the base agent and the curing agent of the two-component curing polyurethane resin.

[0259] The plasticizer may be prepared separately from the base component and curing agent of the two-component curing polyurethane resin. When the plasticizer is prepared separately, the plasticizer may be added simultaneously with the base component and curing agent when they are mixed, or may be added to the mixture after the base component and curing agent are mixed.

[0260] Furthermore, for example, when the curable compound is an acrylic resin raw material, the plasticizer may be mixed in advance with the radical polymerizable monomer. Alternatively, the plasticizer may be mixed in advance with the polymerization initiator. Alternatively, the plasticizer may be added simultaneously with the mixing of the radical polymerizable monomer and the polymerization initiator, or may be added to the mixture after the mixing of the radical polymerizable monomer and the polymerization initiator.

[0261] (5) Subcomponent The curable composition may contain additives as subcomponents, if necessary. The subcomponent is a component whose content relative to the total content is a predetermined value or less. The content ratio of the subcomponent relative to the total content is, for example, 10% by mass or less. In other words, the proportion of the additive is 10% by mass or less relative to the total solid content of the curable composition.

[0262] Examples of additives include ultraviolet absorbers (UV absorbers), light stabilizers (light stabilizers), and antioxidants.Further examples of additives include heat stabilizers, crosslinking agents, silane coupling agents, antifoaming agents, leveling agents, mildew inhibitors, rust inhibitors, matting agents, flame retardants, thixotropic agents, tackifiers, thickeners, lubricants, antistatic agents, surfactants, reaction retarders, hydrolysis inhibitors, dyes, inorganic pigments, organic pigments, anti-tack agents, inorganic fillers, and organic fillers.These may be used alone or in combination of two or more.The amount and timing of addition of the additives are appropriately determined depending on the purpose and application.

[0263] From the viewpoint of the weather resistance of the cured product (described later), preferred additives include an ultraviolet absorber (UV absorber), a light stabilizer (light stabilizer), and an antioxidant. That is, the curable composition preferably contains at least one additive selected from the group consisting of an ultraviolet absorber, a light stabilizer, and an antioxidant. From the viewpoint of the weather resistance of the cured product (described later), the ratio of the additive (at least one additive selected from the group consisting of an ultraviolet absorber, a light stabilizer, and an antioxidant) is, for example, 1 × 10 with respect to 1 part by mass of the above-described curable composition (total amount). －６ Parts by mass (ppm) or more, preferably 10 x 10 －６ Parts by mass (ppm) or more, more preferably 100 x 10 －６ From the viewpoint of cost reduction, the proportion of the additive (at least one additive selected from the group consisting of an ultraviolet absorber, a light stabilizer, and an antioxidant) is, for example, 100,000×10 parts by mass (ppm) or more relative to 1 part by mass of the above-mentioned curable composition (total amount). －６ Parts by mass (ppm) or less, preferably 10,000 x 10 －６ parts by mass (ppm) or less, more preferably 1000 x 10 －６ It is less than parts by mass (ppm).

[0264] The ultraviolet absorber is not particularly limited, and examples thereof include known ultraviolet absorbers (for example, those described in the ADEKA catalog and the CLARIANT catalog). More specific examples of ultraviolet absorbers include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, benzylidene-based ultraviolet absorbers, and triazine-based ultraviolet absorbers. These are used alone or in combination of two or more. From the viewpoint of weather resistance of the cured product (described later), a preferred ultraviolet absorber is a benzotriazole-based ultraviolet absorber. The blending ratio of the ultraviolet absorber is, for example, 1 x 10 relative to 1 part by mass of the above-mentioned curable composition. －６ Parts by mass (ppm) or more, preferably 10 x 10 －６ Parts by mass (ppm) or more, more preferably 100 x 10 －６From the viewpoint of cost reduction, the blending ratio of the ultraviolet absorber is, for example, 100,000×10 parts by mass (ppm) or more relative to 1 part by mass of the curable composition. －６ Parts by mass (ppm) or less, preferably 10,000 x 10 －６ parts by mass (ppm) or less, more preferably 1000 x 10 －６ It is less than parts by mass (ppm).

[0265] The light resistance stabilizer is not particularly limited, and examples thereof include known light resistance stabilizers (for example, those described in the ADEKA catalog). More specific examples of the light resistance stabilizer include hindered amine (HALS) light resistance stabilizers and benzoate light resistance stabilizers. These are used alone or in combination of two or more. From the viewpoint of the weather resistance of the cured product (described later), the light resistance stabilizer is preferably a hindered amine (HALS) light resistance stabilizer. The blending ratio of the light resistance stabilizer relative to 1 part by mass of the above-mentioned curable composition is, for example, 1 x 10 －６ Parts by mass (ppm) or more, preferably 10 x 10 －６ Parts by mass (ppm) or more, more preferably 100 x 10 －６ From the viewpoint of cost reduction, the blending ratio of the light resistance stabilizer is, for example, 100,000×10 parts by mass (ppm) or more relative to 1 part by mass of the curable composition. －６ Parts by mass (ppm) or less, preferably 10,000 x 10 －６ parts by mass (ppm) or less, more preferably 1000 x 10 －６ It is less than parts by mass (ppm).

[0266] The antioxidant is not particularly limited, and examples thereof include known antioxidants (for example, those listed in the ADEKA catalog). More specific examples of the antioxidant include phenol-based antioxidants, phosphorus-based antioxidants, and thiophene-based antioxidants. These are used alone or in combination of two or more. From the viewpoint of weather resistance of the cured product (described later), a phenol-based antioxidant is preferably used as the antioxidant. The blending ratio of the antioxidant is, for example, 1 x 10 relative to 1 part by mass of the above-mentioned curable composition. －６ Parts by mass (ppm) or more, preferably 10 x 10－６ Parts by mass (ppm) or more, more preferably 100 x 10 －６ From the viewpoint of cost efficiency, the blending ratio of the antioxidant is, for example, 100,000×10 parts by mass (ppm) or more relative to 1 part by mass of the curable composition. －６ Parts by mass (ppm) or less, preferably 10,000 x 10 －６ parts by mass (ppm) or less, more preferably 1000 x 10 －６ It is less than parts by mass (ppm).

[0267] (6) Uses The curable composition described above is suitably used in various industrial fields. Examples of uses of the curable composition include coating agents, paints, and adhesives. A preferred use of the curable composition is as an adhesive.

[0268] The adhesive is an uncured curable composition that, when cured, forms a cured adhesive product (described later). The cured adhesive product bonds adherends.

[0269] The curable composition can provide a cured product having an excellent refractive index and excellent flexibility. Therefore, the curable composition is suitable for use as an optical curable composition. Examples of applications of the optical curable composition include optical coating agents, optical paints, and optical adhesives.

[0270] 4. Cured Product (1) Main Component The cured product contains the above-mentioned plasticizer and cured resin as main components. The main component is a component whose content relative to the total is equal to or greater than a predetermined value. The content ratio of the main component relative to the total is, for example, 90% by mass or more. In other words, the total solid content of the plasticizer and cured resin is 90% by mass or more relative to the total solid content of the cured product.

[0271] The cured product is formed by curing the curable composition by a known method. The method for curing the curable composition is appropriately selected depending on the type of curable compound.

[0272] (2) Cured Resin The cured resin contains, for example, a cured product of the above-described curable compound, and preferably consists of a cured product of the above-described curable compound.

[0273] More specifically, examples of the cured resin include cured polyurethane resin, cured polyolefin resin, cured polyamine resin, cured amide resin, cured urea resin, cured phenolic resin, cured epoxy resin, cured acrylic resin, cured melamine resin, and cured alkyd resin. These may be used alone or in combination of two or more.

[0274] As the cured resin, preferably, a cured polyurethane resin and a cured acrylic resin are used, and more preferably, a cured acrylic resin is used.

[0275] Examples of cured polyurethane resins include cured products of the polyurethane resin raw materials described above. More specifically, cured polyurethane resins include reaction products of the base agent containing the polyol described above and the curing agent containing the polyisocyanate described above. Such cured resins can produce cured products that have a better refractive index, better flexibility, and better weather resistance. More specifically, if the cured resin contains a cured polyurethane resin (a reaction product of the base agent containing the acrylic polyol described above and the curing agent containing the polyisocyanate described above), a cured product that satisfies the physical properties (refractive index and flexibility) described below can be more easily obtained.

[0276] Examples of cured acrylic resins include cured products of the above-mentioned acrylic resin raw materials. More specifically, examples of cured acrylic resins include reaction products obtained by radical polymerization of the above-mentioned radically polymerizable monomers. The method for obtaining the cured acrylic resin is not particularly limited. For example, when an active energy ray radical polymerization initiator is used, the acrylic resin raw material is irradiated with active energy rays having a predetermined wavelength. Furthermore, when a thermal radical polymerization initiator is used, the acrylic resin raw material is heated to a predetermined temperature. This activates the polymerization initiator, causing the radically polymerizable monomers to undergo a radical polymerization reaction, resulting in the cured acrylic resin. In particular, when the cured resin contains a cured acrylic resin (a radical polymerization product of the above-mentioned monomer components), a cured product having excellent flexibility and a particularly excellent refractive index can be obtained.

[0277] (3) Subcomponents The cured product may contain the above-mentioned additives (excluding plasticizers) as subcomponents, if necessary. Subcomponents are components whose content relative to the total content is equal to or less than a predetermined value. The content ratio of the subcomponents relative to the total content is, for example, 10% by mass or less. In other words, the proportion of the additives relative to the total solid content of the cured product is 10% by mass or less.

[0278] From the viewpoint of weather resistance of the cured product, preferred additives include an ultraviolet absorber (UV absorber), a light stabilizer (light stabilizer), and an antioxidant. That is, the cured product preferably contains at least one additive selected from the group consisting of an ultraviolet absorber, a light stabilizer, and an antioxidant. From the viewpoint of weather resistance of the cured product, the proportion of the additive (at least one additive selected from the group consisting of an ultraviolet absorber, a light stabilizer, and an antioxidant) is, for example, 1 × 10 per part by mass of the above-mentioned cured product (total amount). －６ Parts by mass (ppm) or more, preferably 10 x 10 －６ Parts by mass (ppm) or more, more preferably 100 x 10 －６ From the viewpoint of cost efficiency, the proportion of the additive (at least one additive selected from the group consisting of an ultraviolet absorber, a light stabilizer, and an antioxidant) is, for example, 100,000×10 parts by mass (ppm) or more relative to 1 part by mass of the above-mentioned cured product (total amount). －６ Parts by mass (ppm) or less, preferably 10,000 x 10 －６ parts by mass (ppm) or less, more preferably 1000 x 10 －６ It is less than parts by mass (ppm).

[0279] The ultraviolet absorber is not particularly limited, and examples thereof include known ultraviolet absorbers (for example, those listed in the ADEKA catalog). More specific examples of ultraviolet absorbers include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, benzylidene-based ultraviolet absorbers, and triazine-based ultraviolet absorbers. These are used alone or in combination of two or more. From the viewpoint of weather resistance of the cured product, the ultraviolet absorber is preferably a benzotriazole-based ultraviolet absorber. The blending ratio of the ultraviolet absorber is, for example, 1 x 10 per part by mass of the above-mentioned cured product.－６ Parts by mass (ppm) or more, preferably 10 x 10 －６ Parts by mass (ppm) or more, more preferably 100 x 10 －６ From the viewpoint of cost reduction, the blending ratio of the ultraviolet absorber is, for example, 100,000×10 parts by mass (ppm) or more relative to 1 part by mass of the cured product. －６ Parts by mass (ppm) or less, preferably 10,000 x 10 －６ parts by mass (ppm) or less, more preferably 1000 x 10 －６ It is less than parts by mass (ppm).

[0280] The light resistance stabilizer (light stabilizer) is not particularly limited, and examples thereof include known light resistance stabilizers (for example, those described in the ADEKA catalog). More specific examples of light resistance stabilizers include hindered amine (HALS) light resistance stabilizers and benzoate light resistance stabilizers. These are used alone or in combination of two or more. From the viewpoint of weather resistance of the cured product, the light resistance stabilizer is preferably a hindered amine (HALS) light resistance stabilizer. The blending ratio of the light resistance stabilizer relative to 1 part by mass of the above-mentioned cured product is, for example, 1 x 10 －６ Parts by mass (ppm) or more, preferably 10 x 10 －６ Parts by mass (ppm) or more, more preferably 100 x 10 －６ From the viewpoint of cost reduction, the blending ratio of the light resistance stabilizer is, for example, 100,000×10 parts by mass (ppm) or more relative to 1 part by mass of the cured product. －６ Parts by mass (ppm) or less, preferably 10,000 x 10 －６ parts by mass (ppm) or less, more preferably 1000 x 10 －６ It is less than parts by mass (ppm).

[0281] The antioxidant is not particularly limited, and examples thereof include known antioxidants (for example, those listed in the ADEKA catalog). More specific examples of the antioxidant include phenol-based antioxidants, phosphorus-based antioxidants, and thiophene-based antioxidants. These are used alone or in combination of two or more. From the viewpoint of weather resistance of the cured product, a phenol-based antioxidant is preferably used as the antioxidant. The blending ratio of the antioxidant is, for example, 1 x 10 per part by mass of the above-mentioned cured product. －６ Parts by mass (ppm) or more, preferably 10 x 10 －６ Parts by mass (ppm) or more, more preferably 100 x 10 －６ From the viewpoint of cost efficiency, the blending ratio of the antioxidant is, for example, 100,000×10 parts by mass (ppm) or more relative to 1 part by mass of the cured product. －６ Parts by mass (ppm) or less, preferably 10,000 x 10 －６ parts by mass (ppm) or less, more preferably 1000 x 10 －６ It is less than parts by mass (ppm).

[0282] (4) Physical Properties The cured product contains the compound described above, and therefore has an excellent refractive index, flexibility, and weather resistance.

[0283] The refractive index of the cured product is relatively high. The refractive index of the cured product is, for example, 1.45 or more, preferably 1.50 or more, more preferably 1.55 or more, even more preferably 1.60 or more, and particularly preferably 1.61 or more. The refractive index of the cured product is, for example, 1.80 or less, preferably 1.70 or less. The refractive index is measured in accordance with the examples described below.

[0284] The tensile storage modulus (E') of the cured product at 25°C is relatively low. The tensile storage modulus (E') of the cured product at 25°C is, for example, 1000 MPa or less, preferably 800 MPa or less, more preferably 500 MPa or less, even more preferably 300 MPa or less, even more preferably 200 MPa or less, still more preferably 100 MPa or less, and particularly preferably 50 MPa or less. The tensile storage modulus (E') of the cured product at 25°C is, for example, 1 MPa or more. The tensile storage modulus (E') is measured in accordance with the examples described below.

[0285] (5) Uses The cured product described above is suitable for use in various industrial fields. Uses of the cured product include, for example, resin molded products, films, and pressure-sensitive adhesives. A preferred use of the cured product is pressure-sensitive adhesives.

[0286] The adhesive is a cured curable composition. For example, the adhesive is a cured product of a curable composition containing a polyurethane resin raw material and / or an acrylic resin raw material (preferably an acrylic resin raw material) as a curable compound. The adhesive has a relatively low glass transition temperature (0°C or lower) and is adhesive (tacky).

[0287] The cured product has an excellent refractive index and flexibility, and is therefore suitable for use as an optical resin, for example, in optical lenses, optical films, and optical pressure-sensitive adhesives.

[0288] The curable composition, adhesive, and pressure-sensitive adhesive each contain the plasticizer, and therefore, such a curable composition can provide a cured product that has a refractive index, flexibility, and weather resistance.

[0289] Next, the present invention will be described based on examples and comparative examples, but the present invention is not limited thereto. Note that "parts" and "%" are by mass unless otherwise specified. Furthermore, specific numerical values ​​such as blending ratios (content ratios), physical property values, parameters, etc. used in the following description can be substituted with the corresponding upper limit values ​​(numerical values ​​defined as "equal to or less than") or lower limit values ​​(numerical values ​​defined as "equal to or more than" or "exceeding") of the blending ratios (content ratios), physical property values, parameters, etc. described in the above "Modes for Carrying Out the Invention."

[0290] 1. Synthesis of Plasticizers Example 1 (POA-GST) 4-phenoxyacetylthiomethyl-1,8-bisphenoxyacetylthio-3,6-dithiaoctane (POA-GST) was synthesized by the following method.

[0291] Phenoxyacetic acid (13.7 g, 90 mmol) was dissolved in 100 mL of acetonitrile to obtain a carboxylic acid solution, which was then placed in a four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet line, and a dropping funnel.

[0292] Next, triethylamine (9.1 g, 90 mmol) was charged to the carboxylic acid solution, thereby obtaining a first mixture. Next, the first mixture was cooled in an ice bath, and the internal temperature of the flask was maintained at 5° C. or less.

[0293] Next, p-toluenesulfonic acid chloride (18.9 g, 99 mmol) was dissolved in 80 mL of acetonitrile to obtain a solution of toluenesulfonic acid halide.

[0294] The solution of toluenesulfonic acid halide was then added dropwise to the first mixture so that the internal temperature of the flask was maintained at 5° C. or less. The addition time was 10 minutes. The contents of the flask were then stirred at the same temperature for 10 minutes.

[0295] Next, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (abbreviated as GST, 5.3 g, 20 mmol, number of functional groups: 3 (mercapto groups: 60 mmol)) was added dropwise to the reaction solution in the flask so that the internal temperature of the flask was maintained at 5°C or below.

[0296] Next, N-methylimidazole (8.9 g, 108 mmol) was added dropwise to the reaction solution in the flask so that the internal temperature of the flask was maintained at 5° C. or less. The addition time was 5 minutes. Thereafter, the contents of the flask were stirred at the same temperature for 60 minutes.

[0297] To the reaction solution, 100 mL of toluene and 60 mL of saturated aqueous sodium bicarbonate solution were added to obtain a mixed solution. Next, an organic phase was separated from the mixed solution by liquid separation. The organic phase was a solution of the reaction product in a toluene / acetonitrile mixed solvent (hereinafter referred to as the reaction product solution).

[0298] The reaction product solution was then washed with 50 mL of 1N diluted hydrochloric acid, then with 50 mL of saturated aqueous sodium bicarbonate solution, and further with 50 mL of pure water.

[0299] The washed solution of the reaction product was passed through activated alumina (300 mesh, for chromatography, basic). After passing the solution through, the reaction product remaining in the alumina was eluted using 100 mL of toluene.

[0300] After passing the reaction product solution through the reaction system, anhydrous sodium sulfate was added to the reaction product solution and stirred to remove the remaining water in the reaction product solution.The sodium sulfate was then filtered off using pleated filter paper.

[0301] The filtered solution of the reaction product (filtrate) was concentrated using an evaporator to remove most of the toluene, yielding a residue. The residue was dried in a vacuum dryer to remove the remaining toluene. This purified the reaction product, yielding a purified product.

[0302] POA-GST was a colorless, transparent liquid. The yield of POA-GST was 10.8 g. The viscosity (25°C) of POA-GST was 17,100 mPa s. The refractive index (nD) of POA-GST was 1.62.

[0303] The POA-GST is as follows: １ H-NMR (400MHz, CDCl ３ ) was identified.

[0304] １ H-NMR (400MHz, CDCl ３ ): δ7.28-7.32 (m, 6H) δ7.01-7.03 (m, 3H) δ6.92-6.93 (m, 6H) δ4.66-4.72 (m, 6H) δ2.71-3.33 (m, 13H)

[0305] POA-GST is a compound represented by the above formula (1), in which A represents a residue (GST residue) obtained by removing the mercapto group from 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (GST).

[0306] In addition, POA-GST is represented by the above formula (1), where n=m=3, and SX １ R １ Y group, SX ２ R ２ It is a compound that does not have a group.

[0307] In addition, POA-GST is a compound represented by the formula (1) above, where X １ represents a carbonyl group, and R １ But methylene (-CH ２ -) group and Y represents a phenoxy group.

[0308] Example 2 (POP-GST) 4-(2-phenoxypropionyl)thiomethyl-1,8-bis(2-phenoxypropionyl)thio-3,6-dithiaoctane (POP-GST) was synthesized by the following method.

[0309] ​2-Phenoxypropionic acid (6.0 g, 36 mmol) was dissolved in 80 mL of acetonitrile to obtain a carboxylic acid solution, which was then placed in a four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet line, and a dropping funnel.

[0310] Next, triethylamine (3.7 g, 36 mmol) was charged to the carboxylic acid solution, thereby obtaining a first mixture. Next, the first mixture was cooled in an ice bath, and the internal temperature of the flask was maintained at 5° C. or less.

[0311] Next, p-toluenesulfonic acid chloride (7.5 g, 40 mmol) was dissolved in 30 mL of acetonitrile to obtain a solution of toluenesulfonic acid halide.

[0312] The solution of toluenesulfonic acid halide was then added dropwise to the first mixture so that the internal temperature of the flask was maintained at 5° C. or less. The addition time was 5 minutes. The contents of the flask were then stirred at the same temperature for 30 minutes.

[0313] Next, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (abbreviated as GST, 2.6 g, 10 mmol, number of functional groups: 3 (mercapto groups: 30 mmol)) was added dropwise to the reaction solution in the flask so that the internal temperature of the flask was maintained at 5°C or below.

[0314] Next, N-methylimidazole (3.6 g, 43 mmol) was added dropwise to the reaction solution in the flask so that the internal temperature of the flask was maintained at 5° C. or less. The addition time was 10 minutes. Thereafter, the contents of the flask were stirred at the same temperature for 60 minutes.

[0315] 100 mL of toluene and 100 mL of pure water were added to the reaction solution to obtain a mixed solution. Next, an organic phase was separated from the mixed solution by liquid separation. The organic phase was a solution of the reaction product in a toluene / acetonitrile mixed solvent (hereinafter referred to as the reaction product solution).

[0316] Next, the solution of the reaction product was washed with 100 mL of 1N diluted hydrochloric acid, then with 100 mL of saturated aqueous sodium bicarbonate solution, and further with 100 mL of pure water.

[0317] The washed solution of the reaction product was passed through activated alumina (300 mesh, for chromatography, basic). After passing the solution through, the reaction product remaining in the alumina was eluted using 100 mL of toluene.

[0318] After passing the reaction product solution through the reaction system, anhydrous sodium sulfate was added to the reaction product solution and stirred to remove the remaining water in the reaction product solution.The sodium sulfate was then filtered off using pleated filter paper.

[0319] The filtered solution of the reaction product (filtrate) was concentrated using an evaporator to remove most of the toluene, yielding a residue. The residue was dried in a vacuum dryer to remove the remaining toluene. This purified the reaction product, yielding a purified product.

[0320] POP-GST was a colorless, transparent liquid. The yield of POP-GST was 4.6 g. The viscosity of POP-GST (35°C) was 5,400 mPa s. The refractive index (nD) of POP-GST was 1.61.

[0321] POP-GST is as follows: １ H-NMR (400MHz, CDCl ３ ) was identified.

[0322] １ H-NMR (400MHz, CDCl ３ ): δ7.24-7.33 (m, 6H) δ6.97-7.01 (m, 3H) δ6.89-6.91 (m, 6H) δ4.76-4.82 (m, 3H) δ2.63-3.24 (m, 13H) δ1.57-1.61 (m, 9H)

[0323] POP-GST is a compound represented by the above formula (1), in which A represents a residue (GST residue) obtained by removing the mercapto group from 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (GST).

[0324] In addition, POP-GST is represented by the above formula (1), where n=m=3, and SX １ R １ Y group, SX ２ ​R ２ It is a compound that does not have a group.

[0325] In addition, POP-GST is a compound represented by the formula (1) above, wherein X １ represents a carbonyl group, and R １ is methylmethylene (-CH(CH ３ )-) group, and Y represents a phenoxy group.

[0326] Example 3 (POA-FSH) 5,7-bis(phenoxyacetylthiomethyl)-1,11-bis(phenoxyacetylthio)-3,6,9-trithiaundecane (POA-FSH) was synthesized by the following method.

[0327] First, 3.67 g (10 mmol) of 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (FSH) was placed in a four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet line, and a dropping funnel.

[0328] Next, 10 g of dichloromethane was added to the flask, thereby obtaining a solution of FSH.

[0329] Next, 4.45 g (44 mmol) of triethylamine was slowly added to the FSH solution while stirring, thereby obtaining a reaction solution of triethylamine and FSH.

[0330] The reaction solution was then cooled in an ice bath, and 7.50 g (44 mmol) of phenoxyacetyl chloride was added dropwise to the reaction solution while maintaining the internal temperature of the reaction solution at 5° C. or lower.

[0331] The equivalent ratio of chlorine atoms in phenoxyacetyl chloride to mercapto groups in FSH (chlorine atoms / mercapto groups) was 1.1.

[0332] After the dropwise addition was completed, the reaction solution was stirred for 2 hours while maintaining the internal temperature at 5°C or below.

[0333] The reaction solution was then diluted with 50 g of dichloromethane, and 50 mL of pure water was added. The mixture was then separated, and the organic phase was removed. The organic phase was then washed with 50 mL of 1N diluted hydrochloric acid, followed by 50 mL of saturated aqueous sodium bicarbonate solution. It was then further washed with 50 mL of 10% aqueous sodium chloride solution.

[0334] Anhydrous sodium sulfate was added to the washings and stirred to remove any remaining water in the washings. The sodium sulfate was filtered off using pleated filter paper to obtain a dichloromethane diluted solution of the product. The diluted solution was then concentrated using an evaporator. This yielded 5,7-bis(phenoxyacetylthiomethyl)-1,11-bis(phenoxyacetylthio)-3,6,9-trithiaundecane (POA-FSH) as the reaction product.

[0335] POA-FSH was a colorless, transparent liquid. The yield of POA-FSH was 8.3 g. The viscosity of POA-FSH (35°C) was 13,700 mPa·s. The refractive index (nD) of POA-FSH was 1.62.

[0336] The POA-FSH is as follows: １ H-NMR (400MHz, CDCl ３ ) was identified.

[0337] １ H-NMR (400MHz, CDCl ３ ): δ7.27-7.31 (m, 8H) δ6.98-7.03 (m, 4H) δ6.90-6.94 (m, 8H) δ4.65-4.70 (m, 8H) δ2.67-3.41 (m, 18H)

[0338] POA-FSH is a compound represented by the above formula (1), in which A represents a residue (FSH residue) obtained by removing the mercapto group from 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (FSH).

[0339] In addition, POA-FSH is represented by the above formula (1), where n=m=4, and SX １ R １ Y group, SX ２ R​２ It is a compound that does not have a group.

[0340] In addition, POA-FSH is a compound represented by the formula (1) above, where X １ represents a carbonyl group, and R １ But methylene (-CH ２ -) group and Y represents a phenoxy group.

[0341] Comparative Example 1 (DOP) Dioctyl phthalate (DOP) was prepared as a known plasticizer.

[0342] Comparative Example 2 (Bz-GST) 4-benzoylthiomethyl-1,8-bisbenzoylthio-3,6-dithiaoctane (Bz-GST) was synthesized by the following method.

[0343] First, 30.0 g (115.2 mmol) of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (GST) was placed in a four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet line, and a dropping funnel.

[0344] Next, 100 mL of dichloromethane was added to the flask, thereby obtaining a solution of GST.

[0345] Next, 38.5 g (380.0 mmol) of triethylamine was slowly added to the GST solution while stirring, thereby obtaining a reaction solution of triethylamine and GST.

[0346] The reaction solution was then cooled in an ice bath, and 53.4 g (380.0 mmol) of benzoyl chloride was added dropwise to the reaction solution while maintaining the internal temperature of the reaction solution at 10° C. or lower.

[0347] The equivalent ratio of chlorine atoms in benzoyl chloride to mercapto groups in GST (chlorine atoms / mercapto groups) was 1.10.

[0348] The ice bath was then removed from the reaction solution, allowing the temperature of the reaction solution to reach room temperature, and the reaction solution was stirred overnight.

[0349] Thereafter, 300 mL of water and 200 mL of dichloromethane were added to the reaction solution. Then, these mixtures were separated, and the organic phase was removed. Next, the organic phase was washed with dilute hydrochloric acid. Furthermore, the organic phase was washed with saturated aqueous sodium bicarbonate solution. Thereafter, the organic phase was concentrated using an evaporator. This resulted in a concentrated reaction solution.

[0350] The concentrate (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. 300 mL of dichloromethane was used to drain the diluted solution. The diluted solution was then concentrated using an evaporator. As a result, 4-benzoylthiomethyl-1,8-bisbenzoylthio-3,6-dithiaoctane (Bz-GST) was obtained as the reaction product.

[0351] Bz-GST was a colorless, transparent liquid. The yield of Bz-GST was 63.2 g. The viscosity of Bz-GST (25°C) was 5000 mPa s. The refractive index (nD) of Bz-GST was 1.65.

[0352] In addition, Bz-GST is as follows: １ H-NMR (400MHz, CDCl ３ ) was identified.

[0353] １ H-NMR (400MHz, CDCl ３ ): δ7.89-8.01 (m, 6H) δ7.51-7.61 (m, 3H) δ7.37-7.48 (m, 6H) δ2.79-3.59 (m, 13H)

[0354] Comparative Example 3 (PA-GST) 4-phenylacetylthiomethyl-1,8-bisphenylacetylthio-3,6-dithiaoctane (PA-GST) was synthesized by the following method.

[0355] First, 50.0 g (191.9 mmol) of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (GST) was placed in a four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet line, and a dropping funnel.

[0356] ​Next, 250 g of toluene was added to the flask, thereby obtaining a solution of GST.

[0357] Next, 61.8 g (610.3 mmol) of triethylamine was slowly added to the GST solution while stirring, thereby obtaining a reaction solution of triethylamine and GST.

[0358] The reaction solution was then cooled in an ice bath, and 91.7 g (593.1 mmol) of phenylacetyl chloride was added dropwise to the reaction solution while maintaining the internal temperature of the reaction solution at 15° C. or lower.

[0359] The equivalent ratio of chlorine atoms in phenylacetyl chloride to mercapto groups in GST (chlorine atoms / mercapto groups) was 1.03.

[0360] After the dropwise addition was completed, the reaction solution was stirred for 2 hours while maintaining the internal temperature of the reaction solution at 15°C or below.

[0361] Then, 550 g of a 10% aqueous solution of sodium chloride was added to the reaction solution. The mixture was then separated, and the organic phase was separated. The organic phase was then washed with 500 mL of 1N diluted hydrochloric acid, followed by 500 mL of saturated aqueous sodium bicarbonate solution. It was then further washed with 500 mL of pure water.

[0362] The washings were passed through activated alumina (300 mesh, basic, for chromatography), and 120 g of toluene was used to flush out the reaction product remaining in the alumina.

[0363] After the liquid was passed through the washings, anhydrous sodium sulfate was added to the washings and stirred to remove any remaining water. The sodium sulfate was filtered off using pleated filter paper to obtain a toluene diluted solution of the product. The diluted solution was then concentrated using an evaporator. This yielded 4-phenylacetylthiomethyl-1,8-bisphenylacetylthio-3,6-dithiaoctane (PA-GST) as the reaction product.

[0364] PA-GST was a pale yellow, transparent liquid. The yield of PA-GST was 105.2 g. The viscosity of PA-GST (25°C) was 1100 mPa s. The refractive index (nD) of PA-GST was 1.62.

[0365] The PA-GST is as follows: １ H-NMR (400MHz, CDCl ３ ) was identified.

[0366] １ H-NMR (400MHz, CDCl ３ ): δ7.21-7.37 (m, 15H) δ3.80-3.84 (m, 6H) δ2.64-3.25 (m, 13H)

[0367] Comparative Example 4 (PP-GST) 4-(3-phenylpropionyl)thiomethyl-1,8-bis(3-phenylpropionyl)thio-3,6-dithiaoctane (PP-GST) was synthesized by the following method.

[0368] First, 50.0 g (191.9 mmol) of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (GST) was placed in a four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet line, and a dropping funnel.

[0369] Next, 250 g of toluene was added to the flask, thereby obtaining a solution of GST.

[0370] Next, 61.8 g (610.3 mmol) of triethylamine was slowly added to the GST solution while stirring, thereby obtaining a reaction solution of triethylamine and GST.

[0371] The reaction solution was then cooled in an ice bath, and 100.0 g (593.1 mmol) of 3-phenylpropionyl chloride was added dropwise to the reaction solution while maintaining the internal temperature of the reaction solution at 15° C. or lower.

[0372] The equivalent ratio of chlorine atoms in 3-phenylpropionyl chloride to mercapto groups in GST (chlorine atoms / mercapto groups) was 1.03.

[0373] ​After the dropwise addition was completed, the reaction solution was stirred for 2 hours while maintaining the internal temperature of the reaction solution at 15°C or below.

[0374] Then, 550 g of a 10% aqueous solution of sodium chloride was added to the reaction solution. The mixture was then separated, and the organic phase was separated. The organic phase was then washed with 500 mL of 1N diluted hydrochloric acid, followed by 500 mL of saturated aqueous sodium bicarbonate solution. It was then further washed with 500 mL of pure water.

[0375] The washings were passed through activated alumina (300 mesh, basic, for chromatography), and 120 g of toluene was used to flush out the reaction product remaining in the alumina.

[0376] After the liquid was passed through the washings, anhydrous sodium sulfate was added to the washings and stirred to remove any remaining water. The sodium sulfate was filtered off using pleated filter paper to obtain a toluene diluted solution of the product. The diluted solution was then concentrated using an evaporator. This yielded the reaction product 4-(3-phenylpropionyl)thiomethyl-1,8-bis(3-phenylpropionyl)thio-3,6-dithiaoctane (PP-GST).

[0377] PP-GST was a pale yellow, transparent liquid. The yield of PP-GST was 119.0 g. The viscosity of PP-GST (25°C) was 400 mPa s. The refractive index (nD) of PP-GST was 1.60.

[0378] The PP-GST is as follows: １ H-NMR (400MHz, CDCl ３ ) was identified.

[0379] １ H-NMR (400MHz, CDCl ３ ): δ7.13-7.33 (m, 15H) δ2.66-3.29 (m, 25H)

[0380] ​2. Preparation of Curable Composition (1) Curable Compound The following curable compounds were prepared: FA512-AS (photocurable monomer, chemical name: dicyclopentenyloxyethyl acrylate, manufactured by Resonac) UC-102M (methacryloyl group-containing isoprene rubber, manufactured by Kuraray)

[0381] The following photopolymerization initiator was also prepared: Omnirad 184 (photopolymerization initiator, chemical name: 1-hydroxycyclohexyl phenyl ketone, manufactured by IGM Resins B.V.)

[0382] (2) Curable Compositions Curable compositions were prepared using the plasticizers of Examples 1 to 3 and Comparative Examples 1 to 4. More specifically, the plasticizers, curable compounds, and photopolymerization initiators were mixed according to the formulations shown in Table 1.

[0383] Furthermore, a curable composition was prepared without using a plasticizer as Comparative Example 5. More specifically, a curable compound and a photopolymerization initiator were mixed according to the formulation shown in Table 1.

[0384] In Table 1, the blending ratio (phr) of the plasticizer indicates the parts by mass of the plasticizer relative to 100 parts by mass of the total amount of the curable compound and the photopolymerization initiator.

[0385] 3. Production of Cured Product The curable composition was cured to obtain a cured product.

[0386] More specifically, a coating of the curable composition was sandwiched between release PET films (polyethylene terephthalate film, Purex A3100, manufactured by Toyobo Co., Ltd.) in a mold frame made of a 200 μm-thick silicone sheet. At this time, the release surface of the release PET film was brought into contact with the curable composition. This resulted in a laminate 1 (release PET film / curable composition / release PET film).

[0387] Next, Laminate 1 (release PET film / curable composition / release PET film) was sandwiched between glass substrates (D263T-eco, manufactured by SCHOTT) and fixed with clips. That is, the coating film of the curable composition was sandwiched between the glass substrates and the release PET films, thereby obtaining Laminate 2 (glass substrate / release PET film / curable composition / release PET film / glass substrate).

[0388] Thereafter, using an LED light source (365 nm), the curable composition of the laminate 2 was irradiated with active energy rays (wavelength 365 nm, illuminance 400 mW / cm ２ , cumulative light intensity 6000 mJ / cm ２ ) was irradiated. Furthermore, Laminate 2 was heated at 120°C for 30 minutes in a nitrogen atmosphere. As a result, the curable composition underwent radical polymerization by the active energy rays and heat, and Laminate 3 (glass substrate / release PET film / cured product / release PET film / glass substrate) containing a cured product was obtained.

[0389] The clips and glass substrate were then removed, and the cured product was peeled off from the release PET film. As a result, a cured product was obtained. The refractive index (nD), tensile storage modulus (E'), and glass transition temperature (Tg) of the cured product were measured by the methods described below. The results are shown in Table 1.

[0390] Separately from the above, the curable composition was sandwiched between glass substrates (Eagle-XG, manufactured by Corning) in a mold made of a 50 μm-thick silicone sheet, thereby obtaining a laminate 4 (glass substrate / curable composition / glass substrate).

[0391] Thereafter, using an LED light source (365 nm), the curable composition of the laminate 4 was irradiated with active energy rays (wavelength 365 nm, illuminance 400 mW / cm ２ , cumulative light intensity 6000 mJ / cm ２ ) was irradiated. Furthermore, Laminate 4 was heated at 120°C for 30 minutes in a nitrogen atmosphere. As a result, the curable composition underwent radical polymerization by the active energy rays and heat, and Laminate 5 (glass substrate / cured product / glass substrate) containing a cured product was obtained.

[0392] 4. Evaluation (1) Refractive Index (nD) The refractive index (nD) of the cured product was measured using an Abbe refractometer (DR-M4, manufactured by Atago Co., Ltd.) at room temperature (20°C). The light used was d-line (wavelength 587.6 nm).

[0393] (2) Flexibility: Tensile storage modulus (E') The solid viscoelasticity of the cured product was measured under the following conditions: Then, the tensile storage modulus (E') at 25°C was determined.

[0394] Apparatus: RSA-G2 (manufactured by TA Instruments) Deformation mode: Tensile mode Temperature range: -50°C to 270°C Temperature rise rate: 3°C / min Frequency: 1Hz Environment: N ２ environment

[0395] (3) Glass transition temperature (Tg) The solid viscoelasticity of the cured product was measured under the conditions in (2) above. Then, tanδ (loss tangent, E" / E') was calculated from the tensile storage modulus (E') and the tensile loss modulus (E"). The temperature at which the loss tangent (tanδ) showed a maximum value (peak value) was calculated as the glass transition temperature.

[0396] (4) Weather Resistance The b* (yellowing index, before weather resistance test) of Laminate 5 (glass substrate / cured product / glass substrate) was measured using a COH-7700 (spectroscopic color haze meter, manufactured by Nippon Denshoku Industries Co., Ltd.).

[0397] Next, the laminate 5 (glass substrate / cured product / glass substrate) was exposed to ultraviolet light under the following conditions.

[0398] Thereafter, the b* (yellowing index, after weather resistance test) of the laminate 5 (glass substrate / cured product / glass substrate) was measured using a COH-7700 (spectroscopic color haze meter, manufactured by Nippon Denshoku Industries Co., Ltd.).

[0399] In general optical applications, if b* (yellowing index) after a weather resistance test is less than 1, the weather resistance is determined to be good.

[0400] <Ultraviolet rays> Equipment: UVACUBE400+SOL500 (manufactured by Honle UV Technology) Light source: Metal halide lamp Irradiation conditions: 70 W / m2 (300-400 nm) Filter: H2 filter (cuts out 295 nm or less, manufactured by Honle UV Technology) Irradiation time: 120 hours

[0401] Examples 1 to 3 were superior in flexibility to Comparative Example 5 (no plasticizer added), confirming that the above compounds functioned as plasticizers.

[0402] The b* values ​​after the weather resistance test for Examples 1 to 3 were 0.67 (POA-GST) to 0.75 (POA-FSH), and it was confirmed that Examples 1 to 3 had good weather resistance.

[0403] It was confirmed that in Comparative Example 1, a sufficient refractive index could not be obtained.

[0404] In Comparative Examples 2 and 3, although the refractive index of the plasticizer and the cured product was higher than that of Examples 1 to 3, the b* value after the weather resistance test exceeded 1, and it was confirmed that the weather resistance was poor.

[0405] Comparative Example 4 had good weather resistance, but the refractive index of the plasticizer and the cured product were lower than those of Examples 1-3.

[0406] From the above results, it was confirmed that Examples 1 to 3 had good flexibility, refractive index, and weather resistance all at the same time.

[0407]

[0408] Details of the abbreviations in the table are as follows: FA-512AS: Photocurable monomer, dicyclopentenyloxyethyl acrylate, manufactured by Resonac UC-102M: Methacryloyl group-containing isoprene rubber, manufactured by Kuraray Omnirad 184: Photopolymerization initiator, chemical name: 1-hydroxycyclohexyl phenyl ketone, manufactured by IGM Resins B.V.

[0409] The above invention is provided as an exemplary embodiment of the present invention, but it is merely an example and should not be interpreted as being limiting. Modifications of the present invention that are obvious to those skilled in the art are intended to be included in the scope of the following claims.

[0410] The compound, additive, plasticizer, curable composition, adhesive, cured product, and pressure-sensitive adhesive of the present invention can be suitably used in various industrial fields, particularly in the fields of coating agents, paints, adhesives, films, and pressure-sensitive adhesives.

Claims

1. A compound represented by the following general formula (1). General formula (1); In formula (1), A represents an n-valent organic group containing a sulfur atom. S represents a sulfur atom. X １ represents a single bond or a carbonyl group. １ represents an alkylene group; Y represents an aryloxy group or an arylalkyloxy group; X ２ represents a single bond or a carbonyl group. ２ represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or an araliphatic hydrocarbon group. １ , R １ , Y, X ２ and R ２ may be the same or different from each other. n represents an integer of 3 or more. m represents an integer of 1 or more and n or less.) 2. The compound according to claim 1, wherein in the above formula (1), A has a molecular weight of 50 or more and 9,000 or less.

3. The compound according to claim 1, wherein in formula (1), A represents an organic group containing a sulfur atom and a typical element atom (excluding sulfur and hydrogen atoms), and the ratio of the number of sulfur atoms to the total number of sulfur atoms and the typical element atoms (excluding sulfur and hydrogen atoms) in A exceeds 20%.

4. The compound according to claim 1, wherein in formula (1), A is a residue (GST residue) obtained by removing the mercapto group from 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (GST).

5. The compound according to claim 1, wherein in formula (1), A is a residue (FSH residue) obtained by removing the mercapto group from 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (FSH).

6. In formula (1), X １ represents a carbonyl group; R １ The compound according to claim 1, wherein: represents an alkylene group having 1 to 2 carbon atoms; and Y represents a phenoxy group.

7. The compound according to claim 1, wherein in the above formula (1), m=n.

8. An additive comprising the compound according to claim 1.

9. A plasticizer comprising the compound according to claim 1.

10. A hardenable composition comprising the plasticizer of claim 9 and a hardenable compound.

11. The composition further comprises at least one additive selected from the group consisting of an ultraviolet absorber, a light stabilizer, and an antioxidant, and the ratio of the additive is 10×10 to 1 part by mass of the total amount of the curable composition. －６ Mass part or more 10,000×10 －６ The curable composition of claim 10, wherein the amount of the curable composition is less than or equal to parts by weight.

12. An adhesive comprising the curable composition of claim 10.

13. A cured product comprising the plasticizer according to claim 9 and a cured resin.

14. The cured product according to claim 13, having a refractive index of 1.60 or more and a tensile storage modulus of 100 MPa or less.

15. The composition further comprises at least one additive selected from the group consisting of an ultraviolet absorber, a light stabilizer, and an antioxidant, and the ratio of the additive is 10×10 to 1 part by mass of the total amount of the cured product. －６ Mass part or more 10,000×10 －６ The cured product according to claim 13, wherein the amount of the cured product is equal to or less than parts by weight.

16. The cured product of claim 13, wherein the cured resin comprises a reaction product of a base agent comprising an acrylic polyol and a curing agent comprising a polyisocyanate.

17. The cured product of claim 13, wherein the cured resin comprises a cured acrylic resin.

18. A pressure sensitive adhesive comprising the cured product according to claim 13.

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