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

Abstract

A compound represented by general formula (1). In formula (1), A represents an n-valent organic group including a sulfur atom. And n represents an integer of 3 or more. And S represents a sulfur atom. And X represents a single bond or a carbonyl group. X may be the same as or different from each other. R represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an aromatic aliphatic hydrocarbon group. R may be the same as or different from each other. General formula (1): A-(SXR) n (1).

Description

Technical Field

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

[0002] Optical resins used as adhesives and pressure-sensitive adhesives in various optical fields have a high refractive index.

[0003] Optical resins sometimes require flexibility depending on the application. In view of this, the addition of plasticizers to optical resins has been studied. As a plasticizer, for example, dioctyl phthalate (DOP) is known. In addition, as a plasticizer, for example, dibenzoate of 2-mercaptoethyl sulfide is known (for example, see Patent Document 1 (Example 11).).

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 61-019654 Summary of the invention

[0007] Problems to be solved by the invention

[0008] If the above-mentioned plasticizer is added to the optical resin, the crystallinity of the optical resin is reduced and the flexibility is improved. However, if the crystallinity of the optical resin is reduced, the refractive index of the optical resin is sometimes reduced. In addition, for example, when the refractive index of the optical resin is not reduced by the plasticizer, the crystallinity of the optical resin is sometimes not fully reduced and the flexibility is not improved.

[0009] The present invention provides a compound, an additive, a plasticizer, a curable composition, an adhesive, a cured product and an adhesive for obtaining a cured product having both a refractive index and flexibility.

[0010] Means for solving problems

[0011] The present invention [1] includes a compound represented by the following general formula (1).

[0012] General formula (1):

[0013] [Chemical formula 1]

[0014] Chemical formula 1

[0015] A-(SXR) n (1)

[0016] (In formula (1), A represents an n-valent organic group containing a sulfur atom. n represents an integer greater than or equal to 3. S represents a sulfur atom. X represents a single bond or a carbonyl group. X may be the same as or different from each other. R represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an aromatic aliphatic hydrocarbon group. R may be the same as or different from each other.)

[0017] The present invention [2] includes the compound described in the above [1], wherein A represents an organic group containing sulfur atoms and typical element atoms (excluding sulfur atoms and hydrogen atoms), and in A, the ratio of the number of sulfur atoms to the total number of sulfur atoms and the number of typical element atoms (excluding sulfur atoms and hydrogen atoms) is greater than 20%.

[0018] The present invention [3] comprises the compound described in the above [1] or [2], which is represented by the following general formula (2) or the following general formula (3).

[0019] General formula (2):

[0020] [Chemical formula 2]

[0021] Chemical formula 2

[0022]

[0023] (In formula (2), S, X and R have the same meanings as S, X and R in formula (1). In formula (2), the portion surrounded by a dotted line represents an organic group A (n=3) in formula (1).)

[0024] General formula (3):

[0025] [Chemical formula 3]

[0026] Chemical formula 3

[0027]

[0028] (In formula (3), S, X and R have the same meanings as S, X and R in formula (1). In formula (3), the portion surrounded by a dotted line represents an organic group A (n=4) in formula (1).)

[0029] The present invention [4] includes the compound described in any one of the above [1] to [3], wherein R represents a methyl group, a phenyl group or a benzyl group.

[0030] The present invention [5] includes the compound described in any one of the above [1] to [3], wherein X represents a carbonyl group and R represents an aromatic aliphatic hydrocarbon group.

[0031] The present invention [6] comprises an additive comprising the compound according to any one of the above [1] to [5].

[0032] The present invention [7] comprises a plasticizer comprising the compound according to any one of the above [1] to [5].

[0033] The present invention [8] comprises a curable composition comprising a curable compound and the plasticizer described in [7] above.

[0034] The present invention [9] comprises the curable composition described in [8] above, further comprising at least one additive selected from the group consisting of an ultraviolet absorber, a light stabilizer and an antioxidant, wherein the ratio of the additive to 1 part by mass of the curable composition is 10×10 -6 Mass parts or more 10000×10 -6 Less than 10 parts by mass.

[0035] The present invention

[10] comprises an adhesive comprising the curable composition described in [8] or [9] above.

[0036] The present invention

[11] comprises a cured product comprising a curing resin and the plasticizer described in the above [7].

[0037] The present invention

[12] comprises the cured product according to the above

[11] , wherein the cured product has a refractive index of 1.60 or more and a tensile storage elastic modulus at 25° C. of 100 MPa or less.

[0038] The present invention

[13] comprises the cured product according to the above

[11] or

[12] , wherein the cured product further comprises at least one additive selected from the group consisting of an ultraviolet absorber, a light stabilizer and an antioxidant, wherein the ratio of the additive to 1 part by mass of the cured product is 10×10 -6 Mass parts or more 10000×10 -6 Less than 10 parts by mass.

[0039] The present invention

[14] comprises the cured product according to any one of the above

[11] to

[13] , wherein the cured resin comprises a reaction product of a main agent containing an acrylic polyol and a curing agent containing a polyisocyanate.

[0040] The present invention

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

[11] to

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

[0041] The present invention

[16] comprises an adhesive comprising the cured product according to any one of the above

[11] to

[15] .

[0042] Effects of the Invention

[0043] The compound, additive, plasticizer, curable composition and adhesive of the present invention can provide a cured product having both a refractive index and flexibility.

[0044] Since the cured product and the adhesive of the present invention contain the above-mentioned compound, they have both a high refractive index and flexibility. DETAILED DESCRIPTION

[0045] 1. Compounds

[0046] (1) Structure of the compound

[0047] The compound of the present invention is represented by the following general formula (1).

[0048] General formula (1):

[0049] [Chemical formula 4]

[0050] Chemical formula 4

[0051] A-(SXR) n (1)

[0052] (In formula (1), A represents an n-valent organic group containing a sulfur atom. n represents an integer greater than or equal to 3. S represents a sulfur atom. X represents a single bond or a carbonyl group. X may be the same as or different from each other. R represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an aromatic aliphatic hydrocarbon group. R may be the same as or different from each other.)

[0053] (2) A in the formula

[0054] 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 typical element atom (excluding a sulfur atom and a hydrogen atom).

[0055] Among the typical element atoms (excluding sulfur atoms and hydrogen atoms), the typical elements (excluding sulfur and hydrogen) represent elements with atomic numbers 2 to 15, elements with atomic numbers 17 to 20, elements with atomic numbers 31 to 38, elements with atomic numbers 49 to 56, and elements with atomic numbers 81 to 88. As typical elements (excluding sulfur and hydrogen), preferably elements with atomic numbers 2 to 15 can be mentioned, more preferably elements with atomic numbers 6 to 9 can be mentioned, and more specifically, carbon, nitrogen, oxygen, and fluorine can be mentioned. These can be used alone or in combination of two or more.

[0056] As typical elements (excluding sulfur and hydrogen), carbon and oxygen are further preferred, and carbon is particularly preferred. From the viewpoint of obtaining a well-balanced refractive index and flexibility, it is more preferred that A represents an organic group containing a sulfur atom and a carbon atom, and it is further preferred that A represents an organic group consisting of a sulfur atom and a carbon atom.

[0057] n is the valence number of A. n represents an integer greater than or equal to 3. n preferably represents an integer greater than or equal to 3 and less than or equal to 8. n more preferably represents an integer greater than or equal to 3 and less than or equal to 6. n further preferably represents 3 or 4.

[0058] Examples of n-valent A include residues of n-functional thiol, and more specifically, residues obtained by removing mercapto groups from trifunctional or higher sulfur-containing polythiol (hereinafter referred to as trifunctional or higher sulfur-containing polythiol residues).

[0059] The trifunctional or higher 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 in addition to the mercapto groups. Examples of the trifunctional or higher sulfur-containing polythiol include sulfur-containing trithiol, sulfur-containing tetrathiol, sulfur-containing pentathiol, sulfur-containing hexathiol, and sulfur-containing octathiol.

[0060] Sulfur-containing trithiol is a trifunctional thiol containing a sulfur atom in addition to a mercapto group. Examples of sulfur-containing trithiol 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-dithiacyclohexane], and the like. tris[(4-mercaptomethyl-2,5-dithiohexyl-1-yl)methylthio]methane, 4-mercaptomethyl-2-(2,3-dimercaptopropylthio)-1,3-dithiolane and 4-mercaptomethyl-2-(1,3-dimercapto-2-propylthio)-1,3-dithiolane.

[0061] Sulfur-containing tetrathiol is a tetrafunctional thiol containing a sulfur atom in addition to a mercapto group. Examples of the sulfur-containing tetrathiol include 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (FSH), 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, bis(2,3-dimercaptopropyl)sulfide, bis(2,3-dimercaptopropylthiodipropionate), and bis(2,3-dimercaptopropyldithiodiglycolate. ester), bis(2,3-dimercaptopropylthiodipropionate), bis(2,3-dimercaptopropyl dithiodipropionate), 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-thiobutyl)-1,4-dithiacyclohexane, 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-dithiacyclohexane, 1,1-bis[4-(6-mercaptomethylthio)-1,3-dithiacyclohexylthio]-1,3-bis(mercaptomethylthio)propane, 3-[2-(1,3-dithiacyclobutyl)]methyl-7,9-bis(mercaptomethylthio)-1,11-dimercapto-2,4,6,10-tetrathiaundecane, 4-[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiacyclohexane 1,3-dithiolane, 1,1,5,5-tetrakis(mercaptomethylthio)-2,4-dithiolane and 1,1,3,3-tetrakis(mercaptomethylthio)-2-thiopropane.

[0062] Sulfur-containing pentathiol is a pentafunctional thiol containing a sulfur atom in addition to a mercapto group. Examples of sulfur-containing pentathiol include 1-[4-(6-mercaptomethylthio)-1,3-dithiacyclohexylthio]-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.

[0063] Sulfur-containing hexathiol is a hexafunctional thiol containing a sulfur atom in addition to a mercapto group. Examples of the sulfur-containing hexathiol 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, 3,4,8,9-tetrakis(mercaptomethylthio)-1,11-dimercapto-2,5,7,10-tetrathiaundecane, 4, 6-Bis[3,5-bis(mercaptomethylthio)-7-mercapto-2,6-dithiaheptylthio]-1,3-dithiacyclohexane, 3-[2-(1,3-dithiacyclobutyl)]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-dithiacyclopentane, 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-dithiolane, 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.

[0064] Sulfur-containing octathiol is an octafunctional thiol containing a sulfur atom in addition to a mercapto group. Examples of the sulfur-containing octathiol include tetrakis(4,4-bis(mercaptomethylthio)-2-thiabutyl)methane, 3,5,9,11,15,17-hexa(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-hexa(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.

[0065] The trifunctional or higher sulfur-containing polythiol residue preferably includes tri- to hexafunctional sulfur-containing polythiol residues, more preferably tri- to tetrafunctional sulfur-containing polythiol residues, and still more preferably trifunctional sulfur-containing polythiol residues.

[0066] That is, in the general formula (1), A is preferably a tri- to hexa-functional sulfur-containing polythiol residue, more preferably a tri- to tetra-functional sulfur-containing polythiol residue, and still more preferably a tri-functional sulfur-containing polythiol residue.

[0067] In other words, A preferably includes a trivalent to hexavalent organic group containing one or more (preferably two or three) sulfur atoms. A more preferably includes a trivalent organic group containing one or more (preferably two or three) sulfur atoms and a tetravalent organic group containing one or more (preferably two or three) sulfur atoms, and further preferably includes a trivalent organic group containing a sulfur atom.

[0068] From the viewpoint of obtaining the refractive index and flexibility in a good balance, it is preferred that A contains sulfur atoms in a ratio greater than a specified ratio. 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, greater than 20%, preferably greater than 21%, and more preferably greater than 22%. In addition, from the viewpoint of obtaining the refractive index and flexibility in a good balance, 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, less than 80%, preferably less than 50%, more preferably less than 30%, and further preferably less than 25%. It should be noted that 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.

[0069] Ratio of the number of sulfur atoms (%) = number of sulfur atoms / [number of sulfur atoms + number of typical element atoms (excluding sulfur atoms and hydrogen atoms)] × 100

[0070] As the trivalent organic group (organic group A (n=3)) containing one or more (preferably 2 or 3, more preferably 2) sulfur atoms, preferably, a residue obtained by removing a mercapto group from the above-mentioned sulfur-containing trithiol, and more preferably, a residue obtained by removing a mercapto group from 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (GST) (GST residue) can be mentioned.

[0071] The residue obtained by removing the mercapto group from 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (GST) (GST residue) is represented by, for example, the following general formula (4).

[0072] General formula (4):

[0073] [Chemical formula 5]

[0074] Chemical formula 5

[0075]

[0076] (In formula (4), the wavy line indicates the bonding position with the SXR group in formula (1).)

[0077] When A in the above formula (1) is a GST residue, a cured product having both a particularly excellent refractive index and particularly excellent flexibility can be obtained.

[0078] The GST residue is an organic group composed of 2 sulfur atoms and 7 carbon atoms. In the GST residue, 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 about 22% (2 / [2+7]×100).

[0079] As the tetravalent organic group (organic group A (n=4)) containing one or more (preferably 2 or 3, more preferably 3) sulfur atoms, preferably, a residue obtained by removing the thiol group from the above-mentioned sulfur-containing tetrathiol, and more preferably, a residue obtained by removing the thiol group from 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (FSH) (FSH residue).

[0080] The residue obtained by removing the mercapto group from 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (FSH) (FSH residue) is represented by, for example, the following general formula (5).

[0081] General formula (5):

[0082] [Chemical formula 6]

[0083] Chemical formula 6

[0084]

[0085] (In formula (5), the wavy line indicates the bonding position with the SXR group in formula (1).)

[0086] When A in the above formula (1) is a FSH residue, a cured product having both a particularly excellent refractive index and particularly excellent flexibility can be obtained.

[0087] The FSH residue is an organic group composed of 3 sulfur atoms and 10 carbon atoms. In the FSH residue, 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 about 23% (3 / [3+10]×100).

[0088] From the viewpoint of refractive index and flexibility, A in the above formula (1) preferably includes a GST residue and a FSH residue, and more preferably includes a GST residue.

[0089] (3) S in the formula

[0090] In the above formula (1), S represents a sulfur atom.

[0091] (4) X in the formula

[0092] In the above formula (1), X represents a single bond or a carbonyl group.

[0093] When X represents a single bond, in the above formula (1), S and R are directly bonded. That is, when X represents a single bond, the SXR group in the above formula (1) represents an SR group.

[0094] When X represents a carbonyl group, in the above formula (1), S and R are indirectly bonded via the carbonyl group. That is, when X represents a carbonyl group, the SXR group in the above formula (1) represents a S(C═O)R group.

[0095] It should be noted that the compound of the above formula (1) has three or more SXR groups depending on the value of n. The X contained in each SXR group may be the same as each other, or may be different from each other. Preferably, in the above formula (1), the X contained in each SXR group is the same as each other.

[0096] (5) R in the formula

[0097] In the above formula (1), R represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an aromatic aliphatic hydrocarbon group.

[0098] Examples of the aliphatic hydrocarbon group include aliphatic hydrocarbon groups having 1 to 20 carbon atoms. More specifically, 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.

[0099] 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. As the linear saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, 2-butyl, 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, isopentyl, tert-pentyl, 3-methyl-2-butyl, neopentyl, n-hexyl, 4-methyl-2-pentyl, 1-heptyl, 3-heptyl, 1-octyl, 2-octyl, 2-ethyl-1-hexyl, 1,1-dimethyl-3,3-dimethylbutyl, 1-nonyl, 1-decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl can be mentioned. As the linear unsaturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, for example, vinyl and 2-propenyl can be mentioned. These can be used alone or in combination of two or more.

[0100] As the cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, for example, a cyclic saturated aliphatic hydrocarbon group having 3 to 20 carbon atoms and a cyclic unsaturated aliphatic hydrocarbon group having 3 to 20 carbon atoms can be mentioned. As the cyclic saturated aliphatic hydrocarbon group having 3 to 20 carbon atoms, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group and a cyclodecyl group can be mentioned. As the cyclic unsaturated aliphatic hydrocarbon group having 3 to 20 carbon atoms, for example, a cyclopentenyl group and a cyclohexenyl group can be mentioned. These can be used alone or in combination of two or more.

[0101] Examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups having 6 to 20 carbon atoms. Examples of the aromatic hydrocarbon group 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. These may be used alone or in combination of two or more.

[0102] Examples of the aromatic aliphatic hydrocarbon group include aromatic aliphatic hydrocarbon groups having 7 to 20 carbon atoms. Examples of the aromatic aliphatic hydrocarbon group 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 may be used alone or in combination of two or more.

[0103] Aliphatic hydrocarbon groups, aromatic hydrocarbon groups and aromatic aliphatic hydrocarbon groups may be provided with substituents. As substituents, for example, halo, cyano, amino, carboxyl, sulfonyl and alkoxy groups may be mentioned. These may be used alone or in combination of two or more. The number of substituents may be appropriately set according to purpose and use. The substitution position may be appropriately set according to purpose and use.

[0104] It should be noted that the compound of the above formula (1) has three or more SXR groups depending on the value of n. The R contained in each SXR group may be the same as each other, or may be different from each other. It is preferred to use one selected from the group consisting of aliphatic hydrocarbon groups, aromatic hydrocarbon groups and aromatic aliphatic hydrocarbon groups alone. That is, it is preferred that in the above formula (1), the R contained in each SXR group is the same as each other.

[0105] When R represents an aliphatic hydrocarbon group, preferably, a linear aliphatic hydrocarbon group having 1 to 10 carbon atoms is used, more preferably, a linear aliphatic hydrocarbon group having 1 to 4 carbon atoms is used, further preferably, a linear aliphatic hydrocarbon group having 1 to 2 carbon atoms is used, and particularly preferably, a methyl group is used.

[0106] When R represents an aromatic hydrocarbon group, preferably, an aromatic hydrocarbon group having 6 to 10 carbon atoms is used, more preferably, an aromatic hydrocarbon group having 6 to 8 carbon atoms is used, and further preferably, a phenyl group is used.

[0107] When R 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 further preferably, a benzyl group and a 2-phenylethyl group are used.

[0108] From the viewpoint of obtaining a cured product having a good balance between refractive index and flexibility, in the above formula (1), R preferably represents a methyl group, a phenyl group or a benzyl group. That is, when R is a methyl group, a phenyl group or a benzyl group, a cured product having both a particularly excellent refractive index and particularly excellent flexibility can be obtained.

[0109] From the viewpoint of the refractive index, it is more preferred that R represents a phenyl group or a benzyl group. From the viewpoint of flexibility, it is more preferred that R represents a methyl group.

[0110] In addition, from the viewpoint of obtaining excellent weather resistance in addition to excellent refractive index and excellent flexibility, in the above formula (1), preferably X represents a carbonyl group and R represents an aromatic aliphatic hydrocarbon group and / or an aliphatic hydrocarbon group, and more preferably X represents a carbonyl group and R represents an aromatic aliphatic hydrocarbon group. That is, when X is a carbonyl group and R is an aromatic aliphatic hydrocarbon group, a cured product having particularly excellent refractive index, particularly excellent flexibility and particularly excellent weather resistance can be obtained.

[0111] From the viewpoint of refractive index, it is more preferred that X represents a carbonyl group and R represents a benzyl group. In addition, from the viewpoint of flexibility and weather resistance, it is more preferred that X represents a carbonyl group and R represents a 2-phenylethyl group and / or a methyl group, and it is particularly preferred that X represents a carbonyl group and R represents a 2-phenylethyl group.

[0112] (6) Specific examples

[0113] Preferred examples of the compound represented by the formula (1) include compounds wherein A in the formula (1) is a GST residue. The compound wherein A in the formula (1) is a GST residue is represented, for example, by the following general formula (2).

[0114] General formula (2):

[0115] [Chemical formula 7]

[0116] Chemical formula 7

[0117]

[0118] (In formula (2), S, X and R have the same meanings as S, X and R in formula (1). In formula (2), the portion surrounded by a dotted line represents an organic group A (n=3) in formula (1).)

[0119] The compound represented by the above formula (2) can provide a cured product having both a particularly excellent refractive index and particularly excellent flexibility.

[0120] More specifically, the compound represented by the formula (2) is 4-benzylthiomethyl-1,8-bisbenzylthio-3,6-dithiaoctane (Bn-GST). In Bn-GST, X in the formula (2) represents a single bond, and R represents a benzyl group.

[0121] In addition, as a compound represented by the above formula (2), more specific examples include 4-benzoylthiomethyl-1,8-bisbenzoylthio-3,6-dithiaoctane (Bz-GST). In Bz-GST, X in the formula (2) represents a carbonyl group, and R represents a phenyl group.

[0122] In addition, as a compound represented by the above formula (2), more specific examples include 4-acetylthiomethyl-1,8-bisacetylthio-3,6-dithiaoctane (Ac-GST). In Ac-GST, X in formula (2) represents a carbonyl group, and R represents a methyl group.

[0123] In addition, as a compound represented by the above formula (2), more specific examples include 4-phenylacetylthiomethyl-1,8-bisphenylacetylthio-3,6-dithiaoctane (PA-GST). In PA-GST, X in the formula (2) represents a carbonyl group, and R represents a benzyl group.

[0124] In addition, as a compound represented by the above formula (2), more specifically, 4-(3-phenylpropionyl)thiomethyl-1,8-bis(3-phenylpropionyl)thio-3,6-dithiaoctane (PP-GST) can also be mentioned. In PP-GST, X in formula (2) represents a carbonyl group, and R represents a 2-phenylethyl group.

[0125] In addition, the compound represented by the above formula (1) is preferably a compound wherein A in the formula (1) is a FSH residue. The compound wherein A in the formula (1) is a FSH residue is represented, for example, by the following general formula (3).

[0126] General formula (3):

[0127] [Chemical formula 8]

[0128] Chemical formula 8

[0129]

[0130] (In formula (3), S, X and R have the same meanings as S, X and R in formula (1). In formula (3), the portion surrounded by a dotted line represents an organic group A (n=4) in formula (1).)

[0131] The compound represented by the above formula (3) can provide a cured product having both a particularly excellent refractive index and particularly excellent flexibility.

[0132] More specifically, the compound represented by the formula (3) is 5,7-bis(benzoylmercaptomethyl)-1,11-bis(benzoylmercapto)-3,6,9-trithiaundecane (Bz-FSH). In Bz-FSH, X in the formula (3) represents a single bond, and R represents a benzyl group.

[0133] 2. Method for producing the compound

[0134] (1) Raw materials of compounds

[0135] The above-mentioned compound can be produced, for example, by reacting the above-mentioned trifunctional or higher-functional sulfur-containing polythiol with a modifying agent.

[0136] The modifying agent is a compound that modifies the mercapto group of the trifunctional or higher sulfur-containing polythiol described above into the SXR group in the above formula (1).

[0137] Examples of the modifying agent include compounds represented by the following general formula (6).

[0138] General formula (6):

[0139] [Chemical formula 9]

[0140] Chemical formula 9

[0141] Y-XR (6)

[0142] (In formula (6), X and R have the same meanings as X and R in formula (1). Y represents a halogen or a hydroxyl group.)

[0143] In the above formula (6), X and R have the same meanings as X and R in formula (1). Y represents a halogen or a hydroxyl group. Examples of the halogen include fluorine, chlorine, bromine and iodine. Preferred halogens include chlorine and bromine.

[0144] In the above formula (6), when Y is a halogen and X is a single bond, as a modifier, a halogenated hydrocarbon can be mentioned. Halogenated alkyl, halogenated aryl and halogenated aralkyl can be mentioned. As a halogenated alkyl, for example, fluoromethane, chloromethane, bromomethane, iodomethane, fluoroethane, chloroethane, bromoethane and iodoethane can be mentioned. As a halogenated aryl, for example, fluorinated benzene, chlorinated benzene, brominated benzene and iodinated benzene can be mentioned. As a halogenated aralkyl, for example, benzyl fluoride, benzyl chloride, benzyl bromide (benzyl bromide) and benzyl iodide can be mentioned. These can be used alone or in combination of two or more. As the above-mentioned modifier, preferably a halogenated aralkyl can be mentioned, and more preferably benzyl bromide (benzyl bromide) can be mentioned.

[0145] In the above formula (6), when Y is a halogen and X is a carbonyl group, an acyl halide may be mentioned as the modifier. As the acyl halide, for example, fluoroacetyl, chloroacetyl, bromoacetyl, iodoacetyl, benzoyl fluoride, benzoyl chloride, benzoyl bromide and benzoyl iodide may be mentioned. These may be used alone or in combination of two or more. As the above modifier, benzoyl chloride may be preferably mentioned.

[0146] In the above formula (6), when Y is a hydroxyl group and X is a carbonyl group, carboxylic acid can be cited as the modifier. As carboxylic acid, for example, monocarboxylic acid and its anhydride can be cited. As monocarboxylic acid, for example, aliphatic monocarboxylic acid, aromatic monocarboxylic acid and aromatic aliphatic monocarboxylic acid can be cited. As aliphatic monocarboxylic acid, for example, acetic acid, propionic acid, butyric acid, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, 2-ethylhexanoic acid, cyclohexanecarboxylic acid and cyclopentanecarboxylic acid can be cited. As aromatic monocarboxylic acid, for example, benzoic acid and toluic acid can be cited. As aromatic aliphatic monocarboxylic acid, for example, diphenylacetic acid can be cited. These can be used alone or in combination of two or more. As the above-mentioned modifier, preferably aliphatic monocarboxylic acid and its anhydride can be cited, more preferably acetic acid and its anhydride can be cited, and further preferably acetic anhydride can be cited.

[0147] (2) Mixing ratio and reaction conditions

[0148] The trifunctional or higher sulfur-containing polythiol and the modifier are mixed in an appropriate ratio and reacted under appropriate conditions. The mixing ratio of the trifunctional or higher sulfur-containing polythiol and the modifier is selected according to the type of the trifunctional or higher sulfur-containing polythiol and the type of the modifier. Examples of the reaction between the trifunctional or higher sulfur-containing polythiol and the modifier include nucleophilic substitution reaction, nucleophilic acylation reaction, cross coupling reaction, and dehydration condensation reaction.

[0149] For example, when the modifier includes a halogenated hydrocarbon, a trifunctional or higher sulfur-containing polythiol and the modifier undergo a nucleophilic substitution reaction in the presence of a known basic compound to produce a compound of the above formula (1). More specifically, the basic compound causes the proton of the trifunctional or higher sulfur-containing polythiol to be detached to produce a nucleophilic agent. Then, the nucleophilic agent derived from the trifunctional or higher sulfur-containing polythiol undergoes a nucleophilic substitution reaction with the halogenated hydrocarbon. As the basic compound, for example, metal alcoholates and amine compounds can be cited. In such a reaction, the mixing ratio of the trifunctional or higher sulfur-containing polythiol and the modifier is adjusted based on the equivalent ratio of the halogen atoms in the modifier (halogenated hydrocarbon) to the mercapto group in the sulfur-containing polythiol. The equivalent ratio (halogen atom / mercapto group) of the halogen atoms in the modifier (halogenated hydrocarbon) to the mercapto group in the sulfur-containing polythiol is, for example, 0.9 or more, preferably 1.0 or more, and more preferably 1.01 or more. The equivalent ratio of the halogen atoms in the modifying agent (halogenated hydrocarbon) to the mercapto groups in the sulfur-containing polythiol (halogen atoms / mercapto groups) is, for example, 5.0 or less, preferably 3.0 or less, and more preferably 1.5 or less.

[0150] In the case where the modifier includes a halogenated hydrocarbon, the reaction conditions of the nucleophilic substitution reaction are appropriately selected according to the type of the sulfur-containing polythiol with three or more functional groups and the type of the modifier. For example, the reaction temperature is, for example, above -20°C, preferably above -10°C. In addition, the reaction temperature is, for example, below 50°C, preferably below 30°C. In addition, the reaction time is, for example, above 3 hours, preferably above 6 hours. In addition, the reaction time is, for example, below 48 hours, preferably below 24 hours. In addition, the sulfur-containing polythiol with three or more functional groups and the modifier can react under solvent-free conditions or under known solvents. The type and amount of solvent added are appropriately set. In addition, the sulfur-containing polythiol with three or more functional groups and the modifier can react under catalyst-free conditions or under known catalysts. It should be noted that the type and amount of catalyst added are appropriately set.

[0151] In addition, for example, when the modifier includes an acyl halide, the trifunctional or higher sulfur-containing polythiol and the modifier undergo a nucleophilic acylation reaction in the presence of the above-mentioned basic compound to produce the compound of the above-mentioned formula (1). More specifically, the basic compound causes the proton of the trifunctional or higher sulfur-containing polythiol to be detached to produce a nucleophilic agent. Then, the nucleophilic agent derived from the trifunctional or higher sulfur-containing polythiol undergoes a nucleophilic acylation reaction with the acyl halide. In such a reaction, the mixing ratio of the trifunctional or higher sulfur-containing polythiol and the modifier is adjusted based on the equivalent ratio of the halogen atoms in the modifier (acyl halide) to the mercapto group in the sulfur-containing polythiol. The equivalent ratio (halogen atom / mercapto group) of the halogen atoms in the modifier (acyl halide) to the mercapto group in the sulfur-containing polythiol is, for example, 0.9 or more, preferably 1.0 or more, and more preferably 1.05 or more. The equivalent ratio of the halogen atoms in the modifying agent (acid halide) to the mercapto groups in the sulfur-containing polythiol (halogen atoms / mercapto groups) is, for example, 5.0 or less, preferably 3.0 or less, and more preferably 1.5 or less.

[0152] When the modifier contains an acyl halide, the reaction conditions of the nucleophilic acylation reaction are appropriately selected according to the type of the sulfur-containing polythiol with three or more functional groups and the type of the modifier. For example, the reaction temperature is, for example, above -20°C, preferably above -10°C. In addition, the reaction temperature is, for example, below 50°C, preferably below 30°C. In addition, the reaction time is, for example, above 3 hours, preferably above 6 hours. In addition, the reaction time is, for example, below 48 hours, preferably below 24 hours. In addition, the sulfur-containing polythiol with three or more functional groups and the modifier can react under solvent-free conditions or under known solvents. The type and amount of solvent added are appropriately set. In addition, the sulfur-containing polythiol with three or more functional groups and the modifier can react under catalyst-free conditions or under known catalysts. It should be noted that the type and amount of catalyst added are appropriately set.

[0153] In addition, for example, when the modifier contains a carboxylic acid, a trifunctional or higher sulfur-containing polythiol and the modifier (carboxylic acid) undergo a dehydration condensation reaction in the presence of the above-mentioned basic compound to produce the compound of the above-mentioned formula (1). In such a reaction, the mixing ratio of the trifunctional or higher sulfur-containing polythiol and the modifier is adjusted based on the equivalent ratio of the carboxyl group in the modifier (carboxylic acid) to the thiol group in the sulfur-containing polythiol. The equivalent ratio (carboxyl group / thiol group) of the carboxyl group in the modifier (carboxylic acid) to the thiol group in the sulfur-containing polythiol is, for example, 0.9 or more, preferably 1.0 or more, and more preferably 1.05 or more. In addition, the equivalent ratio (carboxyl group / thiol group) of the carboxyl group in the modifier (carboxylic acid) to the thiol group in the sulfur-containing polythiol is, for example, 5.0 or less, preferably 3.0 or less, and more preferably 2.5 or less.

[0154] When the modifier contains carboxylic acid, the reaction conditions of the dehydration condensation reaction are appropriately selected according to the type of sulfur-containing polythiol with three or more functional groups and the type of modifier. For example, the reaction temperature is, for example, above -20°C, preferably above -10°C. In addition, the reaction temperature is, for example, below 50°C, preferably below 30°C. In addition, the reaction time is, for example, above 3 hours, preferably above 6 hours. In addition, the reaction time is, for example, below 48 hours, preferably below 24 hours. In addition, the sulfur-containing polythiol with three or more functional groups and the modifier can react under solvent-free conditions or under known solvents. The type and amount of solvent added are appropriately set. In addition, the sulfur-containing polythiol with three or more functional groups and the modifier can react under catalyst-free conditions or under known catalysts. It should be noted that the type and amount of catalyst added are appropriately set.

[0155] And, after the above-mentioned reaction is completed, as required, a known neutralizing agent is added to the reaction liquid to adjust the pH of the reaction liquid. In addition, as required, the reaction product is concentrated or separated using a known method. And then, as required, the reaction product is purified using a known method. Thus, as a reaction product, a compound represented by the above formula (1) is obtained.

[0156] In addition, the modifier and the reaction method are not limited to the above. For example, as a reaction method, an ene-thiol reaction can be mentioned. In addition, as a modifier, for example, a compound that can react with the above-mentioned trifunctional or more sulfur-containing polythiol to react with an ene-thiol can be mentioned. As such a compound, for example, a vinyl compound can be mentioned. As a vinyl compound, for example, styrene, methyl styrene and butyl styrene can be mentioned. These can be used alone or in combination of two or more.

[0157] When a vinyl compound is used as a modifier, a trifunctional or higher sulfur-containing polythiol and the modifier (vinyl compound) undergo an ene-thiol reaction in the presence of a known free radical initiator to produce a compound of the above formula (1) (X represents a single bond, and R represents a hydrocarbon group derived from a vinyl compound).

[0158] In the ene-thiol reaction, the radical polymerization initiator extracts hydrogen atoms from the mercapto group of the trifunctional or higher sulfur-containing polythiol to generate a thiol radical. The thiol radical undergoes radical addition with the vinyl group of the vinyl compound to generate a carbon radical. The carbon radical extracts hydrogen atoms from other mercapto groups. Thus, the alkylation of the mercapto group is completed. In addition, at the same time, the radical chain reaction continues. As a result, the compound of the above formula (1) is obtained.

[0159] As the free radical polymerization initiator, there is no particular limitation, and known free radical polymerization initiators can be cited. As the free radical polymerization initiator, more specifically, for example, a photo radical polymerization initiator and a thermal radical polymerization initiator can be cited. As the photo radical polymerization initiator, for example, 1-hydroxycyclohexane-1-yl phenyl ketone can be cited. As the thermal radical polymerization initiator, for example, organic peroxides and azo compounds can be cited. As the organic peroxide, for example, benzoyl peroxide can be cited. As the azo compound, for example, azobisisobutyronitrile can be cited. These can be used alone or in combination of two or more. The mixing ratio of the free radical polymerization initiator is appropriately set according to the type of the free radical polymerization initiator.

[0160] In the ene-thiol reaction, the mixing ratio of the sulfur-containing polythiol with three or more functional groups and the modifier is adjusted based on the equivalent ratio of the vinyl group in the modifier (vinyl compound) to the mercapto group in the sulfur-containing polythiol. The equivalent ratio (vinyl group / mercapto group) of the vinyl group in the modifier (vinyl compound) to the mercapto group in the sulfur-containing polythiol is, for example, 0.9 or more, preferably 1.0 or more, and more preferably 1.01 or more. In addition, the equivalent ratio (vinyl group / mercapto group) of the vinyl group in the modifier (vinyl compound) to the mercapto group in the sulfur-containing polythiol is, for example, 5.0 or less, preferably 3.0 or less, and more preferably 1.5 or less.

[0161] The reaction conditions of the ene-thiol reaction are appropriately selected according to the type of sulfur-containing polythiol with more than three functions and the type of modifier. For example, the reaction temperature is, for example, above -20°C, preferably above -10°C. In addition, the reaction temperature is, for example, below 150°C, preferably below 100°C. In addition, the reaction time is, for example, above 3 hours, preferably above 6 hours. In addition, the reaction time is, for example, below 48 hours, preferably below 24 hours. In addition, the sulfur-containing polythiol with more than three functions and the modifier can react under solvent-free conditions or under known solvents. The type and amount of solvent added are appropriately set. In addition, the sulfur-containing polythiol with more than three functions and the modifier can react under catalyst-free conditions or under known catalysts. It should be noted that the type and amount of catalyst added are appropriately set.

[0162] After the above reaction is completed, the reaction product is concentrated or separated by a known method as needed. Furthermore, the reaction product is purified by a known method as needed. Thus, the compound represented by the above formula (1) is obtained as a reaction product.

[0163] The above-mentioned compound is a novel compound having a specific structure represented by the above-mentioned formula (1). As the use of such a compound, for example, an additive can be mentioned. That is, the additive preferably contains the above-mentioned compound. As an additive, more specifically, a plasticizer and a refractive index modifier can be mentioned, and preferably a plasticizer can be mentioned. That is, the plasticizer preferably contains the above-mentioned compound. In other words, the use of the above-mentioned compound is preferably a plasticizer. By means of the above-mentioned compound, a cured product having both a refractive index and flexibility can be obtained (described later).

[0164] 3. Curable composition

[0165] (1) Principal component

[0166] The curable composition comprises a plasticizer and a curable compound as main components. The main component is a component whose content ratio relative to the whole is above a prescribed value. The content ratio of the main component relative to the whole is, for example, 90% by mass or more. That is, 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.

[0167] The curable compound is an uncured compound that is cured by a known method to generate a cured resin (described later). The plasticizer is an additive that improves the flexibility of the cured resin (described later). The plasticizer and the curable compound are described in detail below.

[0168] (2) Plasticizer

[0169] The plasticizer contains the compound represented by the above formula (1). The plasticizer is preferably composed of the compound represented by the above formula (1).

[0170] When the plasticizer contains the compound represented by the above formula (1), the plasticizer can improve the flexibility of a cured product (described later) and can suppress a decrease in the refractive index of the cured product (described later) or can increase the refractive index.

[0171] (3) Curable compounds

[0172] The curable compound is not particularly limited, and examples thereof include resin raw materials that can generate a cured resin (described later).

[0173] It should be noted that, as the cured resin, as described later, for example, cured polyurethane resins, cured polyolefin resins, cured polyamine resins, cured amide resins, cured urea resins, cured phenolic resins, cured epoxy resins, cured acrylic resins, cured melamine resins and cured alkyd resins can be cited. These can be used alone or in combination of two or more.

[0174] Preferred examples of the curable resin (described below) include a curable urethane resin and a curable acrylic resin. The curable compound can be selected according to the type of the curable resin (described below).

[0175] For example, when a curable polyurethane resin is used as the curable resin, the curable compound may include, for example, a polyurethane resin raw material. In addition, when a curable acrylic resin is used as the curable resin, the curable compound may include, for example, an acrylic resin raw material.

[0176] Hereinafter, the polyurethane resin raw material and the acrylic resin raw material will be described in detail.

[0177] (3-1) Polyurethane resin raw materials

[0178] 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, polyisocyanate and polyol.

[0179] (3-2) Polyisocyanate

[0180] Polyisocyanate has a plurality of isocyanate groups in one molecule. Examples of polyisocyanate include polyisocyanate monomers and polyisocyanate derivatives.

[0181] Examples of the polyisocyanate monomer include aliphatic polyisocyanate, aromatic polyisocyanate, and aromatic aliphatic polyisocyanate.

[0182] Examples of the aliphatic polyisocyanate include ethylene diisocyanate, trimethylene diisocyanate, 1,4-butylene diisocyanate, 1,5-pentane diisocyanate, 1,6-hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and 2,6-diisocyanatomethylhexanoate. These may be used alone or in combination of two or more.

[0183] In addition, as aliphatic polyisocyanate monomers, alicyclic polyisocyanate monomers can also be mentioned. As alicyclic polyisocyanate monomers, for example, 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, methylene bis (cyclohexyl isocyanate), 2,4-cyclohexane diisocyanate methyl, 2,6-cyclohexane diisocyanate methyl, norbornane diisocyanate and bis (isocyanate methyl) cyclohexane can be mentioned. These can be used alone or in combination of two or more.

[0184] Examples of the aromatic polyisocyanate 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 may be used alone or in combination of two or more.

[0185] Examples of the aromatic aliphatic polyisocyanate include xylylene diisocyanate, tetramethylxylylene diisocyanate, and ω,ω′-diisocyanate-1,4-diethylbenzene. These may be used alone or in combination of two or more.

[0186] Polyisocyanate derivatives are derived from the above-mentioned polyisocyanate monomers. As polyisocyanate derivatives, for example, isocyanurate modified products, imino oxadiazinedione modified products, triol adducts, allophanate modified products, biuret modified products, urea modified products, oxadiazinedione modified products, carbodiimide modified products, uretdione modified products and uretonimine modified products can be enumerated. These can be used alone or in combination of two or more. As polyisocyanate derivatives, preferably isocyanurate modified products can be enumerated.

[0187] The polyisocyanate may be used alone or in combination of two or more. The polyisocyanate preferably contains a polyisocyanate derivative, and more preferably consists of a polyisocyanate derivative.

[0188] As the polyisocyanate derivative, from the viewpoint of improving the refractive index and transparency, preferably, there can be mentioned a polyisocyanate derivative derived from an aromatic aliphatic polyisocyanate (aromatic aliphatic polyisocyanate derivative).

[0189] As the aromatic aliphatic polyisocyanate derivative, more preferably, a derivative of xylylenediisocyanate is used, and still more preferably, a triol adduct of xylylenediisocyanate is used.

[0190] The average number of isocyanate groups of the polyisocyanate is, for example, 2 or more, and preferably 2.5 or more. The average number of isocyanate groups of the polyisocyanate is, for example, 4 or less, and preferably 3.5 or less.

[0191] The isocyanate group content (NCO%) of the polyisocyanate is, for example, 5 mass % or more, preferably 7 mass % or more. The isocyanate group content (NCO%) of the polyisocyanate is, for example, 30 mass % or less, preferably 25 mass % or less.

[0192] (3-3) Polyol

[0193] Polyols include, for example, macromolecular polyols. Macromolecular polyols have two or more hydroxyl groups in one molecule. Macromolecular polyols are relatively high molecular weight organic compounds. The number average molecular weight of the macromolecular polyol is, for example, 400 or more, for example, 20,000 or less. It should be noted that the number average molecular weight can be calculated using a known method based on the hydroxyl equivalent and the average number of hydroxyl groups. In addition, the number average molecular weight can be measured as a molecular weight converted to polystyrene using gel permeation chromatography (the same below).

[0194] Examples of the macropolyol include polyether polyol, polyester polyol, polycarbonate polyol, polyurethane polyol, epoxy polyol, vegetable oil polyol, polyolefin polyol, acrylic polyol, and vinyl monomer-modified polyol. These macropolyols may be used alone or in combination of two or more.

[0195] The number average molecular weight of the macropolyol is, for example, greater 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 further preferably 5,000 or less.

[0196] The hydroxyl value of the macromolecular polyol is, for example, 5 mgKOH / g or more, preferably 10 mgKOH / g or more, more preferably 15 mgKOH / g or more, and further preferably 20 mgKOH / g or more. In addition, the hydroxyl value of the macromolecular polyol is, for example, 500 mgKOH / g or less, preferably 300 mgKOH / g or less, more preferably 200 mgKOH / g or less, further preferably 100 mgKOH / g or less, and particularly preferably 50 mgKOH / g or less. It should be noted that the hydroxyl value is measured according to the description of JIS K 1557-1 (2007) (hereinafter the same).

[0197] As the macropolyol, preferably, acrylic polyol is used.

[0198] Examples of the acrylic polyol include copolymers of acrylic raw material components. The acrylic raw material component contains, for example, a hydroxyl group-containing (meth)acrylate and a copolymerizable vinyl monomer.

[0199] In addition, (meth)acrylate means an acrylate and / or a methacrylate. In addition, the copolymerizable vinyl monomer means a vinyl monomer which can be polymerized with the hydroxyl group-containing (meth)acrylate.

[0200] The hydroxyl-containing (meth)acrylate contains a hydroxyl group and an alkyl group. As the alkyl group, an alkyl group having 1 to 4 carbon atoms can be mentioned. As the hydroxyalkyl (meth)acrylate, specifically, for example, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate and 2,2-dihydroxymethylbutyl (meth)acrylate can be mentioned. These can be used alone or in combination of two or more. As the hydroxyl-containing (meth)acrylate, preferably hydroxyalkyl (meth)acrylate can be mentioned, more preferably 2-hydroxyethyl (meth)acrylate can be mentioned, and further preferably 2-hydroxyethyl methacrylate can be mentioned.

[0201] As copolymerizable vinyl monomers, for example, alkyl (meth)acrylates can be mentioned. Alkyl (meth)acrylates do not contain a hydroxyl group, but contain an alkyl group. As alkyl groups, alkyl groups having 1 to 4 carbon atoms and alkyl groups having 5 to 8 carbon atoms can be mentioned. As alkyl (meth)acrylates having an alkyl group having 1 to 4 carbon atoms, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, and tert-butyl (meth)acrylate can be mentioned. As alkyl (meth)acrylates having an alkyl group having 5 to 8 carbon atoms, for example, pentyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and cyclohexyl (meth)acrylate can be mentioned. These can be used alone or in combination of two or more.

[0202] In addition, as copolymerizable vinyl monomers, for example, vinyl monomers containing aromatic rings can be cited. As vinyl monomers containing aromatic rings, for example, (meth)acrylates containing aromatic rings can be cited. (Meth)acrylates containing aromatic rings contain aromatic rings. As aromatic rings, for example, benzene rings, naphthalene rings, anthracene rings and phenanthrene rings can be cited. As (meth)acrylates containing aromatic rings, more specifically, for example, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, m-phenoxybenzyl (meth)acrylate and 1-naphthylmethyl (meth)acrylate can be cited. These can be used alone or in combination of two or more. As (meth)acrylates containing aromatic rings, m-phenoxybenzyl (meth)acrylate and naphthylmethyl (meth)acrylate can be preferably cited, and m-phenoxybenzyl acrylate and naphthylmethyl acrylate can be more preferably cited. In addition, as vinyl monomers containing aromatic rings, in addition to the above, for example, styrene, α-methylstyrene, vinyltoluene, vinylbiphenyl and divinylbenzene can also be cited. These can be used alone or in combination of two or more. As the aromatic ring-containing vinyl monomer, preferably, an aromatic ring-containing (meth)acrylate is used.

[0203] In addition, as copolymerizable vinyl monomers, for example, vinyl monomers containing functional groups (excluding hydroxyl groups) can be cited. As vinyl monomers containing functional groups (excluding hydroxyl groups), for example, carboxyl-containing vinyl monomers, glycidyl-containing vinyl monomers, amino-containing vinyl monomers, cyano-containing vinyl monomers, acetoacetoxy-containing vinyl monomers, sulfonic acid group-containing vinyl monomers and phosphoric acid group-containing vinyl monomers can be cited. As carboxyl-containing vinyl monomers, for example, acrylic acid can be cited. As glycidyl-containing vinyl monomers, for example, (meth) acrylate glycidyl can be cited. As amino-containing vinyl monomers, for example, (meth) acrylate 2-aminoethyl can be cited. As cyano-containing vinyl monomers, for example, (meth) acrylonitrile can be cited. As acetoacetoxy-containing vinyl monomers, for example, (meth) acrylate acetoacetoxyethyl can be cited. As sulfonic acid group-containing vinyl monomers, for example, allyl sulfonic acid and its salts can be cited. As the vinyl monomer containing phosphoric acid group, for example, 2-methacryloyloxyethyl acid phosphate can be mentioned. These can be used alone or in combination of two or more. As the vinyl monomer containing functional group (excluding hydroxyl group), preferably carboxyl-containing vinyl monomer can be mentioned, and more preferably acrylic acid can be mentioned.

[0204] As copolymerizable vinyl monomers, in addition to the above, for example, vinyl esters, N-substituted unsaturated carboxylic acid amides, heterocyclic vinyl compounds, vinylidene halides, α-olefins, dienes and crosslinkable vinyl monomers can also be cited. As crosslinkable vinyl monomers, for example, multifunctional (meth) acrylates can be cited, and more specifically, bifunctional (meth) acrylates, trifunctional (meth) acrylates and tetrafunctional or higher (meth) acrylates can be cited. As bifunctional (meth) acrylates, for example, ethylene glycol di(meth) acrylate, butanediol di(meth) acrylate, hexanediol di(meth) acrylate and oligoethylene glycol di(meth) acrylate can be cited. As trifunctional (meth) acrylates, for example, trimethylolpropane tri(meth) acrylate can be cited. As tetrafunctional or higher (meth) acrylates, for example, pentaerythritol tetra(meth) acrylate can be cited. These can be used alone or in combination of two or more.

[0205] These copolymerizable vinyl monomers may be used alone or in combination of two or more.

[0206] As the copolymerizable vinyl monomer, preferably, a vinyl monomer containing an aromatic ring can be cited. If the copolymerizable vinyl monomer contains a vinyl monomer containing an aromatic ring, the acrylic polyol contains an aromatic ring. That is, the acrylic polyol is preferably an acrylic polyol containing an aromatic ring. By using an acrylic polyol containing an aromatic ring, a cured product (described later) having an excellent refractive index and excellent flexibility can be obtained.

[0207] In addition, as copolymerizable vinyl monomers, preferably carboxyl-containing vinyl monomers can be mentioned. If a carboxyl-containing vinyl monomer is contained, the acrylic polyol contains a carboxyl group. That is, the acrylic polyol is preferably a carboxyl-containing acrylic polyol. By using a carboxyl-containing acrylic polyol, a cured product (described later) having an excellent refractive index and excellent flexibility can be obtained.

[0208] The proportion of hydroxyl-containing (meth) acrylate and copolymerizable vinyl monomer can be appropriately set according to the purpose and use. For example, relative to the total amount of hydroxyl-containing (meth) acrylate and copolymerizable vinyl monomer 100 parts by mass, hydroxyl-containing (meth) acrylate is, for example, more than 1 part by mass, preferably more than 3 parts by mass. In addition, relative to the total amount of hydroxyl-containing (meth) acrylate and copolymerizable vinyl monomer 100 parts by mass, hydroxyl-containing (meth) acrylate is less than 30 parts by mass, preferably less than 10 parts by mass.

[0209] In addition, relative to the total amount of 100 parts by mass of the hydroxyl-containing (meth)acrylate and the copolymerizable vinyl monomer, the copolymerizable vinyl monomer (total amount) is, for example, 70 parts by mass or more, preferably 90 parts by mass or more. In addition, relative to the total amount of 100 parts by mass of the hydroxyl-containing (meth)acrylate and the copolymerizable vinyl monomer, the copolymerizable vinyl monomer (total amount) is, for example, 99 parts by mass or less, preferably 97 parts by mass or less.

[0210] More specifically, when using an aromatic ring-containing vinyl monomer, the aromatic ring-containing 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-containing (meth)acrylate and the copolymerizable vinyl monomer. In addition, the aromatic ring-containing 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-containing (meth)acrylate and the copolymerizable vinyl monomer.

[0211] 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 the hydroxyl value of the acrylic polyol (carboxyl group-containing acrylic polyol) falls within the range described below.

[0212] For example, relative to 100 parts by weight of the total amount of the hydroxyl-containing (meth)acrylate and the copolymerizable vinyl monomer, the carboxyl-containing vinyl monomer is, for example, 1 part by weight or more, preferably 5 parts by weight or more. In addition, relative to 100 parts by weight of the total amount of the hydroxyl-containing (meth)acrylate and the copolymerizable vinyl monomer, the carboxyl-containing vinyl monomer is, for example, 99 parts by weight or less, preferably 97 parts by weight or less.

[0213] The method for producing acrylic polyol is not particularly limited. For example, the above-mentioned acrylic acid raw material components are copolymerized in the presence of a known organic solvent. As the organic solvent, for example, toluene can be cited. It should be noted that the proportion and timing of the organic solvent can be appropriately set according to the purpose and use.

[0214] In the manufacture of acrylic polyol, known polymerization initiators are used as required. As polymerization initiators, for example, known free radical polymerization initiators (described later) can be cited, more preferably azo compounds (described later) and peroxides (described later), further preferably peroxides (described later), and particularly preferably peroxy-2-ethylhexanoic acid tert-butyl ester can be cited. It should be noted that the mixing ratio and timing of the polymerization initiator can be appropriately set according to the purpose and use.

[0215] The polymerization conditions of the acrylic acid raw material component can be appropriately set according to the purpose and use. For example, the polymerization temperature is, for example, 50° C. or more, preferably 70° C. or more. In addition, the polymerization temperature is, for example, 150° C. or less, preferably 130° C. or less. In addition, the polymerization time is, for example, 30 minutes or more, preferably 1 hour or more. In addition, the polymerization time is, for example, 12 hours or less, preferably 6 hours or less.

[0216] For example, when an organic solvent is used in the above-mentioned polymerization method, a solution and / or dispersion of acrylic polyol is obtained as a reaction product liquid.

[0217] The solid content concentration of the solution and / or dispersion of acrylic polyol is adjusted by known methods. For example, an organic solvent may be added to the above-mentioned reaction solution as required. In addition, a portion of the organic solvent may be removed from the above-mentioned reaction solution.

[0218] The solid content concentration of the acrylic polyol solution and / or dispersion is, for example, 30% by mass or more, preferably 40% by mass or more. In addition, the solid content concentration of the acrylic polyol solution and / or dispersion is, for example, 60% by mass or less, preferably 50% by mass or less.

[0219] The number average molecular weight of the acrylic polyol is, for example, greater than 400, preferably 500 or more, more preferably 1000 or more. The number average molecular weight of the acrylic polyol is, for example, 20,000 or less, preferably 15,000 or less, more preferably 10,000 or less, and further preferably 5,000 or less.

[0220] The hydroxyl value of the acrylic polyol is, for example, 1 mgKOH / g or more, preferably 3 mgKOH / g or more. In addition, the hydroxyl value of the acrylic polyol is, for example, 500 mgKOH / g or less, preferably 300 mgKOH / g or less. It should be noted that the hydroxyl value is measured according to the description of JISK 1557-1 (2007) (the same applies hereinafter).

[0221] In addition, 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, further preferably 15 mgKOH / g or more, and particularly preferably 20 mgKOH / g or more. In addition, the hydroxyl value of the acrylic polyol is preferably 200 mgKOH / g or less, further preferably 100 mgKOH / g or less, and particularly preferably 50 mgKOH / g or less.

[0222] In addition, when the acrylic polyol contains a carboxyl-containing acrylic polyol, the total of the acid value and the hydroxyl value of the acrylic polyol (carboxyl-containing acrylic polyol) is preferably 1 mgKOH / g or more, and more preferably 3 mgKOH / g or more. In addition, the total of the acid value and the hydroxyl value of the acrylic polyol (carboxyl-containing acrylic polyol) is preferably 20 mgKOH / g or less, and more preferably 10 mgKOH / g or less. It should be noted that the total of the acid value and the hydroxyl value is measured according to the description of JIS K 1557-5 (2007) (hereinafter the same).

[0223] In addition, when the acrylic polyol contains a carboxyl-containing acrylic polyol, the acid value of the acrylic polyol (carboxyl-containing acrylic polyol) is, for example, 1 mgKOH / g or more, preferably 3 mgKOH / g or more. In addition, the acid value of the acrylic polyol (carboxyl-containing acrylic polyol) is, for example, 20 mgKOH / g or less, preferably 10 mgKOH / g or less. It should be noted that the acid value is measured according to the description of JIS K 1557-5 (2007) (the same applies hereinafter).

[0224] In addition to the above-mentioned macromolecular polyols, polyols may also include low molecular weight polyols. Low molecular weight polyols have two or more hydroxyl groups in one molecule. Low molecular weight polyols are relatively low molecular weight organic compounds. The molecular weight of low molecular weight polyols is, for example, 40 or more, for example, 400 or less.

[0225] As low molecular weight polyols, for example, dihydric alcohols, trihydric alcohols, and alcohols with a valence of 4 or more can be cited. As dihydric alcohols, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, and dipropylene glycol can be cited. As trihydric alcohols, for example, glycerol and trimethylolpropane can be cited. As alcohols with a valence of 4 or more, for example, pentaerythritol and dipropylene glycol can be cited. In addition, as low molecular weight polyols, polymers obtained by addition polymerization of oxyalkylene (C2-3) to dihydric to tetrahydric alcohols in a manner having a number average molecular weight of less than 400 can also be cited. These can be used alone or in combination of two or more. As low molecular weight polyols, preferably dihydric alcohols and trihydric alcohols can be cited, and more preferably dihydric alcohols can be cited.

[0226] The polyol may be used alone or in combination of two or more. As the polyol, preferably, a macromolecular polyol may be used alone, and more preferably, an acrylic polyol may be used alone.

[0227] (3-4) Form of polyurethane resin raw material

[0228] As the form of the polyurethane resin raw material, for example, a one-component curable polyurethane resin and a two-component curable polyurethane resin can be mentioned. As the form of the polyurethane resin raw material, a two-component curable polyurethane resin can be preferably mentioned. The two-component curable polyurethane resin has a curing agent and a main agent that are independent of each other.

[0229] In the two-component curable polyurethane resin, the curing agent, for example, includes the above-mentioned polyisocyanate. In the two-component curable polyurethane resin, the main agent, for example, includes the above-mentioned polyol. The curing agent and the main agent are matched when used to form a carbamate cured product (cured resin described later). It should be noted that in the main agent, the polyol can be diluted with a known organic solvent. In addition, in the curing agent, the polyisocyanate can be diluted with a known organic solvent.

[0230] The two-component curable polyurethane resin preferably comprises a main agent containing the acrylic polyol and a curing agent containing the polyisocyanate. This provides a cured product having both an excellent refractive index and excellent flexibility (described later).

[0231] Polyisocyanates and polyols are subjected to urethanization reaction using known methods to generate cured polyurethane resins. In the urethanization reaction, the proportion of polyisocyanates and polyols is adjusted based on, for example, the equivalent ratio (OH / NCO) of the hydroxyl groups in the polyols relative to the isocyanate groups in the polyisocyanates. The equivalent ratio (OH / NCO) of the hydroxyl groups in the polyols relative to the isocyanate groups in the polyisocyanates is, for example, 0.5 or more, preferably 0.8 or more, and more preferably 0.95 or more. In addition, the equivalent ratio (OH / NCO) of the hydroxyl groups in the polyols relative to the isocyanate groups in the polyisocyanates is, for example, 2.0 or less, preferably 1.5 or less, and more preferably 1.1 or less.

[0232] In addition, when the polyol includes the above-mentioned carboxyl-containing acrylic polyol, the mixing ratio of the polyisocyanate to the polyol is adjusted based on, for example, the equivalent ratio (OH+COOH / NCO) of the hydroxyl group and the carboxyl group (total amount) in the polyol relative to the isocyanate group in the polyisocyanate. The equivalent ratio (OH+COOH / NCO) of the hydroxyl group and the carboxyl group (total amount) in the polyol relative to the isocyanate group in the polyisocyanate is, for example, 0.5 or more, preferably 0.8 or more, and more preferably 0.95 or more. In addition, the equivalent ratio (OH+COOH / NCO) of the hydroxyl group and the carboxyl group (total amount) in the polyol relative to the isocyanate group in the polyisocyanate is, for example, 2.0 or less, preferably 1.5 or less, and more preferably 1.1 or less.

[0233] (3-5) Acrylic resin raw materials

[0234] 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.

[0235] (3-6) Monomer components

[0236] The monomer component contains, for example, a radical polymerizable monomer. The radical polymerizable monomer is a monomer that can generate a curable acrylic resin by radical polymerization.

[0237] As free radical polymerizable monomers, for example, monomers described above as raw materials of acrylic polyols can be cited. More specifically, as free radical polymerizable monomers, for example, the above-mentioned (meth) alkyl acrylates, the above-mentioned hydroxyl-containing (meth) acrylates, the above-mentioned aromatic ring-containing vinyl monomers, the above-mentioned carboxyl-containing vinyl monomers, the above-mentioned glycidyl-containing vinyl monomers, the above-mentioned amino-containing vinyl monomers, the above-mentioned cyano-containing vinyl monomers, the above-mentioned acetoacetoxy-containing vinyl monomers, the above-mentioned sulfonic acid-containing vinyl monomers, the above-mentioned phosphoric acid-containing vinyl monomers, the above-mentioned vinyl esters, the above-mentioned N-substituted unsaturated carboxylic acid amides, the above-mentioned heterocyclic vinyl compounds, the above-mentioned vinyl halide compounds, the above-mentioned α-olefins, the above-mentioned dienes and the above-mentioned cross-linking vinyl monomers can be cited. These can be used alone or in combination of two or more.

[0238] As the radical polymerizable monomer, preferably a crosslinkable vinyl monomer is used, more preferably a polyfunctional (meth)acrylate is used, further preferably a trifunctional (meth)acrylate is used, and particularly preferably trimethylolpropane tri(meth)acrylate is used.

[0239] That is, the monomer component preferably contains a crosslinkable vinyl monomer, more preferably contains a multifunctional (meth)acrylate, further preferably contains a trifunctional (meth)acrylate, and particularly preferably contains trimethylolpropane tri(meth)acrylate.

[0240] Moreover, as a radical polymerizable monomer, the radical polymerizable monomer other than a crosslinkable vinyl monomer (hereinafter referred to as other monomer) can also be preferably mentioned.

[0241] That is, the monomer component preferably contains a crosslinkable vinyl monomer and other monomers. As other monomers, preferably, the above-mentioned alkyl (meth)acrylate and / or the above-mentioned aromatic ring-containing vinyl monomer can be mentioned.

[0242] The content ratio of the crosslinkable vinyl monomer and other radical polymerizable monomers can be appropriately set depending on the purpose and application.

[0243] For example, the content ratio of the crosslinkable vinyl monomer relative to the total amount of the crosslinkable vinyl monomer and other free radical polymerizable monomers is, for example, 10% by mass or more, preferably 20% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more, and particularly preferably 60% by mass or more. In addition, the content ratio of the crosslinkable vinyl monomer relative to the total amount of the crosslinkable vinyl monomer and other free radical polymerizable monomers is, for example, 99% by mass or less, preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 70% by mass or less, and particularly preferably 65% ​​by mass or less.

[0244] For example, the content ratio of the other radical polymerizable monomers relative to the total amount of the crosslinkable vinyl monomer and the other radical polymerizable monomers is, for example, 1% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, and particularly preferably 35% by mass or more. In addition, the content ratio of the other radical polymerizable monomers relative to the total amount of the crosslinkable vinyl monomer and the other radical polymerizable monomers is, for example, 90% by mass or less, preferably 80% by mass or less, more preferably 60% by mass or less, further preferably 50% by mass or less, and particularly preferably 40% by mass or less.

[0245] (3-7) Polymerization initiator

[0246] Examples of the polymerization initiator include known radical polymerization initiators. Examples of the radical polymerization initiator include active energy ray radical polymerization initiators and thermal radical polymerization initiators.

[0247] As the active energy ray radical polymerization initiator, for example, a photo radical polymerization initiator can be mentioned. As the photo radical polymerization initiator, for example, an alkyl phenone photopolymerization initiator, an acylphosphine oxide photopolymerization initiator, an oxime ester photopolymerization initiator, a carbazole phenone photopolymerization initiator, an acridine photopolymerization initiator, a triazine photopolymerization initiator, and a benzoyl photopolymerization initiator can be mentioned. These can be used alone or in combination of two or more.

[0248] As the thermal free radical polymerization initiator, for example, azo compounds and peroxides can be mentioned. As the azo compound, for example, azoisobutyronitrile and dimethyl azobisisobutyrate can be mentioned. As the peroxide, for example, benzoyl peroxide, ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxyester, peroxy-2-ethylhexanoic acid tert-butyl ester and peroxydicarbonate can be mentioned. These can be used alone or in combination of two or more.

[0249] It should be noted that the active energy ray radical polymerization initiator may also function as a thermal radical polymerization initiator. In addition, the thermal radical polymerization initiator may also function as an active energy ray radical polymerization initiator.

[0250] As the free radical polymerization initiator, commercially available products can also be mentioned. As commercially available free radical polymerization initiators, for example, Omnirad series manufactured by IGM Resins BV and PERCURE series manufactured by NOF Corporation can be mentioned. These can be used alone or in combination of two or more.

[0251] As the polymerization initiator, preferably, an active energy ray radical polymerization initiator is used, and more preferably, a photopolymerization initiator is used. The mixing ratio and mixing timing of the polymerization initiator can be appropriately set according to the purpose and application.

[0252] (3-8) Formula of acrylic resin raw materials

[0253] As the form of the acrylic resin raw material, for example, a mixture containing the above-mentioned free radical polymerizable monomer and the above-mentioned polymerization initiator can be cited. The acrylic resin raw material may also contain a known organic solvent. The acrylic resin raw material preferably does not contain an organic solvent and is composed of the above-mentioned free radical polymerizable monomer and the above-mentioned polymerization initiator.

[0254] (4) Form of curable composition

[0255] 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 a curable compound. More preferably, the curable composition contains a plasticizer and a polyurethane resin raw material, or contains a plasticizer and an acrylic resin raw material.

[0256] The mixing ratio of plasticizer and curable compound is not particularly limited and is appropriately set according to purpose and use. For example, relative to 100 parts by mass of the solid component of the curable compound, the plasticizer is, for example, 1 part by mass (phr) or more, preferably 5 parts by mass (phr) or more. In addition, relative to 100 parts by mass of the solid component of the curable compound, the plasticizer is, for example, 70 parts by mass (phr) or less, preferably 50 parts by mass (phr) or less.

[0257] In addition, for example, the amount of the plasticizer is, for example, 1% by mass or more, preferably 3% by mass or more, relative to the total amount of the plasticizer and the curable compound (solid content basis). In addition, the amount of the plasticizer is, for example, 50% by mass or less, preferably 35% by mass or less, relative to the total amount of the plasticizer and the curable compound (solid content basis).

[0258] In addition, for example, relative to the total amount of the plasticizer and the curable compound (solid content basis), the curable compound is, for example, 50% by mass or more, preferably 65% ​​by mass or more. In addition, relative to the total amount of the plasticizer and the curable compound (solid content basis), the curable compound is, for example, 99% by mass or less, preferably 97% by mass or less.

[0259] In addition, the form of the plasticizer is not particularly limited. For example, when the curable compound is a two-component curable polyurethane resin, the plasticizer can be added to the curing agent (polyisocyanate) of the two-component curable polyurethane resin. In addition, the plasticizer can be added to the main agent (polyol) of the two-component curable polyurethane resin. In addition, the plasticizer can be added to both the main agent and the curing agent of the two-component curable polyurethane resin.

[0260] In addition, the plasticizer can be prepared separately from the main agent and the curing agent of the two-component curable polyurethane resin. When the plasticizer is prepared separately, the plasticizer can be mixed at the same time as the main agent and the curing agent are mixed, and the plasticizer can be mixed in the mixture after the main agent and the curing agent are mixed.

[0261] In addition, for example, when the curable compound is an acrylic resin raw material, the plasticizer may be mixed with the radical polymerizable monomer in advance. In addition, the plasticizer may be mixed with the polymerization initiator in advance. In addition, the plasticizer may be mixed at the same time as the radical polymerizable monomer and the polymerization initiator are mixed, and in addition, the plasticizer may be mixed with the mixture of the radical polymerizable monomer and the polymerization initiator after the radical polymerizable monomer and the polymerization initiator are mixed.

[0262] (5) Sub-components

[0263] The curable composition may contain additives as auxiliary components as needed. The auxiliary component is a component whose content ratio relative to the whole is below a specified value. The content ratio of the auxiliary component relative to the whole is, for example, below 10% by mass. That is, the ratio of the additive is below 10% by mass relative to the total solid content of the curable composition.

[0264] As additives, for example, ultraviolet light absorbers (UV absorbers), light stabilizers (light stabilizers) and antioxidants can be mentioned. In addition, as additives, for example, heat stabilizers, crosslinking agents, silane coupling agents, defoamers, leveling agents, mildew inhibitors, rust inhibitors, matting agents, flame retardants, thixotropic agents, tackifiers, thickeners, lubricants, antistatic agents, surfactants, reaction delay agents, hydrolysis-proof agents, dyes, inorganic pigments, organic pigments, antitackifiers, inorganic fillers and organic fillers can be mentioned. These can be used alone or in combination of more than two. The amount of additives added and the timing of addition can be appropriately set according to purpose and use.

[0265] From the viewpoint of weather resistance of the cured product (described later), as additives, preferably, ultraviolet absorbers (UV absorbers), light stabilizers (light stabilizers) and antioxidants can be cited. That is, the curable composition preferably contains at least one selected from the group consisting of ultraviolet absorbers, light stabilizers and antioxidants. From the viewpoint of weather resistance of the cured product (described later), the ratio of the additive (at least one selected from the group consisting of ultraviolet absorbers, light stabilizers and antioxidants) to 1 part by mass of the above-mentioned curable composition (total amount) is, for example, 1×10 -6 Mass parts (ppm) or more, preferably 10×10 -6 Parts by mass (ppm) or more, more preferably 100×10 -6 In addition, from the viewpoint of low cost, the ratio of the additive (at least one additive selected from the group consisting of ultraviolet absorbers, light resistance stabilizers and antioxidants) to 1 part by mass of the curable composition (total amount) is, for example, 100,000×10 -6 Parts by mass (ppm) or less, preferably 10000×10 -6 Parts by mass (ppm) or less, more preferably 1000×10 -6 Parts by mass (ppm) or less.

[0266] There are no particular limitations on the ultraviolet absorber, and examples include known ultraviolet absorbers (for example, those listed in the catalogs of ADEKA and CLARIANT). More specifically, examples include benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, benzal ultraviolet absorbers, and triazine ultraviolet absorbers. These can be used alone or in combination of two or more. From the perspective of weather resistance of the cured product (described later), a benzotriazole ultraviolet absorber is preferably used as the ultraviolet absorber. The mixing ratio of the ultraviolet absorber is, for example, 1×10 -6 Mass parts (ppm) or more, preferably 10×10 -6 Parts by mass (ppm) or more, more preferably 100×10 -6 In addition, from the viewpoint of low cost, the mixing ratio of the ultraviolet absorber to 1 part by mass of the curable composition is, for example, 100000×10 -6 Parts by mass (ppm) or less, preferably 10000×10 -6 Parts by mass (ppm) or less, more preferably 1000×10 -6 Parts by mass (ppm) or less.

[0267] There are no particular limitations on the light stabilizer, and examples include known light stabilizers (for example, those listed in the ADEKA catalog). More specifically, examples include hindered amine (HALS) light stabilizers and benzoate light stabilizers. These can be used alone or in combination of two or more. From the perspective of weather resistance of the cured product (described later), hindered amine (HALS) light stabilizers are preferred as light stabilizers. The blending ratio of the light stabilizer is, for example, 1×10 -6 Mass parts (ppm) or more, preferably 10×10 -6 Parts by mass (ppm) or more, more preferably 100×10 -6 In addition, from the viewpoint of low cost, the light resistance stabilizer is contained in an amount of, for example, 100,000×10 -6 Parts by mass (ppm) or less, preferably 10000×10 -6 Parts by mass (ppm) or less, more preferably 1000×10 -6 Parts by mass (ppm) or less.

[0268] The antioxidant is not particularly limited, and known antioxidants (for example, those described in the ADEKA catalog) can be cited. More specifically, for example, phenolic antioxidants, phosphorus antioxidants, and thiophene antioxidants can be cited as antioxidants. These can be used alone or in combination of two or more. From the perspective of weather resistance of the cured product (described later), phenolic antioxidants are preferably cited as antioxidants. The mixing ratio of the antioxidant is, for example, 1×10 -6 Mass parts (ppm) or more, preferably 10×10 -6 Parts by mass (ppm) or more, more preferably 100×10 -6 In addition, from the viewpoint of low cost, the blending ratio of the antioxidant to 1 part by mass of the curable composition is, for example, 100,000×10 -6 Parts by mass (ppm) or less, preferably 10000×10 -6 Parts by mass (ppm) or less, more preferably 1000×10 -6 Parts by mass (ppm) or less.

[0269] (6) Application

[0270] The curable composition is suitable for use in various industrial fields. Examples of the use of the curable composition include coatings, paints, and adhesives. Preferably, an adhesive is used as the use of the curable composition.

[0271] The adhesive is an uncured curable composition, and forms an adhesive cured product (cured product described below) by curing. The adhesive cured product bonds adherends.

[0272] In addition, according to the above-mentioned curable composition, a cured product with excellent refractive index and excellent flexibility can be obtained. Therefore, the above-mentioned curable composition is suitable for use as an optical curable composition. As the use of the optical curable composition, for example, optical coatings, optical coatings and optical adhesives can be cited.

[0273] 4. Cured product

[0274] (1) Principal component

[0275] The cured product contains the above-mentioned plasticizer and curing resin as main components. The main component is a component whose content ratio relative to the whole is greater than a specified value. The content ratio of the main component relative to the whole is, for example, greater than 90% by mass. That is, the total solid content of the plasticizer and the curing resin is greater than 90% by mass relative to the total solid content of the cured product.

[0276] The cured product is formed by curing the above-mentioned curable composition by a known method. The curing method of the curable composition is appropriately selected according to the type of the curable compound.

[0277] (2) Curing resin

[0278] The curable resin contains, for example, a cured product of the above-mentioned curable compound, and preferably consists of a cured product of the above-mentioned curable compound.

[0279] More specifically, for example, cured polyurethane resins, cured polyolefin resins, cured polyamine resins, cured amide resins, cured urea resins, cured phenolic resins, cured epoxy resins, cured acrylic resins, cured melamine resins, and cured alkyd resins can be cited. These can be used alone or in combination of two or more.

[0280] As the curable resin, preferably, a curable urethane resin and a curable acrylic resin are mentioned.

[0281] As the cured polyurethane resin, for example, a cured product of the above-mentioned polyurethane resin raw material can be cited. As the cured polyurethane resin, more specifically, a reaction product of a main agent containing the above-mentioned polyol and a curing agent containing the above-mentioned polyisocyanate can be cited. By such a cured resin, a cured product having both a more excellent refractive index and a more excellent flexibility can be obtained. More specifically, as long as the cured resin contains a cured polyurethane resin (a reaction product of a main agent containing the above-mentioned acrylic polyol and a curing agent containing the above-mentioned polyisocyanate), a cured product satisfying the physical properties (refractive index and flexibility) described later can be obtained more easily.

[0282] As the cured acrylic resin, for example, the cured product of the above-mentioned acrylic resin raw material can be cited. As the cured acrylic resin, more specifically, the reaction product obtained by the free radical polymerization reaction of the above-mentioned free radical polymerizable monomer can be cited. The method for obtaining the cured acrylic resin is not particularly limited. For example, when an active energy ray free radical polymerization initiator is used, the acrylic resin raw material is irradiated with active energy rays having a specified wavelength. In addition, when a thermal free radical polymerization initiator is used, the acrylic resin raw material is heated to a specified temperature. Thus, the polymerization initiator is activated, and the free radical polymerizable monomer undergoes a free radical polymerization reaction to obtain a cured acrylic resin. In particular, as long as the cured resin contains a cured acrylic resin (the free radical polymerization product of the above-mentioned monomer components), a cured product having excellent flexibility and a particularly excellent refractive index can be obtained.

[0283] (3) Sub-components

[0284] The solidified material may contain the above-mentioned additives as accessory components as required. The accessory component is a component whose content ratio relative to the whole is below a specified value. The content ratio of the accessory component relative to the whole is, for example, below 10% by mass. That is, the ratio of the additive is below 10% by mass relative to the total solid content of the solidified material.

[0285] From the viewpoint of weather resistance of the cured product, the additives preferably include ultraviolet absorbers (UV absorbers), light stabilizers (light stabilizers) and antioxidants. That is, the cured product preferably contains at least one selected from the group consisting of ultraviolet absorbers, light stabilizers and antioxidants. From the viewpoint of weather resistance of the cured product, the ratio of the additive (at least one selected from the group consisting of ultraviolet absorbers, light stabilizers and antioxidants) to 1 part by mass of the cured product (total amount) is, for example, 1×10 -6 Mass parts (ppm) or more, preferably 10×10 -6 Parts by mass (ppm) or more, more preferably 100×10 -6In addition, from the viewpoint of low cost, the ratio of the additive (at least one additive selected from the group consisting of ultraviolet absorbers, light stabilizers and antioxidants) to 1 part by mass of the above-mentioned cured product (total amount) is, for example, 100,000×10 -6 Parts by mass (ppm) or less, preferably 10000×10 -6 Parts by mass (ppm) or less, more preferably 1000×10 -6 Parts by mass (ppm) or less.

[0286] The ultraviolet absorber is not particularly limited, and known ultraviolet absorbers (for example, those described in the catalog of ADEKA) can be cited. More specifically, for example, benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, benzal ultraviolet absorbers, and triazine ultraviolet absorbers can be cited. These can be used alone or in combination of two or more. From the viewpoint of weather resistance of the cured product, a benzotriazole ultraviolet absorber can be preferably cited as the ultraviolet absorber. The mixing ratio of the ultraviolet absorber relative to 1 part by mass of the above-mentioned cured product is, for example, 1×10 -6 Mass parts (ppm) or more, preferably 10×10 -6 Parts by mass (ppm) or more, more preferably 100×10 -6 In addition, from the viewpoint of low cost, the mixing ratio of the ultraviolet absorber to 1 part by mass of the above-mentioned cured product is, for example, 100000×10 -6 Parts by mass (ppm) or less, preferably 10000×10 -6 Parts by mass (ppm) or less, more preferably 1000×10 -6 Parts by mass (ppm) or less.

[0287] There are no particular limitations on the light stabilizer (photostabilizer), and examples include known light stabilizers (for example, those listed in the ADEKA catalog). More specifically, examples include hindered amine (HALS) light stabilizers and benzoate light stabilizers. These can be used alone or in combination of two or more. From the perspective of weather resistance of the cured product, a preferred light stabilizer is a hindered amine (HALS) light stabilizer. The blending ratio of the light stabilizer is, for example, 1×10 -6 Mass parts (ppm) or more, preferably 10×10 -6 Parts by mass (ppm) or more, more preferably 100×10 -6In addition, from the viewpoint of low cost, the light resistance stabilizer is mixed in a proportion of, for example, 100,000×10 -6 Parts by mass (ppm) or less, preferably 10000×10 -6 Parts by mass (ppm) or less, more preferably 1000×10 -6 Parts by mass (ppm) or less.

[0288] The antioxidant is not particularly limited, and known antioxidants (for example, those described in the ADEKA catalog) can be cited. More specifically, for example, phenolic antioxidants, phosphorus antioxidants, and thiophene antioxidants can be cited as antioxidants. These can be used alone or in combination of two or more. From the perspective of weather resistance of the cured product, phenolic antioxidants can be preferably cited as antioxidants. The mixing ratio of the antioxidant relative to 1 part by mass of the cured product is, for example, 1×10 -6 Mass parts (ppm) or more, preferably 10×10 -6 Parts by mass (ppm) or more, more preferably 100×10 -6 In addition, from the viewpoint of low cost, the blending ratio of the antioxidant to 1 part by mass of the above-mentioned cured product is, for example, 100000×10 -6 Parts by mass (ppm) or less, preferably 10000×10 -6 Parts by mass (ppm) or less, more preferably 1000×10 -6 Parts by mass (ppm) or less.

[0289] (4)Physical properties

[0290] The above-mentioned cured product contains the above-mentioned compound and therefore has both excellent refractive index and excellent flexibility.

[0291] 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, further preferably 1.60 or more, and particularly preferably 1.61 or more. In addition, the refractive index of the cured product is, for example, 1.80 or less, preferably 1.70 or less. It should be noted that the refractive index is measured according to the embodiments described below.

[0292] The tensile storage modulus (E') of the cured product at 25°C is 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, further preferably 300 MPa or less, further preferably 200 MPa or less, further preferably 100 MPa or less, and particularly preferably 50 MPa or less. In addition, the tensile storage modulus (E') of the cured product at 25°C is, for example, 1 MPa or more. It should be noted that the tensile storage modulus (E') is measured according to the examples described below.

[0293] (5) Application

[0294] The above-mentioned cured product is suitable for use in various industrial fields. As the use of the cured product, for example, a resin molded product, a film and an adhesive can be mentioned. As the use of the cured product, preferably an adhesive can be mentioned.

[0295] It should be noted that 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 (below 0°C) and has adhesiveness (tackiness).

[0296] In addition, the above-mentioned cured product has excellent refractive index and excellent flexibility. Therefore, the above-mentioned cured product is suitable for use as an optical resin. As the purpose of the optical resin, for example, an optical lens, an optical film and an optical adhesive can be cited.

[0297] Furthermore, the curable composition, adhesive, and pressure-sensitive adhesive described above contain the plasticizer described above. Therefore, according to such a curable composition, a cured product having both refractive index and flexibility can be obtained.

[0298] Example

[0299] Next, the present invention is described based on embodiments and comparative examples, but the present invention is not limited thereto. It should be noted that, unless otherwise specified, "parts" and "%" are based on mass. In addition, the specific numerical values ​​such as the mixing ratio (containing ratio), physical property values, parameters, etc. used in the following description can be replaced by the upper limit value (defined as "below", "less than" numerical value) or the lower limit value (defined as "above", "greater than") of the corresponding mixing ratio (containing ratio), physical property values, parameters, etc. recorded in the above-mentioned "Specific Implementation Methods" and corresponding to them.

[0300] 1. Synthesis of plasticizer

[0301] Example 1 (Bn-GST)

[0302] 4-Benzylthiomethyl-1,8-bisbenzylthio-3,6-dithiaoctane (Bn-GST) was synthesized by the following method.

[0303] First, 40.5 g (595.0 mmol) of sodium ethoxide and 300 mL of ethanol were added to a four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a dropping funnel, and stirred to obtain a sodium ethoxide solution.

[0304] Next, 50.0 g (191.9 mmol) of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (GST) was slowly added to the sodium ethoxide solution while stirring, thereby obtaining a reaction solution of sodium ethoxide and GST.

[0305] Next, the reaction solution was cooled in an ice bath. Next, 101.8 g (595.0 mmol) of benzyl bromide was added dropwise to the reaction solution while maintaining the internal temperature of the reaction solution at 10°C or less.

[0306] The equivalent ratio of the bromine atoms in benzyl bromide to the mercapto groups in GST (bromine atoms / mercapto groups) was 1.03.

[0307] Next, the ice bath was removed from the reaction solution, thereby adjusting the temperature of the reaction solution to room temperature. In addition, the reaction solution was stirred overnight.

[0308] Then, 300 mL of water was added to the reaction solution. Furthermore, dilute hydrochloric acid was added to the reaction solution. Thus, the pH of the reaction solution was adjusted to 6.0 or less. It should be noted that the pH was confirmed using pH test paper.

[0309] Then, 500 mL of dichloromethane was added to the reaction solution. Then, the mixed solution was separated to take out the organic phase. Then, the organic phase was concentrated using an evaporator. Thus, a concentrated product of the reaction solution was obtained.

[0310] The concentrate (crude product) was diluted with 100 mL of dichloromethane to obtain a diluent. The diluent was passed through 100 mL of silica gel. In addition, 300 mL of dichloromethane was used to make the diluent flow out. Then, the diluent was concentrated using an evaporator. Thus, 4-benzylthiomethyl-1,8-bisbenzylthio-3,6-dithiaoctane (Bn-GST) was obtained as a reaction product.

[0311] Bn-GST was a light yellow transparent liquid. The yield of Bn-GST was 84.2 g. The viscosity (25° C.) of Bn-GST was 500 mPa·s. The refractive index (nD) of Bn-GST was 1.63.

[0312] It should be noted that Bn-GST is as follows 1Identified by H-NMR (400 MHz, CDCl3).

[0313] 1 H-NMR (400MHz, CDCl3):

[0314] δ7.19-7.37 (m, 15H)

[0315] δ3.70-3.78 (m, 6H)

[0316] δ2.49-2.85 (m, 13H)

[0317] Example 2 (Bz-GST)

[0318] 4-Benzoylthiomethyl-1,8-bisbenzoylthio-3,6-dithiaoctane (Bz-GST) was synthesized by the following method.

[0319] First, 30.0 g (115.2 mmol) of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (GST) was placed in a four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a dropping funnel.

[0320] Next, 100 mL of dichloromethane was added to the above flask to obtain a GST solution.

[0321] 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.

[0322] Next, the reaction solution was cooled in an ice bath, and then, while the internal temperature of the reaction solution was maintained at 10° C. or less, 53.4 g (380.0 mmol) of benzoyl chloride was added dropwise to the reaction solution.

[0323] The equivalent ratio of the chlorine atoms in benzoyl chloride to the mercapto groups in GST (chlorine atoms / mercapto groups) was 1.10.

[0324] Next, the ice bath was removed from the reaction solution, thereby adjusting the temperature of the reaction solution to room temperature. In addition, the reaction solution was stirred overnight.

[0325] Then, 300 mL of water and 200 mL of dichloromethane were added to the reaction solution. Then, the mixed solution was separated to take out the organic phase. Next, the organic phase was washed with dilute hydrochloric acid. Furthermore, the organic phase was washed with a saturated sodium bicarbonate aqueous solution. Then, the organic phase was concentrated with an evaporator. Thus, a concentrated product of the reaction solution was obtained.

[0326] The concentrate (crude product) was diluted with 100 mL of dichloromethane to obtain a diluent. The diluent was passed through 100 mL of silica gel. In addition, 300 mL of dichloromethane was used to make the diluent flow out. Then, the diluent was concentrated using an evaporator. Thus, 4-benzoylthiomethyl-1,8-bisbenzoylthio-3,6-dithiaoctane (Bz-GST) was obtained as a reaction product.

[0327] Bz-GST was a colorless transparent liquid. The yield of Bz-GST was 63.2 g. The viscosity (25° C.) of Bz-GST was 5000 mPa·s. The refractive index (nD) of Bz-GST was 1.65.

[0328] It should be noted that Bz-GST is as follows 1 Identified by H-NMR (400 MHz, CDCl3).

[0329] 1 H-NMR (400MHz, CDCl3):

[0330] δ7.89-8.01 (m, 6H)

[0331] δ7.51-7.61 (m, 3H)

[0332] δ7.37-7.48 (m, 6H)

[0333] δ2.79-3.59 (m, 13H)

[0334] Example 3 (Ac-GST)

[0335] 4-Acetylthiomethyl-1,8-bisacetylthio-3,6-dithiaoctane (Ac-GST) was synthesized by the following method.

[0336] First, 5.00 g (19.2 mmol) of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (GST) was placed in a four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a dropping funnel.

[0337] Next, 20 mL of dichloromethane was added to the above flask to obtain a GST solution.

[0338] Next, 6.41 g (63.3 mmol) of triethylamine was slowly added to the GST solution while stirring, thereby obtaining a reaction solution of triethylamine and GST.

[0339] Next, the reaction solution was cooled in an ice bath. Next, 6.47 (63.3 mmol) of acetic anhydride was added dropwise to the reaction solution while maintaining the internal temperature of the reaction solution at 10°C or less.

[0340] The equivalent ratio of the carboxyl group of acetic anhydride to the mercapto group in GST (carboxyl group / mercapto group) was 2.20.

[0341] Next, the ice bath was removed from the reaction solution, thereby adjusting the temperature of the reaction solution to room temperature. In addition, the reaction solution was stirred overnight.

[0342] Then, 30 mL of water and 20 mL of dichloromethane were added to the reaction solution, and the mixed solution was separated to take out the organic phase, and then the organic phase was washed with dilute hydrochloric acid.

[0343] Furthermore, the organic phase was washed with a saturated sodium bicarbonate aqueous solution and then concentrated using an evaporator to obtain a concentrated product of the reaction solution.

[0344] The concentrate (crude product) was diluted with 10 mL of dichloromethane to obtain a diluent. The diluent was passed through 10 mL of silica gel. In addition, 30 mL of dichloromethane was used to make the diluent flow out. Then, the diluent was concentrated using an evaporator. Thus, 4-acetylthiomethyl-1,8-diacetylthio-3,6-dithiaoctane (Ac-GST) was obtained as a reaction product.

[0345] Ac-GST was a colorless transparent liquid. The yield of Ac-GST was 7.21 g. The viscosity (25° C.) of Ac-GST was 200 mPa·s. The refractive index (nD) of Ac-GST was 1.58.

[0346] It should be noted that Ac-GST is as follows 1 Identified by H-NMR (400 MHz, CDCl3).

[0347] 1 H-NMR (400MHz, CDCl3):

[0348] δ2.71-3.34 (m, 13H)

[0349] δ2.33-2.38 (m, 9H)

[0350] Example 4 (PA-GST)

[0351] 4-Phenylacetylthiomethyl-1,8-bisphenylacetylthio-3,6-dithiaoctane (PA-GST) was synthesized by the following method.

[0352] First, 50.0 g (191.9 mmol) of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (GST) was placed in a four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a dropping funnel.

[0353] Next, 250 g of toluene was added to the above flask to obtain a GST solution.

[0354] 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.

[0355] Next, the reaction solution was cooled in an ice bath, and then, while the internal temperature of the reaction solution was maintained at 15° C. or less, 91.7 g (593.1 mmol) of phenylacetyl chloride was added dropwise to the reaction solution.

[0356] The equivalent ratio of chlorine atoms in phenylacetyl chloride to mercapto groups in GST (chlorine atoms / mercapto groups) was 1.03.

[0357] 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 less.

[0358] Then, 550 g of 10% sodium chloride aqueous solution was added to the reaction solution. Then, the mixed solution was separated and the organic phase was taken out. Next, the organic phase was washed with 500 mL of 1N dilute hydrochloric acid, and then washed with 500 mL of saturated sodium bicarbonate aqueous solution. Furthermore, it was washed with 500 mL of pure water.

[0359] The washing liquid was passed through activated alumina (300 mesh, for chromatography, basic), and 120 g of toluene was used to allow the reaction product remaining in the alumina to flow out.

[0360] Anhydrous sodium sulfate is added to the washing liquid after the liquid is passed and stirred to remove the residual water in the washing liquid. The sodium sulfate is filtered out with a folded filter paper to obtain a toluene dilution of the product. Then, the dilution is concentrated with an evaporator. Thus, 4-phenylacetylthiomethyl-1,8-bisphenylacetylthio-3,6-dithiaoctane (PA-GST) is obtained as a reaction product.

[0361] PA-GST was a light yellow transparent liquid. The yield of PA-GST was 105.2 g. The viscosity (25° C.) of PA-GST was 1100 mPa·s. The refractive index (nD) of PA-GST was 1.62.

[0362] It should be noted that PA-GST is implemented as follows: 1 Identified by H-NMR (400 MHz, CDCl3).

[0363] 1 H-NMR (400MHz, CDCl3):

[0364] δ7.21-7.37 (m, 15H)

[0365] δ3.80-3.84 (m, 6H)

[0366] δ2.64-3.25 (m, 13H)

[0367] Example 5 (PP-GST)

[0368] 4-(3-phenylpropionyl)thiomethyl-1,8-bis(3-phenylpropionyl)thio-3,6-dithiaoctane (PP-GST) was synthesized by the following method.

[0369] First, 50.0 g (191.9 mmol) of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (GST) was placed in a four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a dropping funnel.

[0370] Next, 250 g of toluene was added to the above flask to obtain a GST solution.

[0371] 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.

[0372] Next, the reaction solution was cooled in an ice bath, and then 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 less.

[0373] The equivalent ratio of the chlorine atoms in 3-phenylpropionyl chloride to the mercapto groups in GST (chlorine atoms / mercapto groups) was 1.03.

[0374] 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 less.

[0375] Then, 550 g of 10% sodium chloride aqueous solution was added to the reaction solution. Then, the mixed solution was separated and the organic phase was taken out. Next, the organic phase was washed with 500 mL of 1N dilute hydrochloric acid, and then washed with 500 mL of saturated sodium bicarbonate aqueous solution. Furthermore, it was washed with 500 mL of pure water.

[0376] The washing liquid was passed through activated alumina (300 mesh, for chromatography, basic), and 120 g of toluene was used to allow the reaction product remaining in the alumina to flow out.

[0377] Anhydrous sodium sulfate was added to the washing liquid after the liquid was passed and stirred to remove the residual water in the washing liquid. The sodium sulfate was filtered out with folded filter paper to obtain a toluene dilution of the product. Then, the dilution was concentrated with an evaporator. Thus, 4-(3-phenylpropionyl)thiomethyl-1,8-bis(3-phenylpropionyl)thio-3,6-dithiaoctane (PP-GST) was obtained as a reaction product.

[0378] PA-GST was a light yellow transparent liquid. The yield of PP-GST was 119.0 g. The viscosity (25° C.) of PP-GST was 400 mPa·s. The refractive index (nD) of PP-GST was 1.60.

[0379] It should be noted that PP-GST is implemented as follows: 1 Identified by H-NMR (400 MHz, CDCl3).

[0380] 1 H-NMR (400MHz, CDCl3):

[0381] δ7.13-7.33 (m, 15H)

[0382] δ2.66-3.29 (m, 25H)

[0383] Example 6 (Bz-FSH)

[0384] 5,7-bis(benzoylmercaptomethyl)-1,11-bis(benzoylmercapto)-3,6,9-trithiaundecane (Bz-FSH) was synthesized by the following method.

[0385] First, 50.0 g (136.4 mmol) of 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (FSH) was placed in a four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a dropping funnel.

[0386] Next, 500 g of toluene was added to the above flask to obtain a FSH solution.

[0387] Next, 42.8 g (422.7 mmol) of triethylamine was slowly added to the FSH solution while stirring, thereby obtaining a reaction solution of triethylamine and FSH.

[0388] Next, the reaction solution was cooled in an ice bath. Next, 59.4 g (422.7 mmol) of benzoyl chloride was added dropwise to the reaction solution while maintaining the internal temperature of the reaction solution at 15° C. or less.

[0389] The equivalent ratio of the chlorine atoms in benzoyl chloride to the mercapto groups in FSH (chlorine atoms / mercapto groups) is 1.03.

[0390] 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 less.

[0391] Then, 550 g of 10% sodium chloride aqueous solution was added to the reaction solution. Then, the mixed solution was separated and the organic phase was taken out. Next, the organic phase was washed with 500 mL of 1N dilute hydrochloric acid, and then washed with 500 mL of saturated sodium bicarbonate aqueous solution. Furthermore, it was washed with 500 mL of pure water.

[0392] The washing liquid was passed through activated alumina (300 mesh, for chromatography, basic) and 120 g of toluene was used to allow the reaction product remaining in the alumina to flow out.

[0393] Anhydrous sodium sulfate is added to the cleaning liquid after the liquid is passed and stirred to remove the residual water in the cleaning liquid. The sodium sulfate is filtered out with folded filter paper to obtain a toluene dilution of the product. Then, the dilution is concentrated with an evaporator. Thus, 5,7-bis(benzoylmercaptomethyl)-1,11-bis(benzoylmercapto)-3,6,9-trithiaundecane (Bz-FSH) is obtained as a reaction product.

[0394] Bz-FSH was a light yellow transparent liquid. The yield of Bz-FSH was 104.8 g. The viscosity (25° C.) of Bz-FSH was 8000 mPa·s. The refractive index (nD) of Bz-FSH was 1.65.

[0395] It should be noted that Bz-FSH is as follows 1 Identified by H-NMR (400 MHz, CDCl3).

[0396] 1 H-NMR (400MHz, CDCl3):

[0397] δ7.89-8.01 (m, 8H)

[0398] δ7.51-7.61 (m, 4H)

[0399] δ7.37-7.48 (m, 8H)

[0400] δ2.79-3.59 (m, 18H)

[0401] 2. Preparation of curing agent

[0402] Preparation Example 1 (isocyanate curing agent)

[0403] As the isocyanate curing agent, the following commercially available products were prepared.

[0404] D-110N: Trade name: TAKENATE D-110N, trimethylolpropane (TMP) adduct of xylylenediisocyanate, ethyl acetate solution, solid content concentration 75% by mass, isocyanate group content 11.5% by mass, manufactured by Mitsui Chemicals, Inc.

[0405] 3. Synthesis of main agent

[0406] Preparation Example 2 (Acrylic Polyol 1)

[0407] Acrylic polyol 1 was synthesized by the following method.

[0408] First, 120 parts by mass of polymerization solvent toluene and 40 parts by mass of ethyl acetate were added to a four-necked flask equipped with a stirrer, a thermometer, and a nitrogen inlet tube, and then the internal temperature of the flask was heated to 80±2° C. while blowing nitrogen into the flask.

[0409] On the other hand, the following components were added to a brown bottle and mixed to obtain a mixed solution.

[0410] Toluene 40 parts by mass

[0411] NMT-A (1-naphthylmethyl acrylate) 80.0 parts by mass

[0412] POB-A (meta-phenoxybenzyl acrylate) 110 parts by mass

[0413] HEA (2-hydroxyethyl acrylate) 10.0 parts by mass

[0414] PB-O (tert-butyl peroxy-2-ethylhexanoate) 2.0 parts by mass

[0415] The mixed solution was continuously added dropwise to the above flask over 5 hours. After the addition, the content of the flask was kept at 80±2°C for 1 hour.

[0416] Next, 0.4 parts by mass of PB-O was added to the flask twice every hour. In this way, the unreacted components (residual monomers) were treated. After the PB-O was added twice, the contents of the flask were further kept at 80±2° C. for 2 hours. In this way, acrylic polyol 1 was obtained.

[0417] Acrylic polyol 1 is a light yellow transparent liquid. The solid content (non-volatile content) concentration of acrylic polyol 1 is 49.8% by mass. The hydroxyl value (solid content basis) of acrylic polyol 1 is 22.3 mgKOH / g.

[0418] Preparation Example 3 (Acrylic Polyol 2)

[0419] The formulation of the mixed solution was changed as follows. Except for this, the same operation as in Preparation Example 2 was carried out to synthesize acrylic polyol 2.

[0420] Toluene 40 parts by mass

[0421] NMT-A (1-naphthylmethyl acrylate) 40.0 parts by mass

[0422] POB-A (meta-phenoxybenzyl acrylate) 150 parts by mass

[0423] HEA (2-hydroxyethyl acrylate) 10.0 parts by mass

[0424] PB-O (tert-butyl peroxy-2-ethylhexanoate) 2.0 parts by mass

[0425] Acrylic polyol 2 is a yellow transparent liquid. The solid content (non-volatile content) concentration of acrylic polyol 2 is 50.4% by mass. The hydroxyl value (solid content basis) of acrylic polyol 2 is 22.4 mgKOH / g.

[0426] Preparation Example 4 (Acrylic Polyol 3)

[0427] The formulation of the mixed solution was changed as follows. Except for this, the same operation as in Preparation Example 2 was carried out to synthesize acrylic polyol 3.

[0428] Toluene 40 parts by mass

[0429] POB-A (meta-phenoxybenzyl acrylate) 190.0 parts by mass

[0430] HEA (2-hydroxyethyl acrylate) 10.0 parts by mass

[0431] PB-O (tert-butyl peroxy-2-ethylhexanoate) 2.0 parts by mass

[0432] Acrylic polyol 3 is a yellow transparent liquid. The solid content (non-volatile content) concentration of acrylic polyol 3 is 51.0% by mass. The hydroxyl value (solid content basis) of acrylic polyol 3 is 22.4 mgKOH / g.

[0433] Preparation Example 5 (Acrylic Polyol 4)

[0434] As acrylic polyol 4, the following commercially available products were prepared.

[0435] SG-70L: trade name Teisan Resin SG-70L, carboxyl-containing acrylic polyol, solid content concentration 12.5% ​​by mass, viscosity 1600 mPa·s, acid value and hydroxyl value combined 5 mgKOH / g, manufactured by Nagase ChemteX Corporation

[0436] 4. Manufacture of polyurethane resin

[0437] Examples 7 to 20 and Comparative Examples 1 to 5

[0438] A main agent (curing main agent), a curing agent, and a plasticizer were prepared according to the formulations described in Tables 1 and 2. The combination of these was used as a curable composition. In addition, for comparison, dioctyl phthalate (DOP) was prepared as a plasticizer.

[0439] Then, the main agent and the curing agent were mixed so that the equivalent ratio became the value described in Table 1 and Table 2. When the main agent was acrylic polyol 1 to 3, the equivalent ratio indicated the ratio of the hydroxyl group in the main agent to the isocyanate group in the curing agent (OH / NCO).

[0440] When the main agent is acrylic polyol 4 (carboxyl group-containing acrylic polyol), the equivalent ratio indicates the ratio of the total amount of hydroxyl groups and carboxyl groups in the main agent to the isocyanate groups in the curing agent (OH+COOH / NCO).

[0441] Next, a plasticizer is added to the mixture of the main agent and the curing agent, and they are mixed. It should be noted that the amount of the plasticizer added is adjusted according to the records in Table 1 and Table 2. It should be noted that in Table 1 and Table 2, the mixing ratio (phr) of the plasticizer represents the mass part of the plasticizer relative to 100 mass parts of the total solid content of the mixture of the main agent and the curing agent.

[0442] In the above manner, a mixed solution containing a main agent, a curing agent, and a plasticizer is obtained. Next, the mixed solution is applied to the surface of a polypropylene (PP) substrate. It should be noted that the coating amount is adjusted in such a way that the thickness of the coating film becomes 200 μm. Then, the coating film is heated at 60° C. for 2 hours and then aged at 25° C. for 7 days. Thus, the coating film is cured to obtain a cured product. Then, the cured product is peeled off from the PP substrate.

[0443] 5. Evaluation

[0444] (1) Refractive index (nD)

[0445] The refractive index (nD) of the cured product was measured using an Abbe refractometer (DR-M4, manufactured by ATAGO Corporation). The temperature was room temperature (20° C.) and the light was d-line (wavelength 587.6 nm).

[0446] (2) Softness; tensile storage elastic modulus (E')

[0447] The solid viscoelasticity of the cured product was measured under the following conditions. Then, the tensile storage elastic modulus (E') at 25°C was determined.

[0448] Device: RSA-G2 (manufactured by TA Instruments)

[0449] Deformation mode: Stretch mode

[0450] Temperature range: -50℃~270℃

[0451] Heating temperature: 3℃ / min

[0452] Frequency: 1Hz

[0453] Environment: N2 environment

[0454] (3) Glass transition temperature (Tg)

[0455] The solid viscoelasticity of the cured product is measured under the conditions of (2) above. Then, tanδ (loss tangent, E” / E’) is calculated based on the tensile storage elastic modulus (E’) and the tensile loss elastic modulus (E”). Then, as the glass transition temperature, the temperature at which the loss tangent (tanδ) shows a maximum value (peak value) is calculated.

[0456] 6. Additives and their evaluation

[0457] Examples 21 to 38

[0458] Additives were added to the curable compositions of Examples 7 and 10, and the weather resistance of the cured products was confirmed.

[0459] More specifically, a main agent, a curing agent, a plasticizer, and additives were prepared according to the formulations described in Tables 3 and 4. The combination of these was used as a curable composition. Then, the main agent and the curing agent were mixed so that the equivalent ratio became the value described in Table 3.

[0460] Next, add plasticizer and additive to the mixture of main agent and curing agent, and mix them. It should be noted that in Table 3, the mixing ratio (phr) of plasticizer represents the mass part of plasticizer relative to 100 mass parts of the total solid content of the mixture of main agent and curing agent. In addition, in Tables 3 to 4, the mixing ratio (ppm) of additive represents the mass ratio (ppm) of additive relative to the total solid content of main agent, curing agent, plasticizer and additive (resin solid content (i.e., the total amount of curable composition and the total amount of cured product)). It should be noted that in Example 31, no additive is added.

[0461] In addition, the types of additives are as follows.

[0462] LA-24: Trade name ADK STAB LA-24, benzotriazole-based UV absorber, 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, manufactured by ADEKA

[0463] LA-29: Trade name ADK STAB LA-29, benzotriazole-based UV absorber, 2-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, manufactured by ADEKA

[0464] LA-32: Trade name ADK STAB LA-32, benzotriazole-based UV absorber, 2-(2H-benzotriazole-2-yl)-p-cresol, manufactured by ADEKA

[0465] 1413: Trade name ADK STAB 1413, benzophenone-based UV absorber, [2-hydroxy-4-(octyloxy)phenyl](phenyl)methanone, manufactured by ADEKA

[0466] PR-25: Trade name Hostavin PR-25, benzylidene UV absorber, dimethyl 2-(4-methoxybenzylidene)malonate, manufactured by CLARIANT

[0467] LA-46: Trade name ADK STAB LA-46, triazine-based UV absorber, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, manufactured by ADEKA

[0468] LA-72: Trade name ADK STAB LA-72, HALS light stabilizer, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, manufactured by ADEKA

[0469] AO-60: Trade name ADK STAB AO-60, phenolic antioxidant, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], manufactured by ADEKA

[0470] In the above manner, a mixed solution containing a main agent and a curing agent, and a plasticizer and an additive is obtained. Next, the above-mentioned mixed solution is applied to the surface of a glass substrate (D263T-eco, manufactured by SCHOTT, 0.21 mm thickness, 50 mm×50 mm). It should be noted that the coating amount is adjusted in such a way that the thickness of the coating film becomes 50 μm. Then, the coating film is heated at 60°C for 2 hours and then matured at 25°C for 7 days. Thus, the coating film is cured to obtain a cured product. As a result, a laminate comprising a glass substrate and a resin cured film (hereinafter referred to as a glass substrate / cured film laminate) is obtained.

[0471] The YI value and b value of each glass substrate / cured film laminate were measured using COH-7700 (manufactured by Nippon Denshoku Industries, spectral color haze meter). ＊ (Yellowing degree, before weather resistance test) The results are shown in Tables 3 and 4.

[0472] Then, each glass substrate / cured film laminate was subjected to a weather resistance test. More specifically, the glass substrate / cured film laminate was irradiated with ultraviolet rays under the following conditions.

[0473] Light source: Xenon lamp

[0474] Black panel temperature: 55℃

[0475] Humidity: 55%

[0476] Rainfall conditions: None

[0477] Irradiation conditions: 36.5W / m 2 (300-400nm)

[0478] Color filter: Inner / Outer = Right Light / Cica-Quarz

[0479] Irradiated side: Cured film side

[0480] Irradiation time: 100 hours

[0481] Then, the YI value and b value of each glass substrate / cured film laminate were measured using COH-7700 (manufactured by Nippon Denshoku Industries, spectral color haze meter). ＊ (Yellowing degree, after weather resistance test) The results are shown in Tables 3 and 4.

[0482] 7. Manufacture and evaluation of cured acrylic resin

[0483] Preparation Example 6 (Acrylic Acid Complex 1)

[0484] The following components were added to a brown bottle and mixed. Thus, acrylic compound 1 (curable compound, acrylic resin raw material 1) was obtained.

[0485] TMP-A (trimethylpropane triacrylate) 40.0 parts by mass

[0486] 2EHA (2-ethylhexyl acrylate) 60.0 parts by mass

[0487] Omnirad184 (alkyl phenone-based photopolymerization initiator, 1-hydroxycyclohexyl phenyl ketone) 3.0 parts by mass

[0488] Preparation Example 7 (Acrylic Acid Complex 2)

[0489] The following components were added to a brown bottle and mixed. Thus, acrylic compound 2 (curable compound, acrylic resin raw material 2) was obtained.

[0490] TMP-A (trimethylpropane triacrylate) 40.0 parts by mass

[0491] POB-A (meta-phenoxybenzyl acrylate) 60.0 parts by mass

[0492] Omnirad184 (alkyl phenone-based photopolymerization initiator, 1-hydroxycyclohexyl phenyl ketone) 3.0 parts by mass

[0493] Examples 39 to 46 and Comparative Examples 6 to 7

[0494] The plasticizer and the curable compound were blended according to the formulation described in Table 5 to obtain a curable composition (polymerizable composition).

[0495] Next, the coating film of the polymerizable composition was sandwiched between release PET films (polyethylene terephthalate film, Purex A3100, manufactured by Toyobo) in a mold box composed of 200 μm thick silicon wafers. At this time, the release surface of the release PET film was brought into contact with the polymerizable composition. Thus, a laminate 1 (release PET film / polymerizable composition / release PET film) was obtained.

[0496] Next, the laminate 1 (mold release PET film / polymerizable composition / mold release PET film) was sandwiched between glass substrates (D263T-eco, manufactured by SCHOTT) and fixed with a clamp. That is, the coating film of the polymerizable composition was sandwiched between the glass substrates and the mold release PET films to obtain a laminate 2 (glass substrate / mold release PET film / polymerizable composition / mold release PET film / glass substrate).

[0497] Then, the polymerizable composition of the laminate 2 was irradiated with active energy rays (wavelength 365 nm, illuminance 400 mW / cm 2 , cumulative light intensity 6000mJ / cm 2 ). The laminate 2 was then heated at 120°C for 30 minutes in a nitrogen atmosphere. As a result, the polymerizable composition was radically polymerized by active energy rays and heat to obtain a laminate 3 (glass substrate / mold release PET film / cured product / mold release PET film / glass substrate) containing a cured product.

[0498] Then, the fixture and the glass substrate were removed, and the cured product was peeled off from the demoulding PET film. As a result, a cured product was obtained. The refractive index (nD), tensile storage elastic modulus (E') and glass transition temperature (Tg) of the cured product were measured by the above method. The results are shown in Table 5.

[0499] Separately from the above, the polymerizable composition was sandwiched between glass substrates (Eagle-XG, manufactured by CORNIG) in a mold box composed of 50 μm thick silicon wafers. Thus, a laminate 4 (glass substrate / polymerizable composition / glass substrate) was obtained.

[0500] Then, the polymerizable composition of the laminate 4 was irradiated with active energy rays (wavelength 365 nm, illuminance 400 mW / cm 2 , cumulative light intensity 6000mJ / cm 2 ). Furthermore, the laminate 4 was heated at 120° C. for 30 minutes in a nitrogen atmosphere. As a result, the polymerizable composition was radically polymerized by active energy rays and heat, and a laminate 5 including a cured product was obtained (glass substrate / cured product / glass substrate).

[0501] Then, the jig was removed. Then, the YI value and b value of the weather resistance of the laminate 5 (glass substrate / cured product / glass substrate) were measured by the same method as above. ＊ (yellowing degree, before weathering test). Then, the laminate 5 (glass substrate / cured product / glass substrate) was subjected to weathering test in the same manner as above. Then, the YI value and b value of the laminate 5 (glass substrate / cured product / glass substrate) were measured in the same manner as above. ＊ The results are shown in Table 5.

[0502] [Table 1]

[0503]

[0504] [Table 2]

[0505]

[0506] [Table 3]

[0507]

[0508] [Table 4]

[0509]

[0510] [Table 5]

[0511]

[0512] It should be noted that the above invention is provided as an exemplary embodiment of the present invention, but it is only an example and is not to be construed as limiting. Modifications of the present invention that are obvious to those skilled in the art are included in the appended claims.

[0513] Industrial Applicability

[0514] The compound, additive, plasticizer, curable composition, adhesive, cured product and adhesive of the present invention can be suitably used in the fields of coatings, paints, adhesives, films and adhesives.

Claims

1. A compound represented by the following general formula (1): General formula (1): [Chemical formula 1] Chemical formula 1 A-(SXR) n (1) In formula (1), A represents an n-valent organic group containing a sulfur atom; n represents an integer greater than 3; S represents a sulfur atom; X represents a single bond or a carbonyl group; X may be the same as or different from each other; R represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an aromatic aliphatic hydrocarbon group; R may be the same as or different from each other.

2. The compound according to claim 1, wherein A represents an organic group containing a sulfur atom and a typical element atom (excluding a sulfur atom and a hydrogen atom), 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 greater than 20%.

3. The compound according to claim 1, which is represented by the following general formula (2) or the following general formula (3), General formula (2): [Chemical formula 2] Chemical formula 2 In formula (2), S, X and R have the same meanings as S, X and R in formula (1); in formula (2), the portion surrounded by the dotted line represents the organic group A (n=3) of formula (1), General formula (3): [Chemical formula 3] Chemical formula 3 In formula (3), S, X and R have the same meanings as S, X and R in formula (1); in formula (3), the portion surrounded by a dotted line represents an organic group A (n=4) in formula (1).

4. The compound according to claim 1, wherein R represents a methyl group, a phenyl group or a benzyl group.

5. The compound according to claim 1, wherein X represents a carbonyl group, and R represents an aromatic aliphatic hydrocarbon group.

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

7. A plasticizer comprising the compound according to claim 1. 8 . A curable composition comprising a curable compound and the plasticizer according to claim 7 .

9. The curable composition according to claim 8, further comprising at least one additive selected from the group consisting of an ultraviolet absorber, a light stabilizer and an antioxidant, The ratio of the additive to 1 part by mass of the total amount of the curable composition is 10×10 -6 Mass parts or more 10000×10 -6 Less than 10 parts by mass.

10. An adhesive comprising the curable composition according to claim 8.

11. A cured product comprising a curing resin and the plasticizer according to claim 7.

12. The cured product according to claim 11, which has a refractive index of 1.60 or more, and The tensile storage elastic modulus is 100 MPa or less.

13. The cured product according to claim 11, further comprising at least one additive selected from the group consisting of an ultraviolet absorber, a light stabilizer and an antioxidant, The ratio of the additive to the total amount of the cured product is 10×10 -6 Mass parts or more 10000×10 -6 Less than 10 parts by mass.

14. The cured product according to claim 11, wherein The curable resin comprises a reaction product of a main agent containing acrylic polyol and a curing agent containing polyisocyanate.

15. The cured product according to claim 11, wherein The curable resin includes a curable acrylic resin.

16. An adhesive comprising the cured product according to claim 11.

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