Pressure-sensitive adhesive, pressure-sensitive adhesive composition, method for producing compound, and compound

Abstract

This pressure-sensitive adhesive has a structural unit derived from a compound represented by formula (1). In formula (1), R1 represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or an araliphatic hydrocarbon group, the R2 moieties are the same as or different from each other and each represent a hydrogen atom or a methyl group, R3 represents a hydrogen atom or a methyl group, and n indicates an integer of 1 or larger. When n is 1, X represents a sulfur atom and Y represents a sulfur atom. When n is an integer of 2 or larger, X represents a sulfur atom or an oxygen atom and Y represents a sulfur atom or an oxygen atom, at least one of the Y moieties representing a sulfur atom.

Description

Pressure-sensitive adhesive, pressure-sensitive adhesive composition, method for producing compound, and compound

[0001] The present invention relates to a pressure-sensitive adhesive, a pressure-sensitive adhesive composition, a method for producing a compound, and a compound.

[0002] (Meth)acrylic resins are used as pressure-sensitive adhesives and are formed, for example, by radical polymerization of a monomer containing a (meth)acryloyloxy group.

[0003] Examples of the monomer containing a (meth)acryloyloxy group include 1-acryloyloxy-5-phenyl-3-thiapentane [chemical formula: CH ２ =CHCOO-CH ２ CH ２ -S-CH ２ CH ２ -Ph (Ph represents a phenyl group)] has been proposed (see, for example, Patent Document 1 (Chemical Formula 4)).

[0004] International Publication No. 2023 / 080599

[0005] On the other hand, in the field of adhesives, there is a demand for adhesives having higher refractive indexes and flexibility, and compounds for obtaining such adhesives.

[0006] The present invention relates to a pressure-sensitive adhesive having a relatively excellent refractive index and flexibility, a pressure-sensitive adhesive composition containing the pressure-sensitive adhesive, a method for producing a compound for obtaining the pressure-sensitive adhesive, and the compound.

[0007] The present invention [1] includes a pressure-sensitive adhesive having a structural unit derived from a compound represented by the following formula (1):

[0008]

[0009] (In formula (1), R １ represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or an araliphatic hydrocarbon group. ２ are the same or different and represent a hydrogen atom or a methyl group. ３represents a hydrogen atom or a methyl group. n represents an integer of 1 or more. When n represents 1, X represents a sulfur atom and Y represents a sulfur atom. When n represents an integer of 2 or more, X represents a sulfur atom or an oxygen atom and Y represents a sulfur atom or an oxygen atom, with at least one Y representing a sulfur atom.

[0010] The present invention [2] is a compound represented by the formula (1), wherein R １ represents an aromatic hydrocarbon group or an aromatic aliphatic hydrocarbon group.

[0011] The present invention [3] is a compound represented by the formula (1), wherein R １ represents a 2-phenylethyl group.

[0012] The present invention [4] comprises the pressure-sensitive adhesive according to any one of the above [1] to [3], wherein in formula (1), n ​​represents an integer of 2 or more, and X represents a sulfur atom.

[0013] The present invention [5] includes the pressure-sensitive adhesive according to any one of the above [1] to [4], wherein, in formula (1), n ​​represents an integer of 2 or more, and all Ys represent sulfur atoms.

[0014] The present invention [6] further comprises the pressure-sensitive adhesive according to any one of the above [1] to [5], which further comprises a structural unit derived from a hydroxyl group-containing mono(meth)acrylate.

[0015] The present invention [7] includes the pressure-sensitive adhesive according to any one of the above [1] to [6], which is an optical pressure-sensitive adhesive.

[0016] The present invention [8] is a pressure-sensitive adhesive composition containing the pressure-sensitive adhesive according to any one of the above [1] to [7] and an additive, wherein the additive comprises at least one selected from the group consisting of an ultraviolet absorber, a light resistance stabilizer, and an antioxidant, and the ratio of the additive is 10×10 relative to 1 part by mass of the total amount of the pressure-sensitive adhesive composition. －６ Mass part or more 100000×10 －６ The adhesive composition contains less than or equal to parts by mass.

[0017] The present invention [9] includes a method for producing a compound represented by the following formula (1), comprising: a preparation step of preparing a thiol and / or alcohol represented by the following formula (2); and a (meth)acryloyl group-forming step of modifying a mercapto group of the thiol to a (meth)acryloylthio group and / or modifying a hydroxyl group of the alcohol to a (meth)acryloyloxy group.

[0018]

[0019] (In formula (1), R １ represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or an araliphatic hydrocarbon group. ２ are the same or different and represent a hydrogen atom or a methyl group. ３ represents a hydrogen atom or a methyl group. n represents an integer of 1 or more. When n represents 1, X represents a sulfur atom and Y represents a sulfur atom. When n represents an integer of 2 or more, X represents a sulfur atom or an oxygen atom and Y represents a sulfur atom or an oxygen atom, with at least one Y representing a sulfur atom.

[0020] (In formula (2), R １ , R ２ , n, Y and X are defined as R １ , R ２ , n, Y and X have the same meanings as those of the formula (I).

[0021] The present invention

[10] includes the method for producing the compound according to the above [9], wherein the preparation step comprises a thioalkylene group introduction step of introducing a thioalkylene group into the thiol, and the thioalkylene group introduction step comprises an oxyalkylene group introduction step of introducing an oxyalkylene group into the thiol to obtain an oxyalkylene-introduced alcohol, and a mercapto group formation step of converting a hydroxyl group of the oxyalkylene-introduced alcohol to a mercapto group to obtain a thioalkylene-introduced thiol.

[0022] The present invention

[11] includes a compound represented by the following formula (1'): (In formula (1'), n represents an integer of 1 or more.)

[0023] The pressure-sensitive adhesive of the present invention has a structural unit derived from the compound represented by the above formula (1), and therefore has a relatively excellent refractive index and flexibility.

[0024] The pressure-sensitive adhesive composition of the present invention contains the above-mentioned pressure-sensitive adhesive, and therefore has relatively excellent refractive index and flexibility.

[0025] According to the method for producing a compound of the present invention, a compound for obtaining a pressure-sensitive adhesive having an excellent refractive index and flexibility can be efficiently obtained.

[0026] Since the compound of the present invention is represented by the above formula (1'), it is possible to produce a pressure sensitive adhesive having a relatively excellent refractive index and flexibility.

[0027] 1. Pressure-sensitive adhesives Pressure-sensitive adhesives are cured resins that have adhesive properties (pressure-sensitive adhesion, tackiness). More specifically, pressure-sensitive adhesives have a relatively low glass transition temperature.

[0028] The upper limit of the glass transition temperature of the pressure-sensitive adhesive is, for example, 20°C or lower, preferably 0°C or lower, and more preferably -3°C or lower. The lower limit of the glass transition temperature of the pressure-sensitive adhesive is not particularly limited, but is, for example, -50°C or higher. That is, the glass transition temperature of the pressure-sensitive adhesive is, for example, -50°C or higher and 20°C or lower, preferably -50°C or higher and 0°C or lower, and more preferably -50°C or higher and -3°C or lower. The glass transition temperature is measured in accordance with the examples described below.

[0029] More specifically, the pressure-sensitive adhesive includes a (meth)acrylic pressure-sensitive adhesive, where (meth)acrylic refers to acrylic and / or methacrylic.

[0030] The (meth)acrylic pressure-sensitive adhesive can be obtained, for example, by radical polymerization of a polymerizable monomer containing a (meth)acryloyl group. Examples of the (meth)acryloyl group include a (meth)acryloyloxy group and a (meth)acryloylthio group.

[0031] In other words, the PSA is obtained by radical polymerization of a polymerizable monomer containing a (meth)acryloyloxy group and / or a (meth)acryloylthio group. The PSA obtained by the radical polymerization has structural units derived from the polymerizable monomer.

[0032] Here, (meth)acryloyl refers to acryloyl and / or methacryloyl, (meth)acryloyloxy refers to acryloyloxy and / or methacryloyloxy, and (meth)acryloylthio refers to acryloylthio and / or methacryloylthio.

[0033] In the present invention, the pressure-sensitive adhesive is a (meth)acrylic pressure-sensitive adhesive and has a structural unit derived from a compound represented by the following formula (1): In other words, the pressure-sensitive adhesive is obtained by using the compound represented by the following formula (1) as a polymerizable monomer, as will be described in detail later.

[0034]

[0035] (In formula (1), R １ represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or an araliphatic hydrocarbon group. ２ are the same or different and represent a hydrogen atom or a methyl group. ３ represents a hydrogen atom or a methyl group. n represents an integer of 1 or more. When n represents 1, X represents a sulfur atom and Y represents a sulfur atom. When n represents an integer of 2 or more, X represents a sulfur atom or an oxygen atom and Y represents a sulfur atom or an oxygen atom, with at least one Y representing a sulfur atom.

[0036] The compound represented by the formula (1) is a polymerizable monomer containing a (meth)acryloyl group. More specifically, when Y in the formula (1) represents an oxygen atom, the compound represented by the formula (1) is a polymerizable monomer containing a (meth)acryloylthio group. Furthermore, when X in the formula (1) represents an oxygen atom, the compound represented by the formula (1) is a polymerizable monomer containing a (meth)acryloyloxy group.

[0037] The compound represented by the formula (1) and the method for producing a pressure-sensitive adhesive using the compound will be described in detail below.

[0038] 2. Compound <R １ In the above formula (1), R １ represents a hydrocarbon group. More specifically, R １ represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or an araliphatic hydrocarbon group.

[0039] Examples of the aliphatic hydrocarbon group include aliphatic hydrocarbon groups having 1 to 20 carbon atoms. More specific examples of the aliphatic hydrocarbon group include linear aliphatic hydrocarbon groups having 1 to 20 carbon atoms and cyclic aliphatic hydrocarbon groups having 3 to 20 carbon atoms.

[0040] Examples of the linear aliphatic hydrocarbon group having 1 to 20 carbon atoms include a linear saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms and a linear unsaturated aliphatic hydrocarbon group having 1 to 20 carbon atoms. Examples of the linear saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a 2-butyl group, a 1-pentyl group, a 2-pentyl group, a 3-pentyl group, a 2-methyl-1-butyl group, an isopentyl group, a tert-pentyl group, a 3-methyl-2-butyl group, a neopentyl group, an n-hexyl group, a 4-methyl-2-butyl group, a 5-methyl-1-butyl group, a 6-methyl-2-butyl group, a 7-methyl-2-butyl group, a 8-methyl-2-butyl group, a 9-methyl-2-butyl group, a 10-methyl-2-butyl group, a 20-methyl-2-butyl group, a 21-methyl-2-butyl group, a 22-methyl-2-butyl group, a 23-methyl-2-butyl group, a 24-methyl-2-butyl group, a 25-methyl-2-butyl group, a 26-methyl-2-butyl group, a 27-methyl-2-butyl group, a 28-methyl-2-butyl group, a 29-methyl-2-butyl group, a 30-methyl-2-butyl group, a 31-methyl-2-butyl group, a 32-methyl-2-butyl group, a 33-methyl-2-butyl group, a 34-methyl-2-butyl group, a 35-methyl-2-butyl group, a 36-methyl-2-butyl group, a 37-methyl-2-butyl group, a 38-methyl-2-butyl Examples of the linear unsaturated aliphatic hydrocarbon group having 1 to 20 carbon atoms include vinyl and 2-propenyl groups. These may be used alone or in combination of two or more.

[0041] Examples of cyclic aliphatic hydrocarbon groups having 3 to 20 carbon atoms include saturated cyclic aliphatic hydrocarbon groups having 3 to 20 carbon atoms and unsaturated cyclic aliphatic hydrocarbon groups having 3 to 20 carbon atoms. Examples of saturated cyclic aliphatic hydrocarbon groups having 3 to 20 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl groups. Examples of unsaturated cyclic aliphatic hydrocarbon groups having 3 to 20 carbon atoms include cyclopentenyl and cyclohexenyl groups. These can be used alone or in combination of two or more types.

[0042] Examples of aromatic hydrocarbon groups include aromatic hydrocarbon groups having 6 to 20 carbon atoms. Examples of aromatic hydrocarbon groups having 6 to 20 carbon atoms include phenyl (Ph), 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl, 2,3,4-trimethylphenyl, 3,4,5-trimethylphenyl, 2,4,6-trimethylphenyl, 2,3,4,5-tetramethylphenyl, 2,3,4,6-tetramethylphenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 1-naphthyl, and 2-naphthyl groups. These groups can be used alone or in combination of two or more.

[0043] 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 a benzyl group (Ph-CH ２ -), 1-phenylethyl group, 2-phenylethyl group (also known as phenethyl group, Ph-CH ２ CH ２-), 1-phenylpropyl, 2-phenylpropyl, 3-phenylpropyl, o-methylbenzyl, m-methylbenzyl, p-methylbenzyl, o-ethylbenzyl, m-ethylbenzyl, p-ethylbenzyl, o-isopropylbenzyl, m-isopropylbenzyl, p-isopropylbenzyl, 2,3,4-trimethylbenzyl, 3,4,5-trimethylbenzyl, and 2,4,6-trimethylbenzyl. These can be used alone or in combination of two or more.

[0044] R １ In the above, the aliphatic hydrocarbon group, aromatic hydrocarbon group, and araliphatic hydrocarbon group may have a substituent. Examples of the substituent include a halogeno group, a cyano group, an amino group, a carboxy group, a sulfonyl group, and an alkoxy group. These may be used alone or in combination of two or more. The number of substituents is appropriately determined depending on the purpose and application. The substitution position is appropriately determined depending on the purpose and application.

[0045] From the viewpoint of refractive index and weather resistance, in formula (1), R １ preferably represents an aromatic hydrocarbon group or an aromatic aliphatic hydrocarbon group, and more preferably represents an aromatic aliphatic hydrocarbon group.

[0046] In particular, from the viewpoint of refractive index, the aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, and even more preferably a phenyl group (Ph-).

[0047] From the viewpoint of weather resistance, the aromatic aliphatic hydrocarbon group is preferably an aromatic aliphatic hydrocarbon group having 7 to 15 carbon atoms, more preferably an aromatic aliphatic hydrocarbon group having 7 to 10 carbon atoms, and even more preferably a benzyl group (Ph-CH ２ -) and 2-phenylethyl group (Ph-CH ２ CH ２ -), and particularly preferably a 2-phenylethyl group (Ph-CH ２ CH ２ -) are listed.

[0048] In other words, in particular, from the viewpoint of refractive index and weather resistance, in formula (1), R １ is more preferably a phenyl group (Ph-), a benzyl group (Ph-CH ２ -), or a 2-phenylethyl group (Ph-CH ２ CH ２ -), and particularly preferably a 2-phenylethyl group (Ph-CH ２ CH ２ -) is indicated.

[0049] <Structural unit [YCHR ２ CHR ２ The compound represented by the above formula (1) is a compound having a structural unit [YCHR ２ CHR ２ In the above formula (1), the structural unit [YCHR ２ CHR ２ The number of repetitions of ] is indicated by n.

[0050] <n> n represents an integer of 1 or more. That is, n can represent 1 or an integer of 2 or more. More specifically, n represents, for example, 1 to 50, preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 2.

[0051] From the viewpoint of availability, n preferably represents 1. When n represents 1, the compound represented by the above formula (1) has a single (one) structural unit [YCHR ２ CHR ２ ].

[0052] From the viewpoint of refractive index, n preferably represents an integer of 2 or more. When n represents an integer of 2 or more, the compound represented by the above formula (1) has a plurality (two or more) of structural units [YCHR ２ CHR ２ ]. It has a plurality (two or more) of structural units [YCHR ２ CHR ２ ] may be the same as or different from each other. Preferably, all of the structural units [YCHR ２ CHR ２ ] are identical to each other.

[0053] <R ２In the above formula (1), R ２ are the same or different and represent a hydrogen atom or a methyl group.

[0054] In other words, the structural unit [YCHR ２ CHR ２ ], for example, [YCH ２ CH ２ ], [YCH (CH ３ ) CH ２ ], [YCH ２ CH (CH ３ ) )] and [YCH(CH ３ ) CH(CH ３ These can be used alone or in combination of two or more.

[0055] In terms of refractive index, preferably, all R ２ represents a hydrogen atom. ２ CHR ２ ] is preferably [YCH ２ CH ２ ] are examples.

[0056] <Y> In the above formula (1), Y represents a sulfur atom or an oxygen atom. That is, the structural unit [YCHR ２ CHR ２ ] is a thioalkylene group [SCHR ２ CHR ２ ] or an oxyalkylene group [OCHR ２ CHR ２ ] is shown.

[0057] Y is a structural unit [YCHR ２ CHR ２ ] is selected according to the number of repetitions n.

[0058] When n is 1, Y is a sulfur atom. That is, when n is 1, the compound represented by the above formula (1) is a thioalkylene group [SCHR ２ CHR ２ ]. ２ CHR ２ ], for example, [SCH ２ CH ２ ], [SCH (CH３ ) CH ２ ], [SCH ２ CH (CH ３ ) )] and [SCH(CH ３ ) CH(CH ３ These may be used alone or in combination of two or more. ２ CHR ２ ] is preferably [SCH ２ CH ２ ] (i.e., a thioethylene group).

[0059] When n is 1, the compound represented by the formula (1) is an oxyalkylene group [OCHR ２ CHR ２ ] is not included.

[0060] When n is an integer of 2 or more, Y represents a sulfur atom or an oxygen atom, and at least one Y represents a sulfur atom. That is, when n is an integer of 2 or more, the compound represented by the above formula (1) contains at least one thioalkylene group [SCHR ２ CHR ２ ].

[0061] In addition, when n is an integer of 2 or more, as long as at least one Y is a sulfur atom, the other Ys can be oxygen atoms. In other words, when n is an integer of 2 or more, the compound represented by the above formula (1) can optionally contain an oxyalkylene group [OCHR ２ CHR ２ The oxyalkylene group may have, for example, [OCH ２ CH ２ ], [OCH(CH ３ ) CH ２ ], [OCH ２ CH (CH ３ ) )] and [OCH(CH ３ ) CH(CH ３ These may be used alone or in combination of two or more. ２ CHR ２ ] is preferably [OCH ２ CH ２] (that is, an oxyethylene group).

[0062] When n is an integer of 2 or more, preferably, all Y's represent sulfur atoms from the viewpoint of refractive index. That is, when n is an integer of 2 or more, preferably, all Y's represent sulfur atoms from the viewpoint of refractive index. ２ CHR ２ ] is a thioalkylene group [SCHR ２ CHR ２ ] is shown.

[0063] <X> In the above formula (1), X represents a sulfur atom or an oxygen atom. X represents a structural unit [YCHR ２ CHR ２ ] is selected according to the number of repetitions n.

[0064] When n is 1, X is a sulfur atom. That is, when n is 1, the compound represented by the above formula (1) has a (meth)acryloylthio group (CH ２ = C(R ３ ) COS-).

[0065] When n is an integer of 2 or more, X is a sulfur atom or an oxygen atom. That is, when n is an integer of 2 or more, the compound represented by the above formula (1) has a (meth)acryloylthio group (CH ２ = C(R ３ ) COS-) or (meth)acryloyloxy group (CH ２ = C(R ３ )COO-).

[0066] When n is an integer of 2 or more, from the viewpoint of refractive index, X preferably represents a sulfur atom. That is, when n is an integer of 2 or more, the compound represented by the above formula (1) preferably has a (meth)acryloylthio group.

[0067] <R ３ In the above formula (1), R ３ represents a hydrogen atom or a methyl group.

[0068] R ３represents a hydrogen atom, the compound represented by the above formula (1) has an acryloyl group, more specifically, an acryloylthio group (CH ２ ═CHCOS—), or an acryloyloxy group (CH ２ In this case, the compound represented by the formula (1) has a methacryloylthio group (CH ２ =C(CH ３ ) COS-), and methacryloyloxy group (CH ２ =C(CH ３ )COO-) is not present.

[0069] R ３ When represents a methyl group, the compound represented by the above formula (1) has a methacryloyl group, more specifically, a methacryloylthio group (CH ２ =C(CH ３ ) COS-), or a methacryloyloxy group (CH ２ =C(CH ３ In this case, the compound represented by the formula (1) has an acryloylthio group (CH ２ ═CHCOS—), and an acryloyloxy group (CH ２ =CHCOO-).

[0070] R ３ represents a hydrogen atom from the viewpoint of adhesiveness and flexibility (i.e., a reduction in the glass transition temperature). That is, the compound represented by the above formula (1) preferably has an acryloylthio group (CH ２ ═CHCOS—), or an acryloyloxy group (CH ２ =CHCOO-).

[0071] <Specific Examples of the Compound Represented by the Above Formula (1)> Specific examples of the compound represented by the above formula (1) will be described in detail.

[0072] In the above formula (1), n ​​preferably represents an integer of 1 or greater than 2. When n represents 1 in the above formula (1), the compound is represented, for example, by the following formula (1-1).

[0073]

[0074] (In formula (1-1), R １ , R ２ , R ３ The meanings of X and Y are R in formula (1). １ , R ２ , R ３ , X and Y have the same meanings as above.)

[0075] In formula (1-1), X preferably represents a sulfur atom, that is, the above compound preferably has a (meth)acryloylthio group.

[0076] In the above formula (1-1), R ３ represents a hydrogen atom. That is, the above compound more preferably has an acryloylthio group.

[0077] In such a case, the compound is represented by, for example, the following formula (1-1-1).

[0078]

[0079] (In formula (1-1-1), R １ , R ２ and Y are defined as R in formula (1). １ , R ２ and Y have the same meanings as those of the respective groups.)

[0080] In formula (1-1-1), Y preferably represents a sulfur atom, that is, the above compound preferably has a thioalkylene group.

[0081] In such a case, the compound is represented by, for example, the following formula (1-1-1-1).

[0082]

[0083] (In formula (1-1-1-1), R １ and R ２ The meaning of is R in formula (1). １ and R ２ The meanings are the same as those of

[0084] In the above formula (1-1-1-1), preferably, R １ represents a 2-ethylphenyl group, and all R２ indicates a hydrogen atom.

[0085] In such a case, the compound is represented by, for example, the following formula (1-1-1-1-1): The compound represented by the following formula (1-1-1-1-1) is 1-acryloylthio-5-phenyl-3-thiapentane (PE-DMEA).

[0086]

[0087] Furthermore, for example, the compound represented by the above formula (1-1-1-1-1) may have a methacryloylthio group instead of an acryloylthio group, such as 1-methacryloylthio-5-phenyl-3-thiapentane (PE-DMEMA).

[0088] In addition, in the above formula (1-1-1-1), preferably, R １ is a benzyl group (PhCH ２ -), and all R ２ indicates a hydrogen atom.

[0089] In such a case, the compound is represented by, for example, the following formula (1-1-1-1-2): The compound represented by the following formula (1-1-1-1-2) is 1-acryloylthio-2-benzylthioethane.

[0090]

[0091] In addition, in the above formula (1-1-1-1), R １ represents a phenyl group (Ph), and all R ２ indicates a hydrogen atom.

[0092] In such a case, the compound is represented by, for example, the following formula (1-1-1-1-3): The compound represented by the following formula (1-1-1-1-3) is 1-acryloylthio-2-phenylthioethane.

[0093]

[0094] In the above formula (1), when n is an integer of 2 or more, n is preferably 2. In such a case, the above compound is represented, for example, by the following formula (1-2).

[0095]

[0096] (In formula (1-2), R １ , R ２ , R ３ The meanings of X and Y are R in formula (1). １ , R ２ , R ３ , X and Y have the same meanings as above.)

[0097] In formula (1-2), X preferably represents a sulfur atom, that is, the above compound preferably has a (meth)acryloylthio group.

[0098] In the above formula (1-2), R ３ represents a hydrogen atom. That is, the above compound more preferably has an acryloylthio group.

[0099] In such a case, the compound is represented by, for example, the following formula (1-2-1).

[0100]

[0101] (In formula (1-2-1), R １ , R ２ and Y are defined as R in formula (1). １ , R ２ and Y have the same meanings as those of the respective groups.)

[0102] In the above formula (1-2-1), Y represents a sulfur atom or an oxygen atom, and at least one Y represents a sulfur atom. Preferably, all Y represent sulfur atoms. That is, the above compound preferably has a thioalkylene group.

[0103] In such a case, the compound is represented by, for example, the following formula (1-2-1-1).

[0104]

[0105] (In formula (1-2-1-1), R １ and R ２ The meaning of is R in formula (1). １ and R ２ The meanings are the same as those of

[0106] In the above formula (1-2-1-1), preferably, R １ represents a 2-ethylphenyl group, and all R ２ indicates a hydrogen atom.

[0107] In such a case, the compound is represented by, for example, the following formula (1-2-1-1-1): The compound represented by the following formula (1-2-1-1-1) is 1-acryloylthio-8-phenyl-3,6-dithiaoctane (PE-DETGA).

[0108]

[0109] In addition, in the above formula (1), when n is an integer of 2 or more, X can represent an oxygen atom. In such a case, it is preferable that R ３ represents a hydrogen atom. That is, when n represents an integer of 2 or more, the above compound can have an acryloyloxy group.

[0110] In such a case, the compound is represented by, for example, the following formula (1-2-2).

[0111]

[0112] (In formula (1-2-2), R １ , R ２ and Y are defined as R in formula (1). １ , R ２ and Y have the same meanings as those of the formula (I), and n is an integer of 2 or more.

[0113] In the above formula (1-2-2), n preferably represents 2. In such a case, the above compound is represented, for example, by the following formula (1-2-3).

[0114]

[0115] (In formula (1-2-3), R １ , R ２ and Y are defined as R in formula (1). １ , R ２ and Y have the same meanings as those of the respective groups.)

[0116] In formula (1-2-3), Y represents a sulfur atom or an oxygen atom, and at least one Y represents a sulfur atom. Preferably, all Y represent sulfur atoms. That is, the above compound preferably has a thioalkylene group.

[0117] In such a case, the compound is represented by, for example, the following formula (1-2-3-1).

[0118]

[0119] (In formula (1-2-3-1), R １ and R ２ The meaning of is R in formula (1). １ and R ２ The meanings are the same as those of

[0120] In the above formula (1-2-3-1), preferably, R １ represents a 2-ethylphenyl group, and all R ２ indicates a hydrogen atom.

[0121] In such a case, the compound is represented by, for example, the following formula (1-2-3-1-1): The compound represented by the following formula (1-2-3-1-1) is 1-acryloyloxy-8-phenyl-3,6-dithiaoctane.

[0122]

[0123] In the above description, specific examples of the compound represented by formula (1) include compound (1-1) in which n in formula (1) is 1 and compound (1-2) in which n in formula (1) is 2, but the compound is not limited to these.

[0124] A specific example of the compound represented by formula (1) is preferably a compound represented by the following formula (1'): The compound represented by formula (1') is a compound represented by the above formula (1), and specifically, in formula (1), R １ represents a 2-phenylethyl group, and all R ２ represents a hydrogen atom, and R ３ represents a hydrogen atom, X represents a sulfur atom, and Y represents a sulfur atom. (In formula (1'), n represents an integer of 1 or more.)

[0125] In the above formula (1'), the meaning of n is the same as the meaning of n in the above formula (1). For example, in the above formula (1'), n is, for example, 1 to 50, preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 or 2.

[0126] More specifically, examples of the compound represented by the above formula (1') include 1-acryloylthio-5-phenyl-3-thiapentane (PE-DMEA) represented by the above formula (1-1-1-1-1) and 1-acryloylthio-8-phenyl-3,6-dithiaoctane (PE-DETGA) represented by the above formula (1-2-1-1-1).

[0127] By using the compound represented by the above formula (1'), it is possible to obtain a pressure-sensitive adhesive (described below) and a pressure-sensitive adhesive composition (described below) having particularly excellent refractive index, adhesion, and flexibility (i.e., a relatively low glass transition temperature).

[0128] 2. Method for Producing Compound (1) First Embodiment The compound represented by the above formula (1) is produced, for example, by the following method.

[0129] <Preparation Step> In this method, first, a thiol and / or alcohol represented by the following formula (2) is prepared (preparation step).

[0130]

[0131] (In formula (2), R １ , R ２ , n, Y and X are defined as R １ , R ２ , n, Y and X have the same meanings as those of the formula (I).

[0132] In the above formula (2), R １ The meaning of is R in the above formula (1). １ That is, R １represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or an araliphatic hydrocarbon group, preferably an aromatic hydrocarbon group or an araliphatic hydrocarbon group, more preferably an araliphatic hydrocarbon group, and even more preferably a phenyl group (Ph-), a benzyl group (Ph-CH ２ -), or a 2-phenylethyl group (Ph-CH ２ CH ２ -), and particularly preferably a 2-phenylethyl group (Ph-CH ２ CH ２ -) is indicated.

[0133] In the above formula (2), R ２ The meaning of is R in the above formula (1). ２ That is, R ２ are the same or different and represent a hydrogen atom or a methyl group, and preferably, all R ２ indicates a hydrogen atom.

[0134] In the above formula (2), the meaning of n is the same as the meaning of n in the above formula (1). That is, n represents an integer of 1 or more. That is, n can represent 1 or an integer of 2 or more.

[0135] In the above formula (2), the meaning of Y is the same as the meaning of n in the above formula (1). That is, Y represents a sulfur atom or an oxygen atom. For example, when n represents 1, Y represents a sulfur atom. For example, when n represents an integer of 2 or more, Y represents a sulfur atom or an oxygen atom, but at least one Y represents a sulfur atom. Preferably, all Y represent sulfur atoms.

[0136] In the above formula (2), the meaning of X is the same as the meaning of X in the above formula (1). That is, X represents a sulfur atom or an oxygen atom. For example, when n represents 1, X represents a sulfur atom. For example, when n represents an integer of 2 or more, X represents a sulfur atom or an oxygen atom. Preferably, all X represent sulfur atoms.

[0137] In the above formula (2), n preferably represents an integer of 1 or greater than 2. When n represents 1 in the above formula (2), the above thiol and / or alcohol is, for example, represented by the following formula (2-1):

[0138]

[0139] (In formula (2-1), R １ , R ２ The meanings of X and Y are R in formula (1). １ , R ２ , X and Y have the same meanings as above.)

[0140] In formula (2-1), X preferably represents a sulfur atom. That is, the above formula (2) preferably represents a thiol. Such a thiol is represented, for example, by the following formula (2-1-1).

[0141]

[0142] (In formula (2-1-1), R １ , R ２ and Y are defined as R in formula (1). １ , R ２ and Y have the same meanings as those of the respective groups.)

[0143] In the above formula (2-1-1), Y preferably represents a sulfur atom. That is, the above thiol preferably represents a hydrocarbon thio group (R １ —S—) (hereinafter referred to as hydrocarbon thio group-containing thiol).

[0144] In such a case, the hydrocarbon thio group-containing thiol is represented, for example, by the following formula (2-1-1-1).

[0145]

[0146] (In formula (2-1-1-1), R １ and R ２ The meaning of is R in formula (1). １ and R ２ The meanings are the same as those of

[0147] In the above formula (2-1-1-1), preferably, R １represents a 2-ethylphenyl group, and all R ２ indicates a hydrogen atom.

[0148] In such a case, the hydrocarbon thio group-containing thiol is represented, for example, by the following formula (2-1-1-1-1): The hydrocarbon thio group-containing thiol represented by the following formula (2-1-1-1-1) is 1-mercapto-5-phenyl-3-thiapentane.

[0149]

[0150] In addition, in the above formula (2-1-1-1), preferably, R １ is a benzyl group (PhCH ２ -), and all R ２ indicates a hydrogen atom.

[0151] In such a case, the hydrocarbon thio group-containing thiol is represented, for example, by the following formula (2-1-1-1-2): The hydrocarbon thio group-containing thiol represented by the following formula (2-1-1-1-2) is 2-(benzylthio)-ethane-1-thiol.

[0152]

[0153] In addition, in the above formula (2-1-1-1), preferably, R １ represents a phenyl group (Ph-), and all R ２ indicates a hydrogen atom.

[0154] In such a case, the hydrocarbon thio group-containing thiol is represented, for example, by the following formula (2-1-1-1-3): The hydrocarbon thio group-containing thiol represented by the following formula (2-1-1-1-3) is 2-(phenylthio)-ethane-1-thiol.

[0155]

[0156] In the above formula (2), when n is an integer of 2 or more, n is preferably 2. In such a case, the above thiol and / or alcohol is represented, for example, by the following formula (2-2).

[0157]

[0158] (In formula (2-2), R １ , R ２ , R ３ The meanings of X and Y are R in formula (1). １ , R ２ , R ３ , X and Y have the same meanings as above.)

[0159] In formula (2-2), X preferably represents a sulfur atom. That is, the above formula (2) preferably represents a thiol. The thiol is represented, for example, by the following formula (2-2-1).

[0160]

[0161] (In formula (2-2-1), R １ , R ２ and Y are defined as R in formula (1). １ , R ２ and Y have the same meanings as those of the respective groups.)

[0162] In the above formula (2-2-1), Y represents a sulfur atom or an oxygen atom, and at least one Y represents a sulfur atom. Preferably, all Y represent sulfur atoms. That is, the above thiol is preferably a hydrocarbon thio group-containing thiol.

[0163] In such a case, the hydrocarbon thio group-containing thiol is represented, for example, by the following formula (2-2-1-1).

[0164]

[0165] (In formula (2-2-1-1), R １ and R ２ The meaning of is R in formula (1). １ and R ２ The meanings are the same as those of

[0166] In the above formula (2-2-1-1), preferably, R １ represents a 2-ethylphenyl group, and all R ２ indicates a hydrogen atom.

[0167] In such a case, the hydrocarbon thio group-containing thiol is represented, for example, by the following formula (2-2-1-1-1): The hydrocarbon thio group-containing thiol represented by the following formula (2-2-1-1-1) is 1-mercapto-8-phenyl-3,6-dithiaoctane.

[0168]

[0169] In addition, in the above formula (2), when n is an integer of 2 or more, X can represent an oxygen atom. That is, when n is an integer of 2 or more, the above formula (2) can represent an alcohol.

[0170] In such a case, the alcohol is represented by, for example, the following formula (2-2-2).

[0171]

[0172] (In formula (2-2-2), R １ , R ２ and Y are defined as R in formula (1). １ , R ２ and Y have the same meanings as those of the formula (I), and n is an integer of 2 or more.

[0173] In the above formula (2-2-2), n preferably represents 2. In such a case, the alcohol is represented by, for example, the following formula (2-2-3).

[0174]

[0175] (In formula (2-2-3), R １ , R ２ and Y are defined as R in formula (1). １ , R ２ and Y have the same meanings as those of the respective groups.)

[0176] In formula (2-2-3), Y represents a sulfur atom or an oxygen atom, and at least one Y represents a sulfur atom. Preferably, all Y represent sulfur atoms. That is, the alcohol is preferably an alcohol containing a hydrocarbon thio group (hereinafter referred to as a hydrocarbon thio group-containing alcohol).

[0177] In such a case, the hydrocarbon thio group-containing alcohol is represented by, for example, the following formula (2-2-3-1).

[0178]

[0179] (In formula (2-2-3-1), R １ and R ２ The meaning of is R in formula (1). １ and R ２ The meanings are the same as those of

[0180] In the above formula (2-2-3-1), preferably, R １ represents a 2-ethylphenyl group, and all R ２ indicates a hydrogen atom.

[0181] In such a case, the hydrocarbon thio group-containing alcohol is, for example, represented by the following formula (2-2-3-1-1): The hydrocarbon thio group-containing alcohol represented by the following formula (2-2-3-1-1) is 1-hydroxy-8-phenyl-3,6-dithiaoctane.

[0182]

[0183] The thiol and / or alcohol represented by the formula (2) can be used alone or in combination of two or more. As the thiol and / or alcohol represented by the formula (2), a hydrocarbon thio group-containing thiol is preferred, and a hydrocarbon thio group-containing thiol having one to two thioalkylene groups is more preferred.

[0184] In the preparation step, the method for preparing the thiol and / or alcohol is not particularly limited.

[0185] For example, the thiol and / or alcohol represented by the formula (2) can be commercially available. Alternatively, the thiol and / or alcohol represented by the formula (2) can be produced. The method for producing the thiol and / or alcohol represented by the formula (2) is selected depending on the type of thiol and / or alcohol.

[0186] For example, when a hydrocarbon thio group-containing thiol is produced as the thiol, the preparation step includes a hydrocarbon thio group-containing alcohol production step and a mercapto group formation step. Each step will be described in detail below.

[0187] [Hydrocarbon Thio Group-Containing Alcohol Production Step] In the hydrocarbon thio group-containing alcohol production step, a hydrocarbon thio group-containing alcohol is produced by, for example, reacting an alcohol containing a mercapto group (hereinafter referred to as mercapto alcohol) with a modifying agent (hereinafter referred to as first modifying agent) that modifies the mercapto group to a hydrocarbon thio group.

[0188] Mercapto alcohol is an organic compound having both a hydroxyl group (OH) and a mercapto group (SH). Mercapto alcohol is, for example, represented by the following formula (4).

[0189]

[0190] (In formula (4), R ２ The meaning of is R in formula (1). ２ The meaning is the same as that of

[0191] More specifically, the mercapto alcohol represented by the above formula (4) includes mercapto alcohols having 2 to 4 carbon atoms, and more specifically, for example, 2-mercaptoethanol (SHCH ２ CH ２ OH), 2-methyl-2-mercaptoethanol (SHCH(CH ３ ) CH ２ OH), 1-methyl-2-mercaptoethanol (SHCH ２ CH (CH ３ )OH), and 1,2-dimethyl-2-mercaptoethanol (SHCH(CH ３ ) CH(CH ３ These can be used alone or in combination of two or more. 2-mercaptoethanol (SHCH ２ CH ２ OH).

[0192] The first modifying agent converts the mercapto group of the mercapto alcohol into a methyl group represented by R１ and modified with a hydrocarbon group represented by the formula: １ -S-).

[0193] The first modifier is R １ The first modifier is appropriately selected depending on the hydrocarbon group represented by the formula (I). Examples of the first modifier include vinyl compounds and halogenated hydrocarbons. That is, the first modifier contains a vinyl compound and / or a halogenated hydrocarbon, and preferably consists of a vinyl compound and / or a halogenated hydrocarbon.

[0194] The vinyl compound has a vinyl group and a hydrocarbon group. Examples of the vinyl compound include styrene, methylstyrene, and butylstyrene. These may be used alone or in combination of two or more. A preferred vinyl compound is styrene.

[0195] The halogenated hydrocarbon has a halogen and a hydrocarbon group. Examples of the halogenated hydrocarbon include alkyl halides, aryl halides, and aralkyl halides. Examples of the alkyl halides include methyl fluoride, methyl chloride, methyl bromide, methyl iodide, ethyl fluoride, ethyl chloride, ethyl bromide, and ethyl iodide. Examples of the aryl halides include phenyl fluoride, phenyl chloride, phenyl bromide, and phenyl iodide. Examples of the aralkyl halides include benzyl fluoride, benzyl chloride, benzyl bromide (benzyl bromide), and benzyl iodide. These can be used alone or in combination of two or more. Examples of the halogenated hydrocarbon include aralkyl halides, and more preferably benzyl bromide (benzyl bromide).

[0196] The method for reacting the mercapto alcohol with the first denaturing agent is not particularly limited and may be appropriately determined depending on the type of the first denaturing agent.

[0197] More specifically, for example, when the first modifying agent is a vinyl compound, the mercapto alcohol and the vinyl compound undergo an ene-thiol reaction in the presence of a known radical initiator (e.g., azobisisobutyronitrile (AIBN)).

[0198] In the ene-thiol reaction, a known radical initiator abstracts a hydrogen atom from the mercapto group of a mercapto alcohol to generate a thiyl radical, which then undergoes radical addition to the vinyl group of a vinyl compound.

[0199] The mixing ratio and reaction conditions for the ene-thiol reaction are not particularly limited and are appropriately set depending on the purpose and application. For example, a mercapto alcohol and a vinyl compound are mixed in an inert gas (e.g., nitrogen) atmosphere, and the mixture is heated and stirred in the presence of the radical initiator.

[0200] The mixing ratio of the mercapto alcohol and the vinyl compound is not particularly limited, but for example, the vinyl group of the vinyl compound is, for example, 0.8 to 1.2 moles, preferably 0.9 to 1.1 moles, per mole of the mercapto group of the mercapto alcohol.

[0201] The reaction conditions are not particularly limited, but for example, the reaction temperature is, for example, 20 to 100° C., preferably 40 to 80° C. The reaction time is, for example, 1 to 100 hours, preferably 10 to 50 hours.

[0202] In the reaction between the mercapto alcohol and the vinyl compound, a solvent is added as needed. Examples of the solvent include water and known organic solvents (e.g., ethyl acetate), and organic solvents are preferred. The blending ratio of the solvent is appropriately determined depending on the purpose and application.

[0203] Then, the mercapto group of the mercapto alcohol is modified by the ene-thiol reaction between the mercapto alcohol and the vinyl compound to form a hydrocarbon thio group, thereby obtaining an alcohol containing a hydrocarbon thio group.

[0204] Furthermore, for example, when the first modifying agent is a halogenated hydrocarbon, the mercapto alcohol and the halogenated hydrocarbon as the first modifying agent undergo a nucleophilic substitution reaction, for example, in the presence of a known basic compound (e.g., sodium hydroxide).

[0205] In the nucleophilic substitution reaction, for example, a known basic compound dissociates the proton from the mercapto group of mercapto alcohol to generate a nucleophile, and the nucleophile derived from mercaptoethanol then undergoes a nucleophilic substitution reaction with a halogenated hydrocarbon.

[0206] The mixing ratio and reaction conditions for the nucleophilic substitution reaction are not particularly limited and may be appropriately determined depending on the purpose and application. For example, a mercapto alcohol and a halogenated hydrocarbon are mixed and stirred in the presence of a known basic compound.

[0207] The mixing ratio of the mercapto alcohol and the halogenated hydrocarbon is not particularly limited, but for example, the halogen atoms of the halogenated hydrocarbon are, for example, 0.8 to 1.2 moles, preferably 0.9 to 1.1 moles per mole of mercapto groups of the mercapto alcohol.

[0208] The reaction conditions are not particularly limited, but for example, the reaction temperature is, for example, 10 to 40° C., preferably 20 to 30° C. The reaction time is, for example, 0.1 to 10 hours, preferably 1 to 5 hours.

[0209] In the reaction between mercapto alcohol and halogenated hydrocarbon, a solvent is added as needed. Examples of the solvent include water and known organic solvents (e.g., ethyl acetate), and organic solvents are preferred. The blending ratio of the solvent is appropriately determined depending on the purpose and application.

[0210] Then, the mercapto group of the mercapto alcohol is modified by a nucleophilic substitution reaction between the mercapto alcohol and the halogenated hydrocarbon, forming a hydrocarbon thio group, thereby obtaining a hydrocarbon thio group-containing alcohol.

[0211] The hydrocarbon thio group-containing alcohol is represented, for example, by the following formula (5).

[0212]

[0213] (In formula (5), R １ and R ２ The meaning of is R in the above formula (1). １ and R ２ The meanings are the same as those of

[0214] In the above formula (5), preferably, R １ 2 phenylethyl groups (Ph-CH ２ CH ２ -), and all R ２ represents a hydrogen atom. Such a compound can be produced, for example, by the following method.

[0215] That is, in this method, as shown in the following formula (6), 2-mercaptoethanol (SHCH ２ CH ２ OH) and styrene (a vinyl compound) undergo an ene-thiol reaction in the presence of azobisisobutyronitrile (a radical initiator, AIBN).

[0216] As a result, 1-hydroxy-5-phenyl-3-thiapentane is obtained as the hydrocarbon thio group-containing alcohol.

[0217]

[0218] The method for obtaining the hydrocarbon thio group-containing alcohol is not limited to the above, and may be appropriately selected depending on the purpose and application.

[0219] [Mercapto Group Formation Step] In the mercapto group formation step, the hydroxyl group of the hydrocarbon thio group-containing alcohol is converted to a mercapto group to obtain a hydrocarbon thio group-containing thiol.

[0220] The method for converting a hydroxyl group to a mercapto group is not particularly limited. For example, first, the hydrocarbon thio group-containing alcohol is reacted with thiourea to produce an isothiuronium salt, and then the resulting isothiuronium salt is mixed with an aqueous base solution to hydrolyze the isothiuronium salt.

[0221] More specifically, in this method, first, a hydrocarbon thio group-containing alcohol and thiourea are mixed and reacted.

[0222] The mixing ratio of the hydrocarbon thio group-containing alcohol and thiourea is not particularly limited, but for example, the amount of thiourea is, for example, 0.8 to 1.2 moles, preferably 0.9 to 1.1 moles, per mole of hydroxyl groups of the hydrocarbon thio group-containing alcohol.

[0223] The reaction conditions are not particularly limited, but for example, the reaction temperature is, for example, 20 to 100° C., preferably 40 to 80° C. The reaction time is, for example, 0.1 to 10 hours, preferably 1 to 5 hours.

[0224] In the reaction between the hydrocarbon thio group-containing alcohol and the thiourea, a solvent is added as needed. Examples of the solvent include water and known organic solvents, and water is preferred. The amount of the solvent is appropriately determined depending on the purpose and application.

[0225] In the reaction of the hydrocarbon thio group-containing alcohol with thiourea, a hydrohalic acid is added as needed. Examples of the hydrohalic acid include hydrochloric acid and hydrobromic acid, and hydrochloric acid is preferred. The amount of the hydrohalic acid added is appropriately determined depending on the purpose and application.

[0226] The hydrocarbon thio group-containing alcohol is reacted with thiourea to obtain an isothiuronium salt, which is then purified as necessary.

[0227] In this method, an aqueous base solution is then added to the isothiuronium salt to hydrolyze the isothiuronium salt.

[0228] Examples of the aqueous base solution include ammonia water, sodium hydroxide solution, potassium hydroxide solution, hydrazine solution, and sodium carbonate solution. These can be used alone or in combination of two or more. Ammonia water is preferred as the aqueous base solution. The base concentration of the aqueous base solution is appropriately set depending on the purpose and application.

[0229] In the hydrolysis of an isothiuronium salt, the concentration and amount of the aqueous base solution are not particularly limited and are appropriately determined depending on the purpose and application.

[0230] The reaction conditions are not particularly limited, but for example, the reaction temperature is, for example, 20 to 100° C., preferably 40 to 80° C. The reaction time is, for example, 0.1 to 10 hours, preferably 1 to 5 hours.

[0231] The hydrolysis converts the hydroxyl group of the hydrocarbon thio group-containing alcohol into a mercapto group, thereby producing a hydrocarbon thio group-containing thiol.

[0232] More specifically, as described above, a preferred hydrocarbon thio group-containing alcohol is 1-hydroxy-5-phenyl-3-thiapentane.

[0233] In such a case, as shown in the following formula (7), 1-hydroxy-5-phenyl-3-thiapentane reacts with thiourea, and the reaction product (isothiuronium salt) is hydrolyzed with an aqueous base.

[0234] As a result, the hydroxyl group is converted to a mercapto group, and 1-mercapto-5-phenyl-3-thiapentane is obtained as a hydrocarbon thiol group-containing thiol.

[0235]

[0236] The method for converting the hydroxyl group of the hydrocarbon thio group-containing alcohol to a mercapto group is not limited to the above, and may be appropriately selected depending on the purpose and application.

[0237] As described above, in the preparation steps (hydrocarbon thio group-containing alcohol step and mercapto group-forming step), a hydrocarbon thio group-containing thiol is prepared as the thiol represented by the above formula (2).

[0238] <(Meth)acryloyl Group Forming Step> Next, in this method, the mercapto group of the thiol represented by the above formula (2) is modified to a (meth)acryloylthio group, and / or the hydroxyl group of the alcohol represented by the above formula (2) is modified to a (meth)acryloyloxy group ((meth)acryloyl group forming step).

[0239] That is, when the thiol represented by the formula (2) is prepared in the preparation step, the mercapto group of the thiol is modified to a (meth)acryloylthio group in this step, and when the alcohol represented by the formula (2) is prepared in the preparation step, the hydroxyl group of the alcohol is modified to a (meth)acryloyloxy group in this step.

[0240] More specifically, in this step, a thiol and / or alcohol is reacted with a modifying agent (hereinafter referred to as a second modifying agent) for forming a (meth)acryloyl group.

[0241] The second modifying agent is a compound for modifying a mercapto group and / or a hydroxyl group to form a (meth)acryloylthio group and / or a (meth)acryloyloxy group.

[0242] Examples of the second modifying agent include (meth)acrylic acid halides and (meth)acrylic acid anhydrides. Examples of the (meth)acrylic acid halides include (meth)acrylic acid chloride, (meth)acrylic acid bromide, and (meth)acrylic acid iodide. Examples of the (meth)acrylic acid anhydrides include acrylic acid anhydride and methacrylic acid anhydride. These can be used alone or in combination of two or more types.

[0243] Furthermore, as the second modifying agent, two or more compounds can be used in combination so as to be capable of forming a (meth)acryloyl group.

[0244] More specifically, the second modifying agent may contain, for example, (meth)acrylic acid and a dehydration condensation agent. Examples of the dehydration condensation agent include imidazole-based condensation agents, triazine-based condensation agents, phosphonium-based condensation agents, uronium-based condensation agents, and haluronium-based condensation agents. These may be used alone or in combination of two or more.

[0245] The second modifying agent may contain, for example, a propionic acid derivative and a basic compound. Examples of the propionic acid derivative include the propionic acid derivatives described in Japanese Patent Laid-Open No. 4-29967. More specific examples of the propionic acid derivative include β-chloropropionic acid, β-bromopropionic acid, β-hydroxypropionic acid toluenesulfonyl ester, β-hydroxypropionic acid benzenesulfonyl ester, β-hydroxypropionic acid methanesulfonyl ester, α-methyl-β-chloropropionic acid, α-methyl-β-bromopropionic acid, α-methyl-β-hydroxypropionic acid toluenesulfonyl ester, α-methyl-β-hydroxypropionic acid benzenesulfonyl ester, α-methyl-β-hydroxypropionic acid methanesulfonyl ester, and acid halides thereof. More specific examples of acid halides include β-chloropropionic acid chloride (3-chloropropionic acid chloride (3CPC)), β-bromopropionic acid chloride, α-methyl-β-chloropropionic acid chloride, and α-methyl-β-bromopropionic acid chloride. These can be used alone or in combination of two or more. Examples of bases include sodium hydroxide, potassium hydroxide, triethylamine, and pyridine. These can be used alone or in combination of two or more.

[0246] The second denaturant is preferably a combination of a propionic acid derivative and a basic compound, more preferably a combination of 3-chloropropionic acid chloride (3CPC) and triethylamine.

[0247] The mixing ratio of the second denaturing agent to the thiol and / or alcohol is not particularly limited, and is set appropriately depending on the type of thiol and / or alcohol and the type of the second denaturing agent.

[0248] For example, when a hydrocarbon thio group-containing thiol is prepared as the thiol, the hydrocarbon thio group-containing thiol and the second modifying agent are mixed in this step.

[0249] In such a case, when the second modifying agent contains a (meth)acrylic acid halide, the hydrocarbon thio group-containing thiol and the halogen atoms of the (meth)acrylic acid halide are mixed and undergo a condensation reaction. The mixing ratio is not particularly limited, but for example, the ratio of halogen atoms in the second modifying agent ((meth)acrylic acid halide) to 1 mole of mercapto groups of the hydrocarbon thio group-containing thiol is, for example, 0.8 to 1.5 moles, preferably 0.9 to 1.3 moles.

[0250] For example, when the second modifying agent contains (meth)acrylic anhydride, the hydrocarbon thio group-containing thiol and (meth)acrylic anhydride are mixed and undergo a condensation reaction. The mixing ratio is not particularly limited, but for example, the ratio of the second modifying agent ((meth)acrylic anhydride) to 1 mole of mercapto groups of the hydrocarbon thio group-containing thiol is, for example, 0.8 to 1.5 moles, preferably 0.9 to 1.3 moles.

[0251] Furthermore, when the second modifying agent contains (meth)acrylic acid and a dehydration condensing agent, the hydrocarbon thio group-containing thiol and (meth)acrylic acid undergo a condensation reaction in the presence of the dehydration condensing agent. The mixing ratio is not particularly limited, but for example, the ratio of the second modifying agent ((meth)acrylic acid) to 1 mole of mercapto groups of the hydrocarbon thio group-containing thiol is, for example, 0.8 to 1.5 moles, preferably 0.9 to 1.3 moles.

[0252] Furthermore, when the second modifying agent contains a propionic acid derivative and a basic compound, the hydrocarbon thio group-containing thiol is reacted with the propionic acid derivative and the basic compound in accordance with the method described in JP-A-4-29967. More specifically, the hydrocarbon thio group-containing thiol and the propionic acid derivative are first subjected to a condensation reaction. Next, the halogen of the reaction product (condensate) is treated (eliminated) with a basic compound to form an ethylenically unsaturated bond. This results in the formation of a (meth)acryloylthio group. The mixing ratio is not particularly limited, but for example, the ratio of the second modifying agent (propionic acid derivative) to 1 mole of mercapto groups in the hydrocarbon thio group-containing thiol is, for example, 0.8 to 1.5 moles, preferably 0.9 to 1.3 moles.

[0253] The reaction conditions between the thiol and / or alcohol and the second modifying agent are appropriately selected depending on the type of the second modifying agent. A solvent can be added to the reaction between the thiol and / or alcohol and the second modifying agent, if necessary. The type and amount of the solvent are appropriately set. A known catalyst can be added to the reaction between the thiol and / or alcohol and the second modifying agent, if necessary. The type and amount of the catalyst are appropriately selected depending on the type of the thiol and / or alcohol and the type of the second modifying agent.

[0254] The reaction of the thiol and / or alcohol with the second modifying agent results in the modification of the mercapto group and / or hydroxyl group to form a (meth)acryloyl group. That is, the mercapto group of the thiol is modified to form a (meth)acryloylthio group. Also, the hydroxyl group of the alcohol is modified to form a (meth)acryloyloxy group.

[0255] For example, when the hydrocarbon thio group-containing thiol reacts with the second modifying agent, the mercapto group of the hydrocarbon thio group-containing thiol is modified to form a (meth)acryloylthio group, thereby producing a compound containing a (meth)acryloylthio group.

[0256] More specifically, for example, 1-mercapto-5-phenyl-3-thiapentane is used as a hydrocarbon thio group-containing thiol, and for example, 3-chloropropionic acid chloride (3CPC) and triethylamine are used as a second modifying agent.

[0257] In such a case, as shown in the following formula (8), the mercapto group of the hydrocarbon thio group-containing thiol is modified with a second modifying agent (e.g., 3CPC and TEA) to obtain a (meth)acryloylthio group.

[0258] As a result, 1-acryloylthio-5-phenyl-3-thiapentane (PE-DMEA) is obtained as the compound represented by the above formula (1).

[0259]

[0260] As described above, in the first embodiment, a thiol and / or alcohol represented by the formula (2) is prepared (preparation step), and then the mercapto group and / or hydroxyl group is modified to form a (meth)acryloylthio group and / or a (meth)acryloyloxy group ((meth)acryloyl group formation step). As a result, a compound represented by the formula (1) is obtained.

[0261] (2) Second Embodiment In the above formula (1), n ​​can represent an integer of 2 or more. That is, the compound represented by the above formula (1) can be formed by combining a plurality (two or more) of structural units [YCHR ２ CHR ２ Such compounds can be prepared, for example, by reacting the thiol and / or alcohol with the structural unit [YCHR ２ CHR ２ ] is introduced.

[0262] <Preparation Step> In this method, the preparation step is a step of adding a structural unit [YCHR ２ CHR ２ The structural unit [YCHR ２ CHR ２Examples of the step of introducing the group] include an oxyalkylene group introduction step and a thioalkylene group introduction step, and preferably a thioalkylene group introduction step.

[0263] That is, the preparation step preferably includes a thioalkylene group introduction step.

[0264] In the thioalkylene group introduction step, a thioalkylene group is introduced to the above-mentioned thiol and / or alcohol. Preferably, in the thioalkylene group introduction step, a thioalkylene group is introduced to the above-mentioned thiol.

[0265] More specifically, the thioalkylene group introduction step includes an oxyalkylene group introduction step and a mercapto group formation step. Each step will be described in detail below.

[0266] [Oxyalkylene Group Introduction Step] In the oxyalkylene group introduction step, an oxyalkylene group is introduced into the thiol to obtain an oxyalkylene-introduced alcohol.

[0267] The thiol to which the oxyalkylene group is introduced is produced by the method described above. More specifically, first, a hydrocarbon thio group-containing alcohol is obtained by reacting a mercapto alcohol with a first modifying agent (hydrocarbon thio group-containing alcohol production step). Next, the hydrocarbon thio group-containing alcohol is reacted with thiourea, and the reaction product is hydrolyzed to obtain a hydrocarbon thio group-containing thiol (mercapto group formation step). Through the above steps, a hydrocarbon thio group-containing thiol is obtained.

[0268] The method for introducing an oxyalkylene group into a hydrocarbon thio group-containing thiol is not particularly limited. For example, the hydrocarbon thio group-containing thiol is reacted with an alkylene oxide represented by the following formula (9):

[0269]

[0270] (In formula (9), R ２ The meaning of is R in the above formula (1). ２ The meaning is the same as that of

[0271] Examples of the alkylene oxide represented by the formula (9) include ethylene oxide, propylene oxide (2-methyloxirane), and 2,3-dimethyloxirane. These can be used alone or in combination of two or more. Ethylene oxide is preferred as the alkylene oxide.

[0272] The method for reacting the hydrocarbon thio group-containing thiol with the alkylene oxide is not particularly limited, but for example, the hydrocarbon thio group-containing thiol and the alkylene oxide are mixed in the presence of a basic compound (e.g., sodium hydroxide).

[0273] The mixing ratio of the hydrocarbon thio group-containing thiol and the alkylene oxide is appropriately set depending on the number of thioalkylene groups to be introduced, for example, 0.1 to 50 moles, preferably 0.5 to 10 moles, more preferably 1 to 5 moles, and even more preferably 1 to 2 moles of alkylene oxide per mole of the hydrocarbon thio group-containing thiol.

[0274] The reaction conditions are not particularly limited, but for example, the reaction temperature is, for example, −20 to 40° C., preferably 0 to 20° C. The reaction time is, for example, 1 to 100 hours, preferably 10 to 50 hours.

[0275] In the reaction between the hydrocarbon thio group-containing thiol and the alkylene oxide, a solvent is added as needed. Examples of the solvent include water and known organic solvents. The blending ratio of the solvent is appropriately set depending on the purpose and application.

[0276] Then, by the reaction between the hydrocarbon thio group-containing thiol and the alkylene oxide, the alkylene oxide is added to the mercapto group of the hydrocarbon thio group-containing thiol, and an oxyalkylene group is introduced into the hydrocarbon thio group-containing thiol.

[0277] The hydrocarbon thio group-containing thiol having an oxyalkylene group introduced therein has a hydroxyl group at the molecular terminal, i.e., an oxyalkylene-introduced alcohol is obtained as the hydrocarbon thio group-containing thiol having an oxyalkylene group introduced therein.

[0278] For example, when one oxyalkylene group is introduced into one molecule of the hydrocarbon thio group-containing thiol, the oxyalkylene-introduced alcohol is represented by, for example, the following formula (10).

[0279]

[0280] (In formula (10), R １ and R ２ The meaning of is R in the above formula (1). １ and R ２ The meaning is the same as that of

[0281] More specifically, a preferred example of the hydrocarbon thio group-containing thiol is 1-mercapto-5-phenyl-3-thiapentane, and a preferred example of the alkylene oxide is ethylene oxide.

[0282] In such a case, as shown in the following formula (11), one molecule of 1-mercapto-5-phenyl-3-thiapentane reacts with one molecule of ethylene oxide to obtain 1-hydroxy-8-phenyl-3,6-dithiaoctane as an oxyalkylene-introduced alcohol.

[0283]

[0284] [Mercapto Group Formation Step] In the mercapto group formation step, the hydroxyl group of the oxyalkylene-introduced alcohol is converted to a mercapto group to obtain a thioalkylene-introduced thiol.

[0285] That is, in this method, the hydroxyl group of the oxyalkylene-introduced alcohol is converted to a mercapto group in the same manner as above. More specifically, for example, the oxyalkylene-introduced alcohol is reacted with thiourea to produce an isothiuronium salt, and then the isothiuronium salt is hydrolyzed with an aqueous base. In this way, the hydroxyl group of the oxyalkylene-introduced alcohol is converted to a mercapto group, and a thioalkylene-introduced thiol can be obtained.

[0286] For example, when one oxyalkylene group is introduced into one molecule of the hydrocarbon thio group-containing thiol, the above reaction produces a hydrocarbon thio group-containing thiol as a thioalkylene-introduced thiol.

[0287] In other words, the above reaction introduces one thioalkylene group into the hydrocarbon thio group-containing thiol, resulting in a thioalkylene-introduced thiol as the hydrocarbon thio group-containing thiol.

[0288] More specifically, as described above, a preferred example of the oxyalkylene-introduced alcohol is 1-hydroxy-8-phenyl-3,6-dithiaoctane.

[0289] In such a case, as shown in the following formula (12), 1-hydroxy-8-phenyl-3,6-dithiaoctane reacts with thiourea, and the reaction product (isothiuronium salt) is hydrolyzed with an aqueous base.

[0290] As a result, the hydroxyl group is converted to a mercapto group, and 1-mercapto-8-phenyl-3,6-dithiaoctane is obtained as a hydrocarbon thiol group-containing thiol.

[0291]

[0292] <(Meth)acryloyl Group Forming Step> Then, in this method, the mercapto group of the hydrocarbon thio group-containing thiol into which the thioalkylene group has been introduced is modified into a (meth)acryloylthio group by the method described above ((meth)acryloyl group forming step).

[0293] More specifically, for example, the mercapto group of the hydrocarbon thio group-containing thiol having a thioalkylene group introduced therein is reacted with the second modifying agent by the above-described method, thereby obtaining the compound represented by the above formula (1).

[0294] More specifically, as described above, a preferred example of the hydrocarbon thio group-containing thiol into which a thioalkylene group has been introduced is 1-mercapto-8-phenyl-3,6-dithiaoctane.

[0295] In such a case, as shown in the following formula (13), the mercapto group of the hydrocarbon thio group-containing thiol into which a thioalkylene group has been introduced is modified to form a (meth)acryloylthio group.

[0296] As a result, 1-acryloylthio-8-phenyl-3,6-dithiaoctane (PE-DETGA) is obtained as the compound represented by the above formula (1).

[0297]

[0298] <Modifications> In the above description, one thioalkylene group is introduced per molecule of thiol and / or alcohol, but, for example, two or more thioalkylene groups can be introduced per molecule of thiol and / or alcohol.

[0299] When two or more thioalkylene groups are introduced into one molecule of thiol and / or alcohol, for example, in the thioalkylene group introduction step, the oxyalkylene introduction step and the mercapto group formation step are sequentially repeated any number of times. That is, after one thioalkylene group is introduced into the thiol and / or alcohol to obtain a thioalkylene group-introduced thiol, a further thioalkylene group is introduced into the thioalkylene group-introduced thiol.

[0300] By this method, any number of thioalkylene groups can be introduced into a thiol and / or alcohol, i.e., a compound having any number of thioalkylene groups can be produced as the compound represented by the above formula (1).

[0301] The number of thioalkylene groups to be introduced is selected arbitrarily depending on the number of thioalkylene groups in the desired compound (n in the above formula (1)).

[0302] In the above method, an oxyalkylene group is first introduced in the (meth)acryloyl group-forming step, and then the hydroxyl group is converted to a mercapto group. However, depending on the desired compound (the compound represented by the above formula (1)), the mercapto group-forming step can be omitted. That is, an oxyalkylene group can be introduced into a thiol and / or an alcohol. In addition, in the (meth)acryloyl group-forming step, the oxyalkylene group can be modified to form a (meth)acryloyloxy group.

[0303] More specifically, for example, an oxyalkylene is introduced into a thioalkylene-introduced thiol by the above-mentioned method to obtain an oxyalkylene-introduced alcohol, and then the hydroxyl group of the oxyalkylene-introduced alcohol is modified without converting the hydroxyl group to a mercapto group to obtain a (meth)acryloyloxy group. According to this method, a compound having at least one thioalkylene group and any number of oxyalkylene groups can be obtained as the compound represented by the above formula (1).

[0304] As described above, in the second embodiment, a thioalkylene group can be introduced into a thiol and / or alcohol as needed, and an oxyalkylene group can be introduced as needed. Furthermore, a mercapto group can be modified to form a (meth)acryloylthio group, and a hydroxyl group can be modified to form a (meth)acryloyloxy group as needed. By appropriately combining these, any compound represented by the above formula (1) can be produced.

[0305] 3. Method for Producing Pressure-Sensitive Adhesive The pressure-sensitive adhesive has a structural unit derived from the compound represented by the above formula (1). Such a pressure-sensitive adhesive is produced, for example, by the following method.

[0306] More specifically, in this method, first, a polymerizable composition is prepared. The polymerizable composition is a composition containing a monomer component and a radical polymerization initiator.

[0307] The monomer component contains, as an essential component, the compound represented by the above formula (1).

[0308] The monomer component may contain a copolymerizable monomer, if necessary. The copolymerizable monomer is a monomer that can be copolymerized with the compound represented by the above formula (1).

[0309] Examples of the copolymerizable monomer include monofunctional copolymerizable monomers and polyfunctional copolymerizable monomers (described later), and preferably monofunctional copolymerizable monomers. Examples of the monofunctional copolymerizable monomer include monofunctional (meth)acrylates.

[0310] Examples of monofunctional (meth)acrylates include alkyl mono(meth)acrylates, aromatic ring-containing mono(meth)acrylates, alicyclic ring-containing mono(meth)acrylates, heterocyclic ring-containing mono(meth)acrylates, alkoxy group-containing mono(meth)acrylates, hydroxyl group-containing mono(meth)acrylates, and amino group-containing mono(meth)acrylates.

[0311] Examples of alkyl mono(meth)acrylates include ethyl(meth)acrylate, butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate (2EH(M)A), nonyl(meth)acrylate, lauryl(meth)acrylate, tridecyl(meth)acrylate, hexadecyl(meth)acrylate, octadecyl(meth)acrylate, isoamyl(meth)acrylate, isodecyl(meth)acrylate, and isostearyl(meth)acrylate. These can be used alone or in combination of two or more.

[0312] Examples of aromatic ring-containing mono(meth)acrylates include benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, nonylphenoxyethyl (meth)acrylate, (o-, m-, or p-)phenoxybenzyl (meth)acrylate (POB-(M)A), 2-hydroxy-3-phenoxypropyl (meth)acrylate, nonylphenoxyethyl tetrahydrofurfuryl (meth)acrylate, and 1-naphthylmethyl (meth)acrylate. These can be used alone or in combination of two or more.

[0313] Examples of alicyclic ring-containing mono(meth)acrylates include cyclohexyl(meth)acrylate, isobornyl(meth)acrylate, dicyclopentanyl(meth)acrylate, and dicyclopentenyloxyethyl(meth)acrylate. These can be used alone or in combination of two or more.

[0314] Examples of heterocycle-containing mono(meth)acrylates include tetrahydrofurfuryl(meth)acrylate, glycidyl(meth)acrylate, and caprolactone-modified tetrahydrofurfuryl(meth)acrylate. These can be used alone or in combination of two or more.

[0315] Examples of alkoxy group-containing mono(meth)acrylates include methoxyethyl(meth)acrylate and butoxyethyl(meth)acrylate, which can be used alone or in combination of two or more.

[0316] Examples of hydroxyl group-containing mono(meth)acrylates include 3-chloro-2-hydroxypropyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate, and 4-hydroxybutyl(meth)acrylate. These can be used alone or in combination of two or more.

[0317] An example of the amino group-containing mono(meth)acrylate is diethylaminoethyl(meth)acrylate. These may be used alone or in combination of two or more.

[0318] Further, examples of the monofunctional copolymerizable monomer include styrene, α-methylstyrene, vinyltoluene, vinylbiphenyl, and divinylbenzene. These can be used alone or in combination of two or more kinds.

[0319] The copolymerizable monomers can be used alone or in combination of two or more. From the viewpoint of adhesiveness and optical properties, the copolymerizable monomer is preferably a monofunctional (meth)acrylate, more preferably a hydroxyl group-containing mono(meth)acrylate, and even more preferably 4-hydroxybutyl (meth)acrylate.

[0320] That is, from the viewpoint of adhesiveness and optical properties, the pressure-sensitive adhesive preferably has a structural unit derived from a monofunctional (meth)acrylate, more preferably has a structural unit derived from a hydroxyl group-containing mono(meth)acrylate, and even more preferably has a structural unit derived from 4-hydroxybutyl (meth)acrylate.

[0321] In the monomer components, the content ratio of the compound represented by the above formula (1) and the copolymerizable monomer is appropriately set depending on the purpose and application.

[0322] For example, on a molar basis, the content ratio (molar ratio) of the copolymerizable monomer relative to the total amount (total moles) of the compound represented by the above formula (1) and the copolymerizable monomer is, for example, 0 to 50 mol%, preferably 0 to 40 mol%, more preferably 0 to 20 mol%.

[0323] In particular, the content of the hydroxyl group-containing mono(meth)acrylate relative to the total amount (total moles) of the compound represented by the above formula (1) and the copolymerizable monomer is, for example, 0 to 50 mol %, preferably 0 to 35 mol %, and more preferably 0 to 10 mol %.

[0324] Furthermore, on a mass basis, the content ratio (mass ratio) of the copolymerizable monomer relative to the total amount (total mass) of the compound represented by the above formula (1) and the copolymerizable monomer is, for example, 0 to 50 mass%, preferably 1 to 30 mass%, and more preferably 5 to 10 mass%.

[0325] The content (total amount) of the copolymerizable monomers relative to 100 parts by mass of the total amount of the compounds represented by formula (1) is, for example, 0 to 50 parts by mass, preferably 1 to 30 parts by mass, and more preferably 5 to 10 parts by mass.

[0326] Examples of radical polymerization initiators include thermal radical polymerization initiators, photoradical polymerization initiators, and redox initiators. More specifically, examples include organic peroxides, azo compounds (e.g., azobisbutyronitrile), oxime compounds, alkylphenone compounds, aryl ketone compounds, biimidazole compounds, triazine compounds, and acylphosphine compounds. These can be used alone or in combination of two or more. The amount and timing of addition of the radical polymerization initiator are appropriately determined depending on the purpose and application.

[0327] The polymerizable composition may contain additives as needed. Examples of additives include plasticizers, crosslinking agents, silane coupling agents, antifoaming agents, leveling agents, mildew inhibitors, rust inhibitors, matting agents, flame retardants, thixotropic agents, tackifiers, thickeners, lubricants, antistatic agents, surfactants, reaction retarders, crosslinking retarders, antioxidants, UV absorbers, hydrolysis inhibitors, weathering stabilizers, heat stabilizers, dyes, inorganic pigments, organic pigments, anti-tack agents, inorganic fillers, and organic fillers. These may be used alone or in combination of two or more. The amount and timing of addition of the additives are appropriately determined depending on the purpose and application.

[0328] In this method, for example, the polymerizable composition is irradiated with active energy rays and / or heated to cure (radical polymerize) the polymerizable composition. The curing conditions are selected within a range that allows a pressure-sensitive adhesive having relatively excellent adhesiveness to be obtained.

[0329] Examples of active energy rays include ultraviolet rays and electron beams. The wavelength of the active energy rays is appropriately set depending on the purpose and application. The integrated light amount is, for example, 0.1 mJ / cm. ２ The integrated light amount is, for example, 5000 mJ / cm ２ Preferably, 3000 mJ / cm or less ２ The illuminance is, for example, 0.01 mW / cm ２ The illuminance is, for example, 500 mW / cm ２ Preferably, 300 mW / cm or less ２ The following is the result.

[0330] Heating conditions are appropriately set depending on the purpose and application. The heating temperature is, for example, 40°C or higher, preferably 50°C or higher. The heating temperature is, for example, 200°C or lower, preferably 100°C or lower. The heating time is, for example, 1 minute or longer, preferably 5 minutes or longer. The heating time is, for example, 48 hours or shorter, preferably 24 hours or shorter.

[0331] By irradiation with active energy rays and / or heating, the monomer components undergo radical polymerization (photoradical polymerization and / or thermal radical polymerization), thereby obtaining a cured resin product.

[0332] More specifically, when the monomer component contains the compound represented by formula (1) above but does not contain a copolymerizable monomer, the compound represented by formula (1) is homopolymerized by the radical polymerization to obtain a homopolymer. That is, the cured resin product contains, for example, a homopolymer of the compound represented by formula (1) above, and preferably consists of a homopolymer of the compound represented by formula (1).

[0333] Furthermore, when the monomer component contains the compound represented by formula (1) above and a copolymerizable monomer, the compound represented by formula (1) is copolymerized with the copolymerizable monomer by the radical polymerization to obtain a copolymer. The cured resin contains, for example, a copolymer of the compound represented by formula (1) above and the copolymerizable monomer, and preferably consists of a copolymer of the compound represented by formula (1) above and the copolymerizable monomer.

[0334] The weight average molecular weight (Mw) of the cured resin is, for example, 10,000 to 500,000, preferably 20,000 to 450,000, and more preferably 30,000 to 400,000.

[0335] The number average molecular weight (Mn) of the cured resin is, for example, 5,000 to 200,000, preferably 5,000 to 150,000, or more preferably 9,000 to 100,000.

[0336] The polydispersity (Mw / Mn) of the cured resin is, for example, 1.1 to 10.0, preferably 1.5 to 9.0, or more preferably 2.0 to 8.0.

[0337] The weight average molecular weight (Mw), number average molecular weight (Mn) and dispersity (Mw / Mn) are measured as polystyrene equivalent values ​​by gel permeation chromatography (GPC) in accordance with the examples described later.

[0338] Furthermore, the above-mentioned cured resin may be crosslinked if necessary. That is, the cured resin may be a crosslinked cured resin. The method for obtaining the crosslinked cured resin is not particularly limited. For example, when the copolymerizable monomer contains a hydroxyl group-containing mono(meth)acrylate, the cured resin obtained by the above reaction contains a hydroxyl group. In such a case, the cured resin can be crosslinked, for example, by using a crosslinking agent capable of reacting with a hydroxyl group.

[0339] The crosslinking agent is not particularly limited, but examples thereof include crosslinking agents capable of reacting with hydroxyl groups, more specifically, examples thereof include isocyanate crosslinking agents, epoxy crosslinking agents, aziridine crosslinking agents, oxazoline crosslinking agents, melamine crosslinking agents, and metal chelate crosslinking agents, and preferably, isocyanate crosslinking agents. The isocyanate crosslinking agent can undergo a urethane reaction with the hydroxyl groups of the cured resin material, for example, to urethane crosslink the cured resin material.

[0340] Examples of the isocyanate crosslinking agent include known polyisocyanates. Examples of the polyisocyanate include linear aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and araliphatic polyisocyanates. Examples of the linear aliphatic polyisocyanates include pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), and derivatives thereof. Examples of the alicyclic polyisocyanates include isophorone diisocyanate (IPDI), norbornene diisocyanate (NBDI), hydrogenated diphenylmethane diisocyanate (HDI), and derivatives thereof. １２ MDI), hydrogenated xylylene diisocyanate (H ６Examples of aromatic polyisocyanates include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), and derivatives thereof. Examples of araliphatic polyisocyanates include xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), and derivatives thereof. Examples of derivatives include polymers, isocyanurate-modified products, allophanate-modified products, polyol-modified products, biuret-modified products, urea-modified products, oxadiazinetrione-modified products, and carbodiimide-modified products. These can be used alone or in combination of two or more types.

[0341] The method for crosslinking the cured resin material with the crosslinking agent is not particularly limited. For example, first, a cured resin material having hydroxyl groups is dissolved in a known solvent (e.g., toluene) to prepare a solution of the cured resin material (hereinafter, referred to as a resin varnish). The method for preparing the resin varnish is not particularly limited. For example, the resin varnish can be obtained by polymerizing a polymerizable composition in a solvent. The solid content concentration of the resin varnish is, for example, 10 to 50 mass %, preferably 20 to 40 mass %.

[0342] Next, in this method, the crosslinking agent is added to the resin varnish to prepare a coating material (i.e., a crosslinkable composition containing a cured resin and a crosslinking agent). The amount and timing of the crosslinking agent to be added are appropriately determined depending on the purpose and application. For example, the amount of crosslinking agent is, for example, 0.001 to 10 parts by mass, preferably 0.01 to 1.0 part by mass, per 100 parts by mass of the cured resin.

[0343] In addition, a curing catalyst (crosslinking catalyst) can be added together with the crosslinking agent. The crosslinking catalyst is not particularly limited and is appropriately selected depending on the type of crosslinking agent. For example, when an isocyanate crosslinking agent is added, the curing catalyst (crosslinking catalyst) can be, for example, a known urethane catalyst, more specifically, for example, a known organometallic catalyst and a known amine catalyst.

[0344] The amount and timing of addition of the curing catalyst (crosslinking catalyst) are appropriately determined depending on the purpose and application. For example, the amount of the curing catalyst (crosslinking catalyst) is, for example, 0.001 to 10 parts by mass, preferably 0.01 to 1.0 part by mass, per 100 parts by mass of the cured resin.

[0345] Furthermore, the above-mentioned additives can be added to the coating material (crosslinkable composition) as needed. The amount and timing of addition of the additives are appropriately determined depending on the purpose and application.

[0346] If necessary, the solid content of the paint can be adjusted. Specifically, if necessary, the solvent can be removed from the paint, or a solvent can be added to the paint. The solid content of the paint is, for example, 10 to 50 mass%, preferably 20 to 40 mass%.

[0347] Next, in this method, the coating material is applied to an arbitrary substrate to obtain a coating film, and then the obtained coating film is heated to volatilize the solvent and crosslink the cured resin.

[0348] The heating conditions are not particularly limited, but the heating temperature is, for example, 20 to 100° C., preferably 40 to 80° C. The reaction time is, for example, 1 to 100 hours, preferably 10 to 50 hours.

[0349] In this way, the cured resin can be crosslinked.

[0350] The method for obtaining a crosslinked cured resin material is not limited to the above. For example, when the copolymerizable monomer contains a polyfunctional copolymerizable monomer, a crosslinked cured resin material is directly obtained as a reaction product of the radical polymerization reaction.

[0351] Examples of the polyfunctional copolymerizable monomer include polyfunctional (meth)acrylates.

[0352] Examples of polyfunctional (meth)acrylates include bifunctional (meth)acrylates and trifunctional or higher functional (meth)acrylates.

[0353] Examples of bifunctional (meth)acrylates include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate. acrylate, pentaerythritol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, tris(2-hydroxyethyl)isocyanurate-di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and bisphenol A di(meth)acrylate. These can be used alone or in combination of two or more.

[0354] Examples of tri- or higher functional (meth)acrylates include trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and dipentaerythritol-poly(meth)acrylate. These can be used alone or in combination of two or more.

[0355] Examples of polyfunctional copolymerizable monomers include allyl(meth)acrylate, vinyl(meth)acrylate, divinylbenzene, epoxy poly(meth)acrylate, polyester poly(meth)acrylate, urethane poly(meth)acrylate, butyldiol poly(meth)acrylate, and hexyldiol poly(meth)acrylate. These can be used alone or in combination of two or more.

[0356] The polyfunctional copolymerizable monomers can be used alone or in combination of two or more. The content of the polyfunctional copolymerizable monomers in the polymerizable composition is appropriately set depending on the purpose and application.

[0357] Then, by the above-mentioned method, the polymerizable composition containing the polyfunctional copolymerizable monomer is irradiated with active energy rays and / or heated to cure (radical polymerize) the polymerizable composition, thereby obtaining a cured resin product crosslinked by the polyfunctional copolymerizable monomer.

[0358] The cured resin contains a structural unit derived from the compound represented by formula (1), and therefore the cured resin has relatively good adhesiveness, a relatively good refractive index, and a relatively good flexibility.

[0359] That is, the cured resin is a pressure-sensitive adhesive having a relatively excellent refractive index and flexibility. In other words, since the pressure-sensitive adhesive contains a structural unit derived from the compound represented by formula (1), it has a relatively excellent refractive index and flexibility. In particular, if the cured resin is crosslinked with a crosslinking agent, the pressure-sensitive adhesive has a relatively excellent mechanical properties as well as a relatively excellent refractive index and flexibility.

[0360] More specifically, the pressure-sensitive adhesive has a relatively high refractive index. The refractive index of the pressure-sensitive adhesive is, for example, 1.58 or more, preferably 1.59 or more, more preferably 1.60 or more, and even more preferably 1.62 or more. The refractive index of the pressure-sensitive adhesive is, for example, 1.80 or less, preferably 1.70 or less. The refractive index is measured in accordance with the examples described below.

[0361] The pressure-sensitive adhesive also has relatively high flexibility. The lower limit of the shear storage modulus (G') of the pressure-sensitive adhesive at 10°C is, for example, 0.005 MPa or more, preferably 0.010 MPa or more, more preferably 0.020 MPa or more, and even more preferably 0.050 MPa or more. The upper limit of the shear storage modulus (G') of the pressure-sensitive adhesive at 10°C is not particularly limited, but is, for example, 1.0 MPa or less. The shear storage modulus (G') at 10°C is measured in accordance with the examples described below.

[0362] 4. Pressure-sensitive adhesive composition The pressure-sensitive adhesive composition is a resin composition having adhesive properties (pressure-sensitive adhesion, tackiness). More specifically, the pressure-sensitive adhesive composition contains the above-mentioned pressure-sensitive adhesive (i.e., cured resin) and an additive. Preferably, the pressure-sensitive adhesive composition consists of the above-mentioned pressure-sensitive adhesive and an additive.

[0363] Examples of additives include those mentioned above, and specific examples include plasticizers, crosslinking agents, silane coupling agents, antifoaming agents, leveling agents, mildew inhibitors, rust inhibitors, matting agents, flame retardants, thixotropic agents, tackifiers, thickeners, lubricants, antistatic agents, surfactants, reaction retarders, crosslinking retarders, antioxidants, ultraviolet absorbers, hydrolysis inhibitors, weathering stabilizers, heat stabilizers, dyes, inorganic pigments, organic pigments, anti-tack agents, inorganic fillers, and organic fillers. These may be used alone or in combination of two or more.

[0364] From the viewpoint of the weather resistance of the PSA composition, preferred additives include an ultraviolet absorber, a light stabilizer, and an antioxidant. That is, the additive preferably includes at least one selected from the group consisting of an ultraviolet absorber, a light stabilizer, and an antioxidant.

[0365] The ratio of the additive (at least one additive selected from the group consisting of an ultraviolet absorber, a light stabilizer, and an antioxidant) to the total amount of the pressure-sensitive adhesive composition is, for example, 1 × 10 －６ Parts by mass (ppm) or more, preferably 10 x 10 －６ Parts by mass (ppm) or more, more preferably 100 x 10 －６From the viewpoint of cost efficiency, the proportion of the additive (at least one additive selected from the group consisting of an ultraviolet absorber, a light stabilizer, and an antioxidant) is, for example, 100,000×10 parts by mass or more relative to 1 part by mass of the total amount of the pressure-sensitive adhesive composition. －６ Parts by mass (ppm) or less, preferably 50,000 x 10 －６ Parts by mass (ppm) or less, more preferably 30,000 x 10 －６ It is less than parts by mass (ppm).

[0366] The ultraviolet absorber is not particularly limited, and examples thereof include known ultraviolet absorbers (for example, those described in the BASF Japan catalog, the ADEKA catalog, and the CLARIANT catalog). More specific examples of ultraviolet absorbers include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, benzylidene-based ultraviolet absorbers, and triazine-based ultraviolet absorbers. These are used alone or in combination of two or more. From the viewpoint of weather resistance, the ultraviolet absorber is preferably a benzotriazole-based ultraviolet absorber. The blending ratio of the ultraviolet absorber is, for example, 1 x 10 relative to 1 part by mass of the total amount of the pressure-sensitive adhesive composition. －６ Parts by mass (ppm) or more, preferably 10 x 10 －６ Parts by mass (ppm) or more, more preferably 100 x 10 －６ From the viewpoint of cost reduction, the blending ratio of the ultraviolet absorber is, for example, 100,000×10 parts by mass per part by mass of the total amount of the pressure-sensitive adhesive composition. －６ Parts by mass (ppm) or less, preferably 50,000 x 10 －６ Parts by mass (ppm) or less, more preferably 30,000 x 10 －６ It is less than parts by mass (ppm).

[0367] The light resistance stabilizer is not particularly limited, and examples thereof include known light resistance stabilizers (for example, those described in the BASF Japan catalog and the ADEKA catalog). More specific examples of the light resistance stabilizer include hindered amine (HALS) light resistance stabilizers and benzoate light resistance stabilizers. These are used alone or in combination of two or more. From the viewpoint of weather resistance, the light resistance stabilizer is preferably a hindered amine (HALS) light resistance stabilizer. The blending ratio of the light resistance stabilizer relative to 1 part by mass of the total amount of the pressure-sensitive adhesive composition described above is, for example, 1 x 10 －６ Parts by mass (ppm) or more, preferably 10 x 10 －６ Parts by mass (ppm) or more, more preferably 100 x 10 －６ From the viewpoint of cost reduction, the blending ratio of the light resistance stabilizer is, for example, 100,000×10 parts by mass per part by mass of the total amount of the pressure-sensitive adhesive composition. －６ Parts by mass (ppm) or less, preferably 50,000 x 10 －６ Parts by mass (ppm) or less, more preferably 30,000 x 10 －６ It is less than parts by mass (ppm).

[0368] The antioxidant is not particularly limited, and examples thereof include known antioxidants (for example, those described in the BASF Japan catalog and the ADEKA catalog). More specific examples of the antioxidant include phenol-based antioxidants, phosphorus-based antioxidants, and thiophene-based antioxidants. These are used alone or in combination of two or more. From the viewpoint of weather resistance, a phenol-based antioxidant is preferably used as the antioxidant. The blending ratio of the antioxidant is, for example, 1 x 10 relative to 1 part by mass of the total amount of the pressure-sensitive adhesive composition. －６ Parts by mass (ppm) or more, preferably 10 x 10 －６ Parts by mass (ppm) or more, more preferably 100 x 10 －６ From the viewpoint of cost efficiency, the blending ratio of the antioxidant is, for example, 100,000×10 parts by mass per part by mass of the total amount of the pressure-sensitive adhesive composition. －６ Parts by mass (ppm) or less, preferably 50,000 x 10 －６Parts by mass (ppm) or less, more preferably 30,000 x 10 －６ It is less than parts by mass (ppm).

[0369] The method for obtaining the pressure-sensitive adhesive composition is not particularly limited. For example, the additive is added to the polymerizable composition and / or coating material (crosslinkable composition). Then, a pressure-sensitive adhesive (i.e., a cured resin) is obtained using the polymerizable composition and / or coating material containing the additive by the above-mentioned method. As a result, a pressure-sensitive adhesive composition containing the pressure-sensitive adhesive and the additive is obtained.

[0370] 5. Effects The pressure-sensitive adhesive has a relatively excellent refractive index and flexibility because it has a structural unit derived from the compound represented by formula (1). Furthermore, according to the method for producing the compound, a compound for obtaining a pressure-sensitive adhesive having an excellent refractive index and flexibility can be efficiently obtained.

[0371] Furthermore, the pressure-sensitive adhesive composition contains the pressure-sensitive adhesive, and therefore has a relatively excellent refractive index and flexibility.

[0372] Therefore, the above-mentioned pressure-sensitive adhesive and pressure-sensitive adhesive composition are suitably used in various industrial fields as pressure-sensitive adhesives that can adhere to various adherends.

[0373] The adherend is not particularly limited, but examples thereof include paper, cloth, leather, resin sheets, rubber sheets, foams, metals, glass, and wood.

[0374] Furthermore, the pressure-sensitive adhesive and pressure-sensitive adhesive composition contain sulfur atoms. Therefore, the pressure-sensitive adhesive and pressure-sensitive adhesive composition have excellent adhesion to metals. As a result, the pressure-sensitive adhesive is suitable for use in fields where the adherend is metal. Examples of such fields include the fields of building materials, electronic components, semiconductors, component sealing, automotive components, aviation components, and sporting goods.

[0375] Examples of building materials include barrier materials, roofing materials, solar panel materials, battery packaging materials, window materials, outdoor flooring materials, lighting protection materials, automotive parts, signs, and stickers. Examples of electronic components include electronic materials and laminates for electrical and electronic circuits, more specifically, flexible copper-clad laminates, coverlays, bonding sheets, resin-coated copper foils, multilayer printed wiring boards, capacitors, underfill materials, interchip fills for 3D-LSIs, insulating sheets, heat dissipation substrates, and metal foil adhesives for heat dissipation films.

[0376] Furthermore, the pressure-sensitive adhesive and pressure-sensitive adhesive composition have an excellent refractive index. As a result, the pressure-sensitive adhesive and pressure-sensitive adhesive composition are suitable for use in the optical field. That is, the pressure-sensitive adhesive and pressure-sensitive adhesive composition are preferably optical pressure-sensitive adhesives and optical pressure-sensitive adhesive compositions.

[0377] Examples of applications of the optical pressure-sensitive adhesive and the optical pressure-sensitive adhesive composition include displays, antireflection films (e.g., antireflection films attached to displays), film mirrors, optical waveguides (e.g., sheet-like optical waveguides and optical waveguide films), and optical connectors.

[0378] Particularly preferably, the optical pressure-sensitive adhesive and the optical pressure-sensitive adhesive composition are used as materials for displays.

[0379] More specifically, in recent years, bendable and / or flexible displays have been put to practical use as displays for organic EL display devices. Examples of such displays include foldable displays and rollable displays. Bendable and / or flexible displays require optical pressure-sensitive adhesives that can adapt to bending and / or curvature. More specifically, pressure-sensitive adhesives that combine a relatively high refractive index and relatively high flexibility are required. However, from the perspective of refractive index, relatively high crystallinity is required, while from the perspective of flexibility, relatively low crystallinity is required. Therefore, there is a trade-off between refractive index and flexibility, making it difficult to achieve both a relatively high refractive index and a relatively high flexibility.

[0380] In contrast, the above-mentioned pressure-sensitive adhesive and pressure-sensitive adhesive composition have relatively excellent refractive index and flexibility because they contain structural units derived from the compound represented by formula (1), and are therefore particularly suitable for use as optical pressure-sensitive adhesives and optical pressure-sensitive adhesive compositions that can conform to bending and / or curvature.

[0381] The method for producing the compound described above is suitable for use in obtaining various pressure-sensitive adhesives and pressure-sensitive adhesive compositions in the various industrial fields described above. Note that the above fields are merely examples, and the present invention is not limited to the above.

[0382] Specific numerical values ​​of the blending ratios (content ratios), physical property values, parameters, etc. used in the following description can be replaced with the upper limit values ​​(numerical values ​​defined as "not more than" or "less than") or lower limit values ​​(numerical values ​​defined as "not less than" or "exceeding") of the corresponding blending ratios (content ratios), physical property values, parameters, etc. described in the above "Modes for Carrying Out the Invention." Furthermore, unless otherwise specified in the following description, "parts" and "%" are based on mass.

[0383] 1. Compounds (Polymerizable Monomers) Example 1 (1) Synthesis of PE-DMEA 1-Acryloylthio-5-phenyl-3-thiapentane (PE-DMEA) was synthesized by the following method.

[0384] More specifically, a hydrocarbon thio group-containing thiol was prepared (preparation step) as shown in the following synthesis steps 1 and 2. More specifically, as shown in synthesis step 1, mercaptoethanol was reacted with a first modifying agent to produce a hydrocarbon thio group-containing alcohol. Next, as shown in synthesis step 2, the hydrocarbon thio group-containing alcohol was reacted with thiourea to produce a hydrocarbon thio group-containing thiol. Thereafter, as shown in the following synthesis step 3, the hydrocarbon thio group-containing thiol was reacted with a second modifying agent to produce a compound containing a (meth)acryloylthio group ((meth)acryloyl group-forming step).

[0385] (Synthesis Step 1: Synthesis of 1-hydroxy-5-phenyl-3-thiapentane) Into a four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet line, and a dropping funnel, 67.6 g (865 mmol) of 2-mercaptoethanol and 150 mL of ethyl acetate (solvent) were charged and mixed.

[0386] Next, while stirring the contents of the flask, 92.8 g (891 mmol) of styrene (a vinyl compound) and 0.71 g (4.3 mmol) of AIBN (azobisisobutyronitrile, a radical initiator) were slowly added to the flask to obtain a homogeneous solution.

[0387] Next, nitrogen gas was bubbled into the above solution at a rate of 10 mL / min for 3 hours. After stopping the nitrogen gas bubbling, the temperature of the solution was raised to 60°C and stirred under a nitrogen atmosphere for 24 hours. That is, 2-mercaptoethanol and styrene were subjected to an ene-thiol reaction.

[0388] The temperature of the solution was lowered to room temperature, and 200 mL of ethyl acetate and 200 mL of a 10% by mass aqueous potassium carbonate solution were added, followed by stirring for 1 hour.

[0389] After stopping the stirring and allowing to stand for 1 hour, the organic layer was separated and concentrated under reduced pressure to obtain 167 g of a crude product containing 1-hydroxy-5-phenyl-3-thiapentane as a hydrocarbon thio group-containing alcohol.

[0390] The resulting crude product was purified by vacuum distillation (pressure: 0.3 kPa), and the fraction with a vapor temperature of 127 to 130° C. was collected to obtain 114.0 g of 1-hydroxy-5-phenyl-3-thiapentane.

[0391] 1-hydroxy-5-phenyl-3-thiapentane is as follows: １ H-NMR (400MHz, CDCl ３ ) was identified.

[0392] １ H-NMR (400MHz, CDCl ３ ​): δ7.34-7.27 (m, 2H) δ7.25-7.18 (m, 3H) δ3.71 (tt, J=6.0, 6.0Hz, 2H) δ2.93-2.87 (m, 2H) δ2.82-2.77 (m, 2H) δ2.74 (t, J=6.0Hz, 2H) δ2.08 (t, J=6.0Hz, 1H)

[0393] (Synthesis Step 2: Synthesis of 1-mercapto-5-phenyl-3-thiapentane)

[0394] A four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet line and a dropping funnel was charged with 50.0 g (274 mol) of 1-hydroxy-5-phenyl-3-thiapentane and 40 mL of water, and these were mixed.

[0395] Next, while stirring the contents of the flask, 38.9 g of 36% hydrochloric acid (hydrohalic acid) and 21.9 g (288 mmol) of thiourea were slowly added to the flask to obtain a solution. The solution was heated to reflux and then stirred at reflux for 3 hours. That is, the hydrocarbon thio group-containing alcohol and thiourea were reacted to obtain an isothiuronium salt.

[0396] The temperature of the solution was then lowered to 60° C. Then, while stirring the solution in the flask, 100 mL of toluene was slowly added to the flask.

[0397] Next, the temperature of the solution was adjusted to be maintained at 55° C. to 60° C., and while stirring the contents of the flask, 28.9 g of a 26% aqueous ammonia solution (aqueous base solution) was slowly added to the flask, followed by stirring for 2 hours at 60° C. In other words, the isothiuronium salt was hydrolyzed by the aqueous ammonia solution.

[0398] The temperature of the solution was then lowered to room temperature, and 100 mL of 1N hydrochloric acid was added to the flask, followed by stirring for 1 hour.

[0399] Then, stirring was stopped, and the solution was allowed to stand for 1 hour. The organic layer was then separated from the solution, and the resulting organic layer was concentrated under reduced pressure. As a result, 54.0 g of 1-mercapto-5-phenyl-3-thiapentane was obtained as a hydrocarbon thio group-containing thiol.

[0400] 1-mercapto-5-phenyl-3-thiapentane is as follows: １ H-NMR (400MHz, CDCl ３ ) was identified.

[0401] １ H-NMR (400MHz, CDCl ３ ): δ7.34-7.27 (m, 2H) δ7.25-7.18 (m, 3H) δ2.94-2.65 (m, 8H) δ1.71 (t, J=7.6, 1H)

[0402] (Synthesis Step 3: Synthesis of 1-acryloylthio-5-phenyl-3-thiapentane (PE-DMEA)) In a four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet line, and a dropping funnel, 5.0 g (25.2 mmol) of 1-mercapto-5-phenyl-3-thiapentane as a hydrocarbon thio group-containing thiol was dissolved in 10 mL of dichloromethane (solvent).

[0403] Next, while stirring the contents of the flask, 3.36 g (26.5 mmol) of 3-chloropropionic acid chloride (second modifier) ​​was slowly charged into the flask, and the contents of the flask were stirred at room temperature until 1-mercapto-5-phenyl-3-thiapentane disappeared.

[0404] Next, 20 mL of saturated sodium bicarbonate water was added to the flask, and the contents of the flask were stirred for 1 hour. Then, stirring was stopped and the contents were allowed to stand for 1 hour. After that, the organic layer was separated from the contents of the flask.

[0405] The separated organic layer was then placed in a four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet line, and a dropping funnel, and 2.8 g (27.7 mmol) of triethylamine (second modifier) ​​was then added to the flask while adjusting the reaction temperature to maintain it at 5 to 15°C.​

[0406] Next, 20 mL of 1N hydrochloric acid was added to the flask while stirring the contents of the flask, and the mixture was stirred for 1 hour. Then, the stirring was stopped, and the contents of the flask were allowed to stand for 1 hour. That is, the mercapto group was modified by the reaction of the hydrocarbon thiol group-containing thiol with the second modifying agent, and a (meth)acryloylthio group was formed.

[0407] Thereafter, the organic layer was separated from the content of the flask, and the obtained organic layer was concentrated under reduced pressure to distill off dichloromethane (solvent), thereby obtaining 5.44 g of a crude product containing PE-DMEA.

[0408] The crude product was then purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate=20 / 1 (volume ratio)) to obtain 5.25 g of PE-DMEA.

[0409] PE-DMEA is as follows: １ H-NMR (400MHz, CDCl ３ ) was identified.

[0410] １ H-NMR (400MHz, CDCl ３ ): δ7.33-7.27 (m, 2H) δ7.26-7.18 (m, 3H) δ6.39 (dd, J=9.6Hz, 17.2Hz, 1H) δ6.32 (dd, J=1.6Hz, 17.2Hz, 1H) δ5.71 (dd, J=1.6Hz, 9.6Hz, 1H) δ3.19-3.12 (m, 2H) δ2.96-2.83 (m, 4H) δ2.76-2.70 (m, 2H)

[0411] That is, PE-DMEA is a compound represented by the above formula (1) (R １ represents a 2-phenylethyl group, and R ２ represents a hydrogen atom, and R ３ represents a hydrogen atom, n represents 1, Y represents a sulfur atom, and X represents a sulfur atom.

[0412] ​(2) Evaluation of Physical Properties <Refractive Index nD and Abbe Number> The refractive index and Abbe number of PE-DMEA were measured in accordance with ASTM D 542. The results are shown in Table 1.

[0413] More specifically, the refractive index of PE-DMEA was measured using an Abbe refractometer (DR-M4 / 1550, manufactured by Atago Co., Ltd.). The interference filters used were D line (589 nm, manufactured by Atago Co., Ltd.; RE-16501), F line (486 nm, manufactured by Atago Co., Ltd.; RE-16502), and C line (656 nm, manufactured by Atago Co., Ltd.; RE-16503). The sample temperature was set to 20°C.

[0414] Thereafter, the Abbe number was calculated from the refractive index measurement results using the following formula: Abbe number = (nD-1) / (nF-nC) nD: refractive index at D line nF: refractive index at F line nC: refractive index at C line

[0415] <Viscosity> The viscosity of PE-DMEA was measured using an E-type viscometer (TVE-25L, manufactured by Toki Sangyo Co., Ltd.) at a temperature of 25° C. and a rotation speed of 2.5 rpm. The results are shown in Table 1.

[0416] Example 2 (1) Synthesis of PE-DETGA 1-Acryloylthio-8-phenyl-3,6-dithiaoctane (PE-DETGA) was synthesized by the following method.

[0417] More specifically, as shown in the following synthesis step 1, an oxyalkylene group was introduced into the hydrocarbon thio group-containing thiol obtained in Example 1 above to synthesize an oxyalkylene-introduced alcohol (oxyalkylene group introduction step). Next, the hydroxyl group of the oxyalkylene-introduced alcohol was converted into a mercapto group (mercapto group formation step) to obtain a thioalkylene-introduced thiol (preparation step). Thereafter, as shown in the following synthesis step 2, the thioalkylene-introduced thiol was reacted with a second modifying agent to produce a compound containing a (meth)acryloylthio group ((meth)acryloyl group formation step).

[0418] (Synthesis Step 1: Synthesis of 1-mercapto-8-phenyl-3,6-dithiaoctane) Into a four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet line, and a dropping funnel, 5.0 g (25.2 mmol) of 1-mercapto-5-phenyl-3-thiapentane as the hydrocarbon thio group-containing thiol synthesized in Synthesis Step 2 of Example 1 and 10 mL of dichloromethane (solvent) were placed and dissolved.

[0419] Next, 10.0 mL of purified water and 1.01 g (25.2 mmol) of sodium hydroxide (base) were slowly added to the flask while stirring the contents of the flask to obtain a solution.

[0420] The solution was then cooled in an ice bath. Next, while stirring the solution in the flask, 7.61 g of a tetrahydrofuran solution of ethylene oxide (14.6% solution, 25.2 mmol) was added dropwise to the flask. The rate of addition was adjusted so that the temperature of the solution was maintained at 0 to 10°C.

[0421] The solution was then returned to room temperature and stirred at room temperature for 1 hour. To the solution, 20 mL of toluene and 20 mL of 1N hydrochloric acid were then added, and the mixture was stirred for 1 hour. After stirring was stopped, the organic layer was separated from the solution. The resulting organic layer was concentrated under reduced pressure to obtain 6.0 g of a crude product containing 1-hydroxy-8-phenyl-3,6-dithiaoctane as the oxyalkylene-introduced alcohol.

[0422] Into a four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet line, and a dropping funnel, 5.0 g of the obtained crude product and 3.0 mL of water were added, and the mixture was stirred.

[0423] Next, while stirring the contents of the flask, 2.92 g of 36% hydrochloric acid (hydrohalic acid) and 1.65 g (21.7 mmol) of thiourea were slowly added to the flask to obtain a solution. The solution was heated to reflux and then stirred at reflux for 3 hours. That is, the oxyalkylene-introduced alcohol and thiourea were reacted to obtain an isothiuronium salt.

[0424] The temperature of the solution was then lowered to 60° C. Then, while stirring the solution in the flask, 10 mL of toluene was slowly added to the flask.

[0425] Next, the temperature of the solution was adjusted to be maintained at 55°C to 60°C, and then, while stirring the content of the flask, 2.2 g of a 26% aqueous ammonia solution (aqueous base solution) was slowly added to the flask, and the mixture was stirred at 60°C for 2 hours. That is, the isothiuronium salt was hydrolyzed by the aqueous ammonia solution.

[0426] The temperature of the solution was then lowered to room temperature, and 10 mL of 1N hydrochloric acid was added to the flask, followed by stirring for 1 hour.

[0427] Then, stirring was stopped, and the solution was allowed to stand for 1 hour. The organic layer was then separated from the solution, and the resulting organic layer was concentrated under reduced pressure. As a result, 5.6 g of a crude product containing 1-mercapto-8-phenyl-3,6-dithiaoctane as a thioalkylene-introduced thiol was obtained.

[0428] The obtained crude product was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate=20 / 1 (volume ratio)) to obtain 4.5 g of 1-mercapto-8-phenyl-3,6-dithiaoctane.

[0429] 1-mercapto-8-phenyl-3,6-dithiaoctane is as follows: １ H-NMR (400MHz, CDCl ３ ) was identified.

[0430] １ H-NMR (400MHz, CDCl ３ ): δ7.33-7.27 (m, 2H) δ7.25-7.15 (m, 3H) δ2.93-2.68 (m, 12H) δ1.73 (t, J=7.6, 1H)

[0431] ​(Synthesis Step 2: Synthesis of 1-acryloylthio-8-phenyl-3,6-dithiaoctane (PE-DETGA)) Into a four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet line, and a dropping funnel, 2.0 g (7.7 mmol) of 1-mercapto-8-phenyl-3,6-dithiaoctane as a thioalkylene-introduced thiol (hydrocarbon thio group-containing thiol) and 10 mL of dichloromethane (solvent) were added and dissolved.

[0432] Next, while stirring the contents of the flask, 0.98 g (7.7 mmol) of 3-chloropropionic acid chloride (second modifier) ​​was slowly added to the flask, and the contents of the flask were stirred at room temperature until 1-mercapto-8-phenyl-3,6-dithiaoctane disappeared.

[0433] Next, 20 mL of saturated sodium bicarbonate water was added to the flask, and the contents of the flask were stirred for 1 hour. Then, stirring was stopped and the contents were allowed to stand for 1 hour. After that, the organic layer was separated from the contents of the flask.

[0434] The separated organic layer was then placed in a four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet line, and a dropping funnel, and 0.81 g (8.0 mmol) of triethylamine (second modifier) ​​was added to the flask while adjusting the reaction temperature to maintain it at 5 to 15°C.

[0435] Next, 20 mL of 1N hydrochloric acid was added to the flask while stirring the contents of the flask, and the mixture was stirred for 1 hour. Then, the stirring was stopped, and the contents of the flask were allowed to stand for 1 hour. That is, the mercapto group was modified by the reaction of the hydrocarbon thiol group-containing thiol with the second modifying agent, and a (meth)acryloylthio group was formed.

[0436] Thereafter, the organic layer was separated from the contents of the flask, and the obtained organic layer was concentrated under reduced pressure to distill off dichloromethane (solvent), thereby obtaining 2.1 g of a crude product containing PE-DETGA.

[0437] The crude product was then purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate=20 / 1 (volume ratio)) to obtain 2.0 g of PE-DETGA.

[0438] PE-DETGA is as follows: １ H-NMR (400MHz, CDCl ３ ) was identified.

[0439] １ H-NMR (400MHz, CDCl ３ ): δ7.33-7.27 (m, 2H) δ7.25-7.18 (m, 3H) δ6.38 (dd, J=9.6Hz, 17.2Hz, 1H) δ6.30 (dd, J=1.6Hz, 17.2Hz, 1H) δ5.71 (dd, J=1.6Hz, 9.6Hz, 1H) δ3.19-3.12 (m, 2H) δ2.94-2.70 (m, 10H)

[0440] That is, PE-DETGA is a compound represented by the above formula (1) (R １ represents a 2-phenylethyl group, and R ２ represents a hydrogen atom, and R ３ represents a hydrogen atom, n represents 2, Y represents a sulfur atom, and X represents a sulfur atom.

[0441] (2) Evaluation of Physical Properties The refractive index and Abbe number of PE-DETGA were measured in the same manner as in Example 1. The results are shown in Table 1. The viscosity of PE-DETGA was also measured in the same manner as in Example 1. The results are shown in Table 1.

[0442] Example 3 (1) Synthesis of Ph-DMEA 1-Acryloylthio-2-phenylthioethane (Ph-DMEA) was synthesized by the following method.

[0443] More specifically, a hydrocarbon thio group-containing thiol was prepared (preparation step) as shown in the following synthesis step 1. Then, as shown in the following synthesis step 2, the hydrocarbon thio group-containing thiol was reacted with a second modifying agent to produce a compound containing a (meth)acryloylthio group ((meth)acryloyl group-forming step).

[0444] ​(Synthesis Step 1: Synthesis of 2-(phenylthio)-ethane-1-thiol)

[0445] A four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet line, and a dropping funnel was charged with 29.0 g (188 mol) of 2-(phenylthio)ethanol (commercially available product) and 10 mL of water, and these were mixed.

[0446] Next, while stirring the contents of the flask, 28.6 g of 36% hydrochloric acid (hydrohalic acid) and 15.7 g (207 mmol) of thiourea were slowly added to the flask to obtain a solution. The solution was heated to reflux and then stirred at reflux for 3 hours. That is, the hydrocarbon thio group-containing alcohol and thiourea were reacted to obtain an isothiuronium salt.

[0447] The temperature of the solution was then lowered to 60° C. Then, while stirring the solution in the flask, 100 mL of toluene was slowly added to the flask.

[0448] Next, the temperature of the solution was adjusted to be kept at 55°C to 60°C, and while stirring the solution in the flask, 20.9 g of a 26% aqueous ammonia solution (aqueous base solution) was slowly added to the flask, followed by stirring at 60°C for 2 hours.

[0449] The temperature of the solution was then lowered to room temperature, and 100 mL of 1N hydrochloric acid was added to the flask, followed by stirring for 1 hour.

[0450] Then, stirring was stopped, and the solution was allowed to stand for 1 hour. The organic layer was then separated from the solution, and the resulting organic layer was concentrated under reduced pressure. As a result, 31.0 g of 2-(phenylthio)-ethane-1-thiol was obtained as a hydrocarbon thio group-containing thiol.

[0451] 2-(phenylthio)-ethane-1-thiol is as follows: １ H-NMR (400MHz, CDCl ３ ) was identified.

[0452] １ H-NMR (400MHz, CDCl ３ ​): δ7.39-7.20 (m, 5H) δ3.15-3.10 (m, 2H) δ2.76-2.69 (m, 2H) δ1.71 (t, J=8.4Hz, 1H)

[0453] (Synthesis Step 2: Synthesis of 1-acryloylthio-2-phenylthioethane (Ph-DMEA)) In a four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet line, and a dropping funnel, 35.2 g (207 mmol) of 2-(phenylthio)-ethane-1-thiol as a hydrocarbon thio group-containing thiol was dissolved in 200 mL of dichloromethane (solvent).

[0454] Next, while stirring the contents of the flask, 27.6 g (217 mmol) of 3-chloropropionic acid chloride (second modifying agent) was slowly charged into the flask, and the contents of the flask were stirred at room temperature until 2-(phenylthio)-ethane-1-thiol disappeared.

[0455] Next, 200 mL of saturated sodium bicarbonate water was added to the flask, and the contents of the flask were stirred for 1 hour. Then, stirring was stopped and the contents were allowed to stand for 1 hour. After that, the organic layer was separated from the contents of the flask.

[0456] The separated organic layer was then placed in a four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet line, and a dropping funnel, and 26.4 g (260 mmol) of triethylamine (second modifier) ​​was then added while adjusting the reaction temperature to maintain it at 5 to 15°C.

[0457] Next, 20 mL of 1N hydrochloric acid was added to the flask while stirring the contents of the flask, and the mixture was stirred for 1 hour. Then, the stirring was stopped, and the contents of the flask were allowed to stand for 1 hour. That is, the mercapto group was modified by the reaction of the hydrocarbon thiol group-containing thiol with the second modifying agent, and a (meth)acryloylthio group was formed.

[0458] Thereafter, the organic layer was separated from the contents of the flask, and the obtained organic layer was concentrated under reduced pressure to distill off dichloromethane (solvent), thereby obtaining 5.44 g of a crude product containing Ph-DMEA.

[0459] The obtained crude product was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate=20 / 1 (volume ratio)) to obtain 38.2 g of Ph-DMEA.

[0460] Ph-DMEA is as follows: １ H-NMR (400MHz, CDCl ３ ) was identified.

[0461] １ H-NMR (400MHz, CDCl ３ ): δ7.45-7.19 (m, 5H) δ6.38 (dd, J=9.6Hz, 17.2Hz, 1H) δ6.31 (dd, J=17.2Hz, 1.6Hz, 1H) δ5.72 (dd, J=1.6Hz, 9.6Hz, 1H) δ3.20-3.08 (m, 4H)

[0462] That is, Ph-DMEA is a compound represented by the above formula (1) (R １ represents a phenyl group (Ph), and R ２ represents a hydrogen atom, and R ３ represents a hydrogen atom, n represents 1, Y represents a sulfur atom, and X represents a sulfur atom.

[0463] (2) Evaluation of Physical Properties The refractive index and Abbe number of Ph-DMEA were measured in the same manner as in Example 1. The results are shown in Table 1. The viscosity of Ph-DMEA was also measured in the same manner as in Example 1. The results are shown in Table 1.

[0464] Example 4 (1) Synthesis of Bn-DMEA 1-Acryloylthio-2-benzylthioethane (Bn-DMEA) was synthesized by the following method.

[0465] ​More specifically, a hydrocarbon thio group-containing thiol was prepared (preparation step) as shown in the following synthesis steps 1 and 2. More specifically, as shown in synthesis step 1, mercaptoethanol was reacted with a first modifying agent to produce a hydrocarbon thio group-containing alcohol. Next, as shown in synthesis step 2, the hydrocarbon thio group-containing alcohol was reacted with thiourea to produce a hydrocarbon thio group-containing thiol. Thereafter, as shown in the following synthesis step 3, the hydrocarbon thio group-containing thiol was reacted with a second modifying agent to produce a compound containing a (meth)acryloylthio group ((meth)acryloyl group-forming step).

[0466] (Synthesis Step 1: Synthesis of 2-(benzylthio)-ethanol) 134.6 g (1723 mol) of 2-mercaptoethanol and 500 mL of water (solvent) were placed in a four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet line, and a dropping funnel, and then mixed.

[0467] Next, while stirring the contents of the flask, 68.9 g (1723 mmol) of sodium hydroxide (basic compound) was slowly charged into the flask to obtain a homogeneous solution.

[0468] Next, the temperature of the solution was adjusted to be kept at 10°C or less, and 294.7 g (1723 mmol) of benzyl bromide (halogenated hydrocarbon) was slowly added to the flask while stirring the contents of the flask, followed by stirring at 25°C for 1 hour.

[0469] Next, while stirring the contents of the flask, 500 mL of toluene was slowly added to the flask and stirred for 1 hour, thereby allowing a nucleophilic substitution reaction between 2-mercaptoethanol and benzyl bromide.

[0470] Then, stirring was stopped, and the solution was allowed to stand. The organic layer was separated from the solution, and the obtained organic layer was concentrated under reduced pressure. As a result, 279.1 g of 2-(benzylthio)-ethanol was obtained as a hydrocarbon thio group-containing alcohol.

[0471] 2-(benzylthio)-ethanol is as follows: １H-NMR (400MHz, CDCl ３ ) was identified.

[0472] １ H-NMR (400MHz, CDCl ３ ): δ7.35-7.22 (m, 5H) δ3.73 (s, 2H) δ3.67 (dd, J=6.0Hz, 6.0Hz, 2H) δ2.64 (d, J=6.0Hz, 2H) δ2.07 (d, J=6.0Hz, 1H)

[0473] (Synthesis Step 2: Synthesis of 2-(benzylthio)-ethane-1-thiol) Into a four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet line, and a dropping funnel, 150.0 g (892 mmol) of 2-(benzylthio)-ethanol and 150 mL of water were placed and mixed.

[0474] Next, while stirring the contents of the flask, 135.4 g of 36% hydrochloric acid (hydrohalic acid) and 74.7 g (981 mmol) of thiourea were slowly added to the flask to obtain a solution. The solution was heated to a reflux state and then stirred at reflux for 3 hours. That is, the hydrocarbon thio group-containing alcohol and thiourea were reacted to obtain an isothiuronium salt.

[0475] The temperature of the solution was then lowered to 60° C. Then, while stirring the solution in the flask, 100 mL of toluene was slowly added to the flask.

[0476] Next, the temperature of the solution was adjusted to be maintained at 55° C. to 60° C., and while stirring the contents of the flask, 85.0 g (1,516 mmol) of potassium hydroxide was slowly added to the flask, followed by stirring for 2 hours at 60° C. In other words, the isothiuronium salt was hydrolyzed by the aqueous potassium hydroxide solution.

[0477] The temperature of the solution was then lowered to room temperature, and 100 mL of 1N hydrochloric acid was added to the flask, followed by stirring for 1 hour.

[0478] ​Then, stirring was stopped, and the solution was allowed to stand for 1 hour. The organic layer was then separated from the solution, and the resulting organic layer was concentrated under reduced pressure. As a result, 143.0 g of 2-(benzylthio)-ethane-1-thiol was obtained as a hydrocarbon thio group-containing thiol.

[0479] 2-(benzylthio)-ethane-1-thiol is as follows: １ H-NMR (400MHz, CDCl ３ ) was identified.

[0480] １ H-NMR (400MHz, CDCl ３ ): δ7.35-7.23 (m, 5H) δ3.74 (s, 2H) δ2.67-2.62 (m, 4H) δ1.69-1.64 (m, 1H)

[0481] (Synthesis Step 3: Synthesis of 1-acryloylthio-2-benzylthioethane (Bn-DMEA)) In a four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet line, and a dropping funnel, 20.0 g (109 mmol) of 2-(benzylthio)-ethane-1-thiol as a hydrocarbon thio group-containing thiol was dissolved in 100 mL of dichloromethane (solvent).

[0482] Next, while stirring the contents of the flask, 15.2 g (119 mmol) of 3-chloropropionic acid chloride (second modifying agent) was slowly charged into the flask, and the contents of the flask were stirred at room temperature until 2-(benzylthio)-ethane-1-thiol disappeared.

[0483] Next, 200 mL of saturated sodium bicarbonate water was added to the flask, and the contents of the flask were stirred for 1 hour. Then, stirring was stopped and the contents were allowed to stand for 1 hour. After that, the organic layer was separated from the contents of the flask.

[0484] The separated organic layer was then placed in a four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet line, and a dropping funnel, and 14.5 g (143 mmol) of triethylamine (second modifier) ​​was then placed in the flask while adjusting the reaction temperature to maintain it at 5 to 15°C. ​

[0485] Next, while stirring the contents of the flask, 200 ml of 1N hydrochloric acid was added to the flask, and the mixture was stirred for 1 hour. Then, the stirring was stopped, and the contents of the flask were allowed to stand for 1 hour. The mercapto group was modified by the reaction of the hydrocarbon thiol group-containing thiol with the second modifying agent, and a (meth)acryloylthio group was formed.

[0486] Thereafter, the organic layer was separated from the content of the flask, and the obtained organic layer was concentrated under reduced pressure to distill off dichloromethane (solvent), thereby obtaining 25.6 g of a crude product containing Bn-DMEA.

[0487] The crude product was then purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate=20 / 1 (volume ratio)) to obtain 24.3 g of Bn-DMEA.

[0488] The Bn-DMEA is as follows: １ H-NMR (400MHz, CDCl ３ ) was identified.

[0489] １ H-NMR (400MHz, CDCl ３ ): δ7.37-7.22 (m, 5H) δ6.37 (dd, J=9.2Hz, 17.2Hz, 1H) δ6.30 (dd, J=17.2Hz, 1.6Hz, 1H) δ5.70 (dd, J=1.6Hz, 9.2Hz, 1H) δ3.79 (s, 2H) δ3.16-3.10 (m, 2H) δ2.66-2.61 (m, 2H)

[0490] That is, Bn-DMEA is a compound represented by the above formula (1) (R １ represents a benzyl group (Bz), and R ２ represents a hydrogen atom, and R ３ represents a hydrogen atom, n represents 1, Y represents a sulfur atom, and X represents a sulfur atom.

[0491] (2) Evaluation of Physical Properties The refractive index and Abbe number of Bn-DMEA were measured in the same manner as in Example 1. The results are shown in Table 1. The viscosity of Bn-DMEA was also measured in the same manner as in Example 1. The results are shown in Table 1.​

[0492] Example 5 (1) Synthesis of PE-DMEMA 1-methacryloylthio-5-phenyl-3-thiapentane (PE-DMEMA) was synthesized by the following method.

[0493] More specifically, 3.34 g (26.5 mmol) of 3-chloropropionic acid chloride used in step 3 of the synthesis of PE-DMEA in Example 1 was changed to 3.74 g (26.5 mmol) of 3-chloro-2-methyl-propionic acid chloride. Except for the above, PE-DMEMA was synthesized in the same manner as PE-DMEA in Example 1.

[0494] PE-DMEMA is as follows: １ H-NMR (400MHz, CDCl ３ ) was identified.

[0495] １ H-NMR (400MHz, CDCl ３ ): δ7.33-7.27 (m, 2H) δ7.26-7.18 (m, 3H) δ6.05 (m, 1H) δ5.60 (m, 1H) δ3.19-3.12 (m, 2H) δ2.96-2.83 (m, 4H) δ2.76-2.70 (m, 2H) δ1.93 (d, J=2Hz, 3H)

[0496] That is, PE-DMEMA is a compound represented by the above formula (1) (R １ represents a 2-phenylethyl group, and R ２ represents a hydrogen atom, and R ３ represents a methyl group, n represents 1, Y represents a sulfur atom, and X represents a sulfur atom.

[0497] (2) Evaluation of Physical Properties The refractive index and Abbe number of PE-DMEMA were measured in the same manner as in Example 1. The results are shown in Table 1. The viscosity of PE-DMEMA was also measured in the same manner as in Example 1. The results are shown in Table 1.

[0498] Comparative Example 1 (1) Synthesis of PE-HMEA 1-Acryloyloxy-5-phenyl-3-thiapentane (PE-HMEA) was synthesized by the following method.

[0499] ​A four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet line, and a dropping funnel was charged with 2.0 g (11.0 mmol) of 1-hydroxy-5-phenyl-3-thiapentane synthesized in Synthesis Step 1 of Example 1 and 10 mL of dichloromethane (solvent), and these were dissolved.

[0500] Then, 2.79 g (21.9 mmol) of 3-chloropropionic acid chloride was slowly charged to the flask while stirring the contents of the flask, and the contents of the flask were stirred at room temperature until 1-hydroxy-5-phenyl-3-thiapentane disappeared.

[0501] Next, 20 mL of saturated sodium bicarbonate water was added to the flask, and the contents of the flask were stirred for 1 hour. Then, stirring was stopped and the contents were allowed to stand for 1 hour. After that, the organic layer was separated from the contents of the flask.

[0502] The separated organic layer was then placed in a four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet line, and a dropping funnel, and 1.7 g (16.5 mmol) of triethylamine was then added while adjusting the reaction temperature to maintain it at 5 to 15°C.

[0503] 20 mL of 1N hydrochloric acid was then added to the flask while stirring the contents of the flask, and the stirring was continued for 1 hour. Then, stirring was stopped and the contents of the flask were allowed to stand for 1 hour.

[0504] Thereafter, the organic layer was separated from the content of the flask, and the obtained organic layer was concentrated under reduced pressure to distill off dichloromethane (solvent), thereby obtaining 2.20 g of a crude product containing PE-HMEA.

[0505] The crude product was then purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate=20 / 1) to obtain 2.10 g of PE-HMEA.

[0506] The PE-HMEA is as follows: １ H-NMR (400MHz, CDCl ３ ) was identified. １ H-NMR (400MHz, CDCl ３): δ7.33-7.27 (m, 2H) δ7.26-7.18 (m, 3H) δ6.42 (dd, J=1.6Hz, 17.2Hz, 1H) δ6.13 (dd, J=10.4Hz, 17.2Hz, 1H) δ5.85 (dd, J=1.6Hz, 10.4Hz, 1H) δ4.31 (t, J=7.0Hz, 2H) δ2.94-2.82 (m, 4H) δ2.80 (t, J=7.0Hz, 2H)

[0507] That is, PE-HMEA was not a compound represented by the above formula (1). １ represents a phenyl group (Ph), and R ２ represents a hydrogen atom, and R ３ represents a hydrogen atom, Y represents a sulfur atom, n represents 1, and X represents an oxygen atom.

[0508] (2) Evaluation of Physical Properties The refractive index and Abbe number of PE-HMEA were measured in the same manner as in Example 1. The results are shown in Table 1. The viscosity of PE-HMEA was also measured in the same manner as in Example 1. The results are shown in Table 1.

[0509] 2. Pressure-sensitive adhesive (homopolymer) Examples 6 to 10 and Comparative Example 2 According to the formulations shown in Table 2, 1.0 g (100 parts by mass) of the compound (polymerizable monomer) obtained in Examples 1 to 5 and Comparative Example 1 was placed in a brown test tube. Furthermore, 4.0 g of toluene and 19.5 mg (3 mol %) of AIBN were also placed in the test tube. The contents of the test tube were then mixed to obtain a polymerizable composition.

[0510] Next, the polymerizable composition was degassed and the reaction system was substituted with nitrogen by a freeze vacuum degassing method using liquid nitrogen.

[0511] The temperature of the polymerizable composition was then raised to 60°C and stirred for 12 hours to polymerize the polymerizable composition. The temperature of the reaction product was then lowered to room temperature, and dry air was ventilated into the test tube. The contents of the test tube were then concentrated under reduced pressure to remove toluene. Thus, a pressure-sensitive adhesive was obtained.

[0512] (2) Physical Property Evaluation <Molecular Weight> 10 mg of adhesive was dissolved in 2 ml of tetrahydrofuran to prepare a sample. The sample was then analyzed by gel permeation chromatography (GPC) under the following conditions to determine the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (Mw / Mn). The results are shown in Table 2.

[0513] (Measurement conditions) Apparatus: LC-40D (Shimadzu Corporation) Column: GPC-80M (Shimadzu Corporation) Detector: Differential refractive index detector Free liquid: Tetrahydrofuran Flow rate: 0.75 mL / min Column temperature: 40°C Detector temperature: 40°C Injection volume: 10 μL

[0514] <Refractive Index nD and Abbe Number> The refractive index and Abbe number of the pressure-sensitive adhesive were measured in the same manner as in Example 1. The results are shown in Table 2.

[0515] <Storage Modulus and Glass Transition Temperature> The dynamic viscoelasticity of the pressure-sensitive adhesive was measured under the following conditions. The shear storage modulus (G') and glass transition temperature (Tg) at 10°C were then determined. The results are shown in Table 2.

[0516] Equipment; MCR １ 02 (manufactured by Anton Paar) Deformation mode: Shear mode Shape: Parallel plate (8.0 mm φ, gap 0.1 mm) Temperature range: -30°C to 50°C Temperature rise rate: 5°C / min Frequency: 1 Hz Environment: Dry air

[0517] The glass transition temperature was calculated by the following method. First, the shear storage modulus (G') and shear loss modulus (G'') were determined, and tan δ (loss tangent, G'' / G') was calculated. The temperature at which the loss tangent (tan δ) showed a maximum value (peak value) was calculated as the glass transition temperature.

[0518] 3. Pressure-Sensitive Adhesive (Copolymer) Examples 11-15 and Comparative Example 3 (1) Preparation of Resin Varnish According to the formulation shown in Table 3, 9.5 g (95 parts by mass) of the compound (polymerizable monomer) obtained in Examples 1-5 and Comparative Example 1 and 0.5 g (5 parts by mass) of 4-hydroxybutyl acrylate (copolymerizable monomer, 4HBA) were placed in a brown four-neck flask equipped with a stirrer, thermometer, and nitrogen inlet line. Furthermore, 15.0 g of toluene (solvent, 150 parts by mass) and 50.0 mg of AIBN (polymerization initiator, 0.5 parts by mass) were placed in the flask. The contents of the flask were then mixed to obtain a polymerizable composition.

[0519] Next, the polymerizable composition was degassed and the reaction system was substituted with nitrogen by a freeze vacuum degassing method using liquid nitrogen.

[0520] The temperature of the contents of the flask was then raised to 60°C and stirred for 12 hours to polymerize the polymerizable composition. Thereafter, the temperature of the contents of the flask was lowered to room temperature, and dry air was ventilated into the flask. As a result, a toluene solution of a cured resin (hereinafter referred to as resin varnish) AP-1 (solids concentration 40%) was obtained.

[0521] (2) Preparation of Paint The above resin varnish AP-1 was mixed with iron (III) acetylacetonate (urethane catalyst) as a curing catalyst, acetylacetone as a crosslinking retarder, and an isocyanurate derivative of hexamethylene diisocyanate (isocyanate crosslinking agent, trade name Takenate D-170N, manufactured by Mitsui Chemicals) as a crosslinking agent. This mixture was then diluted with toluene. As a result, paint AA-1 (a crosslinkable composition containing a cured resin and a crosslinking agent) with a solids concentration of 25% by mass was obtained.

[0522] The amount of the curing catalyst was 0.1 parts by mass, the amount of the crosslinking retarder was 2.0 parts by mass, and the amount of the crosslinking agent was 0.1 parts by mass, relative to 100 parts by mass of the solid content of the resin varnish AP-1.

[0523] (3) Preparation of Pressure-Sensitive Adhesive and Laminate The above-mentioned coating material (crosslinkable composition) AA-1 was applied to one side of a corona-treated polyethylene terephthalate film (thickness 38 μm, manufactured by Toray Industries, model number: Lumirror 38S10 (hereinafter referred to as corona-treated PET film)) to obtain a coating film. The coating film was then heated at 130°C for 5 minutes to obtain a pressure-sensitive adhesive having a thickness of 30 μm.

[0524] Also, a polyethylene terephthalate film (thickness: 40 μm (hereinafter referred to as silicone-treated PET film)) that had been subjected to a release treatment with a silicone-based release agent was prepared. The silicone-treated PET film was then attached to one side of the pressure-sensitive adhesive.

[0525] As a result of the above, a laminate (AS-1) was obtained which had the corona-treated PET film, the pressure-sensitive adhesive, and the silicone-treated PET film in that order in the thickness direction.

[0526] In addition, a laminate (AL-1) having a silicone-treated PET film, a pressure-sensitive adhesive, and a silicone-treated PET film in that order in the thickness direction was obtained by the same procedure as above, except that a silicone-treated PET film was used instead of the corona-treated PET film.

[0527] The laminate (AS-1) was then cut to a width of 25 mm, and the silicone-treated PET film was peeled off to expose the adhesive, which was then pressure-bonded to the surface of a glass substrate (size: 26 × 76 mm, thickness: 0.9 to 1.2 mm, manufactured by Matsunami Glass Industrial Co., Ltd., model number: S7213).

[0528] As a result of the above, a laminate (GP-1) was obtained which had the corona-treated PET film, the pressure-sensitive adhesive, and the glass substrate in this order in the thickness direction.

[0529] (2) Evaluation of Physical Properties <Refractive Index nD and Abbe Number> The silicone-treated PET films on both sides of the laminate (AL-1) were peeled off, and the pressure-sensitive adhesive was taken out.

[0530] The refractive index and Abbe number of the adhesive were measured in the same manner as in Example 1. The results are shown in Table 3.

[0531] <Storage Modulus (Flexibility) and Glass Transition Temperature> The silicone-treated PET films on both sides of the laminate (AL-1) were peeled off to remove the pressure-sensitive adhesive.

[0532] A plurality of adhesives were laminated to obtain a sample having a thickness of about 0.5 mm.

[0533] The dynamic viscoelasticity of the sample was measured in the same manner as in Example 1. The shear storage modulus (G') and glass transition temperature (Tg) at 10°C were then determined. The results are shown in Table 3.

[0534] <Peel strength, yellowness (b ＊ Peel strength and haze value> The peel strength of the laminate (GP-1) was measured in accordance with JIS Z 0237 (2000).

[0535] The temperature was 23°C, the humidity was 50% RH, the pulling speed was 300 mm / min, and the peeling direction was 180°. The peel strengths of the four laminates were measured and the average values ​​of the obtained results were calculated. The average values ​​are shown in Table 3.

[0536] b of the above laminate (GP-1) ＊ The value and haze value were measured using a spectral color haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., model number COH-7700).

[0537] In addition, the b of the glass substrate ＊ The b value and haze value of the silicone-treated PET film were measured by the above-mentioned method. ＊ The thickness and haze values ​​were measured by the methods described above.

[0538] And, b of the laminate (GP-1) ＊ From the value, the b ＊ value and b of silicone-treated PET film ＊ By subtracting the value, the b ＊ The values ​​were calculated, and the results are shown in Table 3.

[0539] The haze value of the adhesive was calculated by subtracting the haze value of the glass substrate and the haze value of the silicone-treated PET film from the haze value of the laminate (GP-1). The results are shown in Table 3.

[0540] <Weather Resistance Test> The laminate (GP-1) was subjected to a weather resistance test. More specifically, the laminate (GP-1) was exposed to ultraviolet light under the following conditions.

[0541] Light source: Xenon lamp Black panel temperature: 55°C Humidity: 55% Rain conditions: None Irradiation conditions: 36.5 W / m ２ (300-400 nm) Filter: inside / outside = Right Light / Cira-Quartz Irradiation surface: cured film side Irradiation time: 100 hours

[0542] After the weather resistance test, the peel strength and yellowness index (b ＊ The results are shown in Table 3.

[0543] <Heat Resistance Test> The laminate (GP-1) was subjected to a heat resistance test. More specifically, the laminate (GP-1) was exposed to the following conditions.

[0544] Temperature: 85°C Humidity: 20% Test time: 100 hours

[0545] After the heat resistance test, the peel strength and yellowness index (b ＊ The results are shown in Table 3.

[0546] 4. Pressure-sensitive adhesive compositions Examples 16 to 21 (1) Preparation of resin varnish According to the formulation shown in Table 4, the compound (polymerizable monomer) obtained in Example 1 and 4-hydroxybutyl acrylate (copolymerizable monomer, 4HBA) were polymerized to obtain a polymerizable composition. Next, according to the formulation shown in Table 4, additives were added to the polymerizable composition. Except for the above, a resin varnish (solid concentration 40%) was obtained in the same manner as in Example 11.

[0547] The following ultraviolet absorbers and light stabilizers were used as additives.

[0548] Tinuvin 1600: Triazine-based UV absorber, (2-[4,6-bis(biphenyl-4-yl)-1,3,5-triazin-2-yl]-5-[(2-ethylhexyl)oxy]phenol), manufactured by BASF Japan. Tinuvin 360: Benzotriazole-based UV absorber, (2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-tert-octylphenol]), manufactured by BASF Japan. Tinuvin PA144: Hindered amine-based light stabilizer, (bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate), manufactured by BASF Japan. Tinuvin 765: hindered amine-based light stabilizer, a mixture of 75 parts by mass of bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and 25 parts by mass of 1-methyl 10-(1,2,2,6,6-pentamethyl-4-piperidinyl) decanedioate, manufactured by BASF Japan. Tinuvin 249: hindered amine-based light stabilizer, 2,2,6,6-tetramethyl-1-{2-[(3,5,5-trimethylhexanoyl)oxy]ethyl}-4-piperidyl 3,5,5-trimethylhexanoate, manufactured by BASF Japan.

[0549] (2) Preparation of Paint A paint having a solid content concentration of 25% by mass was obtained in the same manner as in Example 11, except that a resin varnish containing the above additives was used.

[0550] (3) Preparation of adhesive composition and laminate: A coating was heated at 130°C for 5 minutes on one side of a film to obtain an adhesive, and an adhesive composition containing the adhesive and the additives was obtained in the same manner as in Example 11, except that the resin varnish was used. Furthermore, a laminate (GP-1) was produced in the same manner as in Example 11, except that the adhesive composition was used to bond the film. Table 4 shows the formulation of Example 11, along with the formulations of Examples 16 to 21.

[0551] (2) Evaluation of Physical Properties <Weather Resistance Test No. 2> The laminates (GP-1) of Examples 11 and 16 to 21 were evaluated under conditions stricter than those of the above weather resistance test.

[0552] More specifically, the laminates (GP-1) of Examples 11 and 16 to 21 were exposed to light under the following conditions using a solar simulator.

[0553] Device name: UVACUBE400 / SOL500 (manufactured by Honle) Light source: Metal halide lamp Irradiation conditions: 80 W / m ２ (295-3000 nm) Filter: H2 filter Irradiation surface: cured film side Irradiation time: 100 hours

[0554] After the weather resistance test, the peel strength and yellowness index (b ＊ The results are shown in Table 4.

[0555]

[0556]

[0557]

[0558]

[0559] Details of the abbreviations in the table are as follows: PE-DMEA: 1-acryloylthio-5-phenyl-3-thiapentane PE-DETGA: 1-acryloylthio-8-phenyl-3,6-dithiaoctane Ph-DMEA: 1-acryloylthio-2-phenylthioethane Bn-DMEA: 1-acryloylthio-2-benzylthioethane PE-HMEA: 1-acryloyloxy-5-phenyl-3-thiapentane PE-DMEMA: 1-methacryloylthio-5-phenyl-3-thiapentane 4HBA: 4-hydroxybutyl acrylate Tinuvin 1600: triazine-based ultraviolet absorber, (2-[4,6-bis(biphenyl-4-yl)-1,3,5-triazin-2-yl]-5-[(2-ethylhexyl)oxy]phenol), manufactured by BASF Japan Tinuvin 360: benzotriazole-based ultraviolet absorber, (2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-tert-octylphenol]), manufactured by BASF Japan. Tinuvin PA144: hindered amine-based light stabilizer, (bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate), manufactured by BASF Japan. Tinuvin 765: hindered amine-based light stabilizer, a mixture of 75 parts by mass of bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and 25 parts by mass of 1-methyl 10-(1,2,2,6,6-pentamethyl-4-piperidinyl) decanedioate, manufactured by BASF Japan. Tinuvin 249: hindered amine light stabilizer, 2,2,6,6-tetramethyl-1-{2-[(3,5,5-trimethylhexanoyl)oxy]ethyl}-4-piperidyl 3,5,5-trimethylhexanoate, manufactured by BASF Japan

[0560] The above invention is provided as an exemplary embodiment of the present invention, but it is merely an example and should not be interpreted as being limiting. Modifications of the present invention that are obvious to those skilled in the art are intended to be included in the scope of the following claims.

[0561] The pressure-sensitive adhesive and the method for producing the compound of the present invention are suitably used in the fields of building materials, electronic parts, semiconductors, component sealing, automotive parts, aircraft parts, and sporting goods.

Claims

1. A pressure-sensitive adhesive having a structural unit derived from a compound represented by the following formula (1): (In formula (1), R １ represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or an araliphatic hydrocarbon group. ２ are the same or different and represent a hydrogen atom or a methyl group. ３ represents a hydrogen atom or a methyl group. n represents an integer of 1 or more. When n represents 1, X represents a sulfur atom and Y represents a sulfur atom. When n represents an integer of 2 or more, X represents a sulfur atom or an oxygen atom and Y represents a sulfur atom or an oxygen atom, with at least one Y representing a sulfur atom.

2. In formula (1), R １ The pressure-sensitive adhesive according to claim 1 , wherein represents an aromatic hydrocarbon group or an araliphatic hydrocarbon group.

3. In formula (1), R １ The pressure-sensitive adhesive according to claim 1, wherein represents a 2-phenylethyl group.

4. The pressure-sensitive adhesive according to claim 1, wherein in formula (1), n ​​is an integer of 2 or more, and X is a sulfur atom.

5. The pressure-sensitive adhesive according to claim 1, wherein in formula (1), n ​​represents an integer of 2 or more, and all Y's represent sulfur atoms.

6. The pressure-sensitive adhesive according to claim 1, further comprising a structural unit derived from a hydroxyl group-containing mono(meth)acrylate.

7. The pressure-sensitive adhesive according to claim 1, which is an optical pressure-sensitive adhesive.

8. A pressure-sensitive adhesive composition containing the pressure-sensitive adhesive of claim 1 and an additive, wherein the additive comprises at least one selected from the group consisting of an ultraviolet absorber, a light stabilizer, and an antioxidant, and the ratio of the additive to 1 part by mass of the total amount of the pressure-sensitive adhesive composition is 10 x 10 －６ Mass part or more 100000×10 －６ The pressure-sensitive adhesive composition is 0.05 parts by mass or less.

9. A method for producing a compound represented by the following formula (1), comprising: a preparation step of preparing a thiol and / or alcohol represented by the following formula (2): and a (meth)acryloyl group formation step of modifying a mercapto group of the thiol to a (meth)acryloylthio group and / or modifying a hydroxyl group of the alcohol to a (meth)acryloyloxy group. (In formula (1), R １ represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or an araliphatic hydrocarbon group. ２ are the same or different and represent a hydrogen atom or a methyl group. ３ represents a hydrogen atom or a methyl group. n represents an integer of 1 or more. When n represents 1, X represents a sulfur atom and Y represents a sulfur atom. When n represents an integer of 2 or more, X represents a sulfur atom or an oxygen atom and Y represents a sulfur atom or an oxygen atom, with at least one Y representing a sulfur atom. (In formula (2), R １ , R ２ , n, Y and X are defined as R １ , R ２ , n, Y and X have the same meanings as those of the formula (I).

10. The method for producing a compound according to claim 9, wherein the preparation step comprises a thioalkylene group introduction step of introducing a thioalkylene group into the thiol, and the thioalkylene group introduction step comprises: an oxyalkylene group introduction step of introducing an oxyalkylene group into the thiol to obtain an oxyalkylene-introduced alcohol; and a mercapto group formation step of converting a hydroxyl group of the oxyalkylene-introduced alcohol to a mercapto group to obtain a thioalkylene-introduced thiol.

11. A compound represented by the following formula (1'): (In formula (1'), n represents an integer of 1 or more.)

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