Pressure-sensitive adhesive, pressure-sensitive adhesive composition, and compound

Abstract

This pressure-sensitive adhesive includes a structural unit derived from a compound represented by formula (1). (In formula (1), R1 represents an aromatic hydrocarbon group or an araliphatic hydrocarbon group, the R2 moieties are the same or different and each represent a hydrogen atom or a methyl group, R3 represents a hydrogen atom or a methyl group, m is an integer of 1 or larger, n is an integer of 1 or larger, and X represents a sulfur atom or an oxygen atom.)

Description

Adhesive, adhesive composition and compound

[0001] The present invention relates to a pressure-sensitive adhesive, a pressure-sensitive adhesive composition 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 monomers containing a (meth)acryloyloxy group include 8-acryloyloxy-3,6,10,13-tetrathiapentadecane (Et-ECHA-A) [chemical formula: CH ２ =CHCOO-CH(CH ２ SCH ２ CH ２ SCH ２ CH ３ ) has been proposed (see, for example, Patent Document 1 (Chemical Formula 5)).

[0004] International Publication No. 2023 / 080599

[0005] In recent years, there has been a demand for adhesives with a relatively high refractive index, but adhesives obtained using the above-mentioned 8-acryloyloxy-3,6,10,13-tetrathiapentadecane (Et-ECHA-A) may not have a sufficient refractive index.

[0006] The present invention relates to a pressure-sensitive adhesive having a relatively excellent refractive index, a pressure-sensitive adhesive composition containing the pressure-sensitive adhesive, and a novel 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 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; m represents an integer of 1 or more; n represents an integer of 1 or more; and X represents a sulfur atom or an oxygen atom.

[0010] The present invention [2] is a compound represented by the formula (1), wherein R １ represents a 2-phenylethyl group.

[0011] The present invention [3] further comprises the pressure-sensitive adhesive according to the above [1] or [2], which further comprises a structural unit derived from a hydroxyl group-containing mono(meth)acrylate.

[0012] The present invention [4] further comprises the pressure-sensitive adhesive according to any one of the above [1] to [3], which further comprises a structural unit derived from a crosslinking agent.

[0013] The present invention [5] includes the pressure-sensitive adhesive according to any one of the above [1] to [4], which is an optical member.

[0014] The present invention [6] comprises the pressure-sensitive adhesive according to any one of the above [1] to [4], which is a pressure-sensitive adhesive film.

[0015] The present invention [7] is a pressure-sensitive adhesive composition containing the pressure-sensitive adhesive according to any one of the above [1] to [6] 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 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.

[0016] The present invention [8] includes a compound represented by the following formula (1'): (In formula (1′), R ３ represents a hydrogen atom or a methyl group; m represents an integer of 1 or more; and n represents an integer of 1 or more.

[0017] The pressure-sensitive adhesive of the present invention has a relatively excellent refractive index because it has a structural unit derived from the compound represented by the above formula (1).

[0018] The pressure-sensitive adhesive composition of the present invention contains the above-mentioned pressure-sensitive adhesive, and therefore has a relatively excellent refractive index.

[0019] The compound of the present invention is a novel compound. The above-mentioned adhesive and adhesive composition can be produced using the compound of the present invention.

[0020] 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.

[0021] The glass transition temperature of the pressure-sensitive adhesive is, for example, 20°C or lower, preferably 0°C or lower, more preferably -3°C or lower, and even more preferably -10°C or lower. 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, more preferably -50°C or higher and -3°C or lower, and even more preferably -50°C or higher and -10°C or lower. The glass transition temperature is measured in accordance with the examples described below.

[0022] More specifically, the pressure-sensitive adhesive includes a (meth)acrylic pressure-sensitive adhesive, where (meth)acrylic refers to acrylic and / or methacrylic.

[0023] 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.

[0024] 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.

[0025] 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.

[0026] 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.

[0027]

[0028] (In formula (1), R １ represents 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; m represents an integer of 1 or more; n represents an integer of 1 or more; and X represents a sulfur atom or an oxygen atom.

[0029] The compound represented by the formula (1) is a polymerizable monomer containing a (meth)acryloyl group. More specifically, when X in the formula (1) represents a sulfur atom, the compound represented by the formula (1) is a polymerizable monomer containing a (meth)acryloylthio group. 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.

[0030] 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.

[0031] 2. Compound <R １ In the above formula (1), R １ represents an aromatic hydrocarbon group or an araliphatic hydrocarbon group.

[0032] 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. Preferred aromatic hydrocarbon groups include aromatic hydrocarbon groups having 6 to 10 carbon atoms, and more preferably phenyl (Ph).

[0033] 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 may be used alone or in combination of two or more. As the aromatic aliphatic hydrocarbon group, an aromatic aliphatic hydrocarbon group having 7 to 15 carbon atoms is preferably used, and a 2-phenylethyl group (also known as a phenethyl group, Ph-CH ２ CH ２ -) are listed.

[0034] R １In the above, the aromatic hydrocarbon group and the aromatic aliphatic hydrocarbon group may have a substituent. Examples of the substituent include a halogeno group, a cyano group, an amino group, a carboxy group, a sulfonyl group, and an alkoxy group. 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.

[0035] From the viewpoint of refractive index and weather resistance, in formula (1), R １ represents preferably an aromatic aliphatic hydrocarbon group, more preferably an aromatic aliphatic hydrocarbon group having 7 to 15 carbon atoms, even more preferably an aromatic aliphatic hydrocarbon group having 7 to 10 carbon atoms, and particularly preferably a 2-phenylethyl group (Ph-CH ２ CH ２ -) is indicated.

[0036] <R ２ In the above formula (1), R ２ are the same or different and represent a hydrogen atom or a methyl group.

[0037] More specifically, the compound represented by the formula (1) contains the structural unit [SCHR ２ CHR ２ More specifically, the compound represented by the formula (1) has m structural units [SCHR ２ CHR ２ ] and n structural units [SCHR ２ CHR ２ and the structural unit [SCHR ２ CHR ２ ], in which R ２ are the same or different and represent a hydrogen atom or a methyl group.

[0038] That is, the structural unit [SCHR ２ CHR ２ ], for example, [SCH ２ CH ２ ], [SCH (CH ３ ) CH ２ ], [SCH ２ CH (CH ３ ) )] and [SCH(CH３ ) CH(CH ３ These can be used alone or in combination of two or more.

[0039] In terms of refractive index, preferably, all R ２ represents a hydrogen atom. ２ CHR ２ ] is preferably [SCH ２ CH ２ ] are examples.

[0040] <m and n> In the above formula (1), m and n each represent a structural unit [SCHR ２ CHR ２ ] indicates the number of repeating units.

[0041] In the above formula (1), m represents an integer of 1 or more. More specifically, m represents, for example, 1 to 50, preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 2. m preferably represents 1.

[0042] In the above formula (1), n ​​represents an integer of 1 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 or 2. n preferably represents 1.

[0043] In the above formula (1), m and n may be the same or different from each other. When m and n are the same, the compound represented by the above formula (1) has a symmetric structure. When m and n are different from each other, the compound represented by the above formula (1) has an asymmetric structure. Preferably, in the above formula (1), m and n are the same. That is, the compound represented by the above formula (1) preferably has a symmetric structure. More preferably, in the above formula (1), m and n both represent 1.

[0044] <R ３ In the above formula (1), R ３ represents a hydrogen atom or a methyl group.

[0045] R ３represents a hydrogen atom, the compound represented by the above formula (1) is ２ More specifically, when X represents a sulfur atom, the compound represented by the above formula (1) has an acryloylthio group (CH ２ When X represents an oxygen atom, the compound represented by the formula (1) has an acryloyloxy group (CH ２ =CHCOO-).

[0046] R ３ represents a methyl group, the compound represented by the above formula (1) is ２ =C(CH ３ )COX-). More specifically, when X represents a sulfur atom, the compound represented by the above formula (1) has a methacryloylthio group (CH ２ =C(CH ３ When X represents an oxygen atom, the compound represented by the formula (1) has a methacryloyloxy group (CH ２ =C(CH ３ )COO-).

[0047] R ３ In view of adhesiveness, preferably represents a hydrogen atom. 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-).

[0048] <X> In the above formula (1), X represents a sulfur atom or an oxygen atom. From the viewpoint of refractive index, X preferably represents an oxygen atom. In other words, the compound represented by the above formula (1) preferably has a (meth)acryloyloxy group. The compound represented by the above formula (1) more preferably has an acryloyloxy group (CH ２ =CHCOO-).

[0049] <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.

[0050] In the above formula (1), m and n preferably represent 1. When m and n represent 1 in the above formula (1), the compound is represented, for example, by the following formula (1-1).

[0051]

[0052] (In formula (1-1), R １ , R ２ , R ３ and X are defined as R in formula (1). １ , R ２ , R ３ and X have the same meanings as those of X.)

[0053] In formula (1-1), X preferably represents an oxygen atom, that is, the above compound preferably has a (meth)acryloyloxy group.

[0054] In such a case, the compound is represented by, for example, the following formula (1-1-1).

[0055]

[0056] (In formula (1-1-1), R １、 R ２ and R ３ The meaning of is R in formula (1). １、 R ２ and R ３ The meanings are the same as those of

[0057] In formula (1-1-1), preferably, R ３ represents a hydrogen atom. That is, the above compound more preferably has an acryloyloxy group.

[0058] In such a case, the compound is represented by, for example, the following formula (1-1-1-1).

[0059]

[0060] In formula (1-1-1-1), preferably, all R ２ represents a hydrogen atom. That is, the above compound preferably has a thioethylene group.

[0061] In such a case, the compound is represented by, for example, the following formula (1-1-1-1-1).

[0062]

[0063] (In formula (1-1-1-1-1), R １ The meaning of is R in formula (1). １ The meanings are the same as those of

[0064] In the above formula (1-1-1-1-1), preferably, R １ represents a phenyl group or a 2-ethylphenyl group, and more preferably represents a 2-ethylphenyl group.

[0065] R １ represents a 2-ethylphenyl group, the above compound is represented by the following formula (1-1-1-1-2): The compound represented by the following formula (1-1-1-1-2) is 8-acryloyloxy-1,15-diphenyl-3,6,10,13-tetrathiapentadecane (PE-ECHA-A).

[0066]

[0067] R １ represents a phenyl group, the above compound is represented by the following formula (1-1-1-1-3): The compound represented by the following formula (1-1-1-1-3) is 5-acryloyloxy-1,9-bis(phenylthio)-3,7-dithianonane (Ph-ECHA-A).

[0068]

[0069] In the above description, as specific examples of the compound represented by formula (1), compounds (1-1) to (1-1-1-1-3) in which both m and n in formula (1) are 1 are given; however, the compounds are not limited to the above.

[0070] 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 ２represents a hydrogen atom, and X represents an oxygen atom.

[0071] (In formula (1′), R ３ represents a hydrogen atom or a methyl group; m represents an integer of 1 or more; and n represents an integer of 1 or more.

[0072] In the above formula (1′), R ３ The meaning of is R in the above formula (1). ３ That is, R ３ represents a hydrogen atom or a methyl group, and preferably represents a hydrogen atom from the viewpoint of adhesiveness.

[0073] In the above formula (1'), the meanings of m and n are the same as those of m and n in the above formula (1). That is, m is, for example, 1 to 50, preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 2. Furthermore, n is, for example, 1 to 50, preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 2.

[0074] m and n may be the same as or different from each other. Preferably, m and n are the same as each other. Preferably, both m and n are 1 to 2, and particularly preferably, both m and n are 1.

[0075] A more specific example of the compound represented by the above formula (1') is 8-acryloyloxy-1,15-diphenyl-3,6,10,13-tetrathiapentadecane (PE-ECHA-A) represented by the above formula (1-1-1-1-2).

[0076] 2. Method for Producing Compound The compound represented by the above formula (1) can be produced, for example, by the following method.

[0077] <Preparation Step> In this method, first, a thiol represented by the following formula (2A) and a thiol represented by the following formula (2B) are prepared (preparation step).

[0078]

[0079]

[0080] (In formula (2A) and formula (2B), R １ , R ２ The meanings of n and m are as follows: １ , R ２ , n and m have the same meanings as those of

[0081] In the above formula (2A) and the above formula (2B), R １ The meaning of is R in the above formula (1). １ That is, R １ represents an aromatic hydrocarbon group or an aromatic aliphatic hydrocarbon group, preferably a phenyl group or a 2-ethylphenyl group, more preferably a 2-ethylphenyl group.

[0082] In the above formula (2A) and the above formula (2B), 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.

[0083] In the formula (2A), the meaning of m is the same as the meaning of m in the formula (1). That is, m represents an integer of 1 or more, and preferably represents 1.

[0084] In the formula (2B), n has the same meaning as n in the formula (1). That is, n is an integer of 1 or more, and preferably 1.

[0085] In the formula (2A) and the formula (2B), m and n may be the same or different from each other. Preferably, in the formula (1), the formula (2A) and the formula (2B) are the same, and more preferably, both m and n are 1.

[0086] In the formula (2A) and the formula (2B), the meaning of X is the same as the meaning of X in the formula (1). That is, X represents a sulfur atom or an oxygen atom, and preferably represents an oxygen atom.

[0087] The thiol represented by the formula (2A) and the thiol represented by the formula (2B) are preferably the same as each other. For example, when m and n are both 1 in the formulas (2A) and (2B), the thiol represented by the formula (2A) and the thiol represented by the formula (2B) are both hydrocarbon thio group-containing thiols represented by the following formula (2-1):

[0088]

[0089] (In formula (2-1), 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

[0090] In the above formula (2-1), preferably, R １ represents a phenyl group or a 2-ethylphenyl group, and more preferably represents a 2-ethylphenyl group. ２ indicates a hydrogen atom.

[0091] In the above formula (2-1), R １ represents a 2-ethylphenyl group, and all R ２ When represents a hydrogen atom, the hydrocarbon thio group-containing thiol is represented, for example, by the following formula (2-1-1): The hydrocarbon thio group-containing thiol represented by the following formula (2-1-1) is 1-mercapto-5-phenyl-3-thiapentane.

[0092]

[0093] In addition, in the above formula (2-1), R １ represents a phenyl group, and all R ２ represents a hydrogen atom, the hydrocarbon thio group-containing thiol is represented, for example, by the following formula (2-1-2): The hydrocarbon thio group-containing thiol represented by the following formula (2-1-2) is 2-(phenylthio)-ethane-1-thiol.

[0094]

[0095] The method for preparing the thiol represented by the formula (2) is not particularly limited. For example, the thiol represented by the formula (2) can be obtained as a commercial product. Alternatively, the thiol represented by the formula (2) can be produced. The method for producing the thiol represented by the formula (2) is selected depending on the type of thiol.

[0096] For example, the preparation process includes a hydrocarbon thio group-containing alcohol production process and a mercapto group formation process to produce the thiol represented by the above formula (2). Each process will be described in detail below.

[0097] [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.

[0098] 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 (3):

[0099]

[0100] (In formula (3), R ２ The meaning of is R in formula (1). ２ The meaning is the same as that of

[0101] More specifically, the mercapto alcohol represented by the above formula (3) 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(CH３ These can be used alone or in combination of two or more. 2-mercaptoethanol (SHCH ２ CH ２ OH).

[0102] The first modifying agent converts the mercapto group of the mercapto alcohol into a methyl group represented by R １ and modified with a hydrocarbon group represented by the formula: １ -S-).

[0103] 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.

[0104] 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.

[0105] 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).

[0106] 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.

[0107] 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)).

[0108] 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.

[0109] 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.

[0110] 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.

[0111] 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.

[0112] 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.

[0113] 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.

[0114] 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).

[0115] 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.

[0116] 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.

[0117] 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.

[0118] 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.

[0119] 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.

[0120] 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.

[0121] The hydrocarbon thio group-containing alcohol is represented, for example, by the following formula (4).

[0122]

[0123] (In formula (4), 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

[0124] In the above formula (4), preferably, R １ represents a phenyl group or a 2-ethylphenyl group, and more preferably represents a 2-ethylphenyl group. ２ indicates a hydrogen atom.

[0125] In the above formula (4), R １ represents a 2-ethylphenyl group, and all R ２ When represents a hydrogen atom, the hydrocarbon thio group-containing alcohol is represented, for example, by the following formula (4-1): The hydrocarbon thio group-containing alcohol represented by the following formula (4-1) is 1-hydroxy-5-phenyl-3-thiapentane.

[0126]

[0127] 1-Hydroxy-5-phenyl-3-thiapentane is produced, for example, by the following method. That is, in this method, as shown in the following formula (5), 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), resulting in the production of 1-hydroxy-5-phenyl-3-thiapentane as a hydrocarbon thio group-containing alcohol.

[0128]

[0129] 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.

[0130] [Mercapto Group Formation Step] In the mercapto group formation step, the hydroxyl group of the hydrocarbon thio group-containing alcohol is converted into a mercapto group.

[0131] 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.

[0132] More specifically, in this method, first, a hydrocarbon thio group-containing alcohol and thiourea are mixed and reacted.

[0133] 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.

[0134] 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.

[0135] 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.

[0136] 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.

[0137] The hydrocarbon thio group-containing alcohol is reacted with thiourea to obtain an isothiuronium salt, which is then purified as necessary.

[0138] In this method, an aqueous base solution is then added to the isothiuronium salt to hydrolyze the isothiuronium salt.

[0139] 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.

[0140] 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.

[0141] 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.

[0142] The hydrolysis converts the hydroxyl group of the hydrocarbon thio group-containing alcohol to a mercapto group, resulting in the hydrocarbon thio group-containing thiol represented by the formula (2-1).

[0143] More specifically, when the hydrocarbon thio group-containing alcohol is 1-hydroxy-5-phenyl-3-thiapentane (the above formula (4-1)), in the mercapto group-forming step, as shown in the following formula (6), 1-hydroxy-5-phenyl-3-thiapentane reacts with thiourea, and the reaction product is hydrolyzed with an aqueous base solution (e.g., aqueous ammonia).

[0144] As a result, the hydroxyl group of 1-hydroxy-5-phenyl-3-thiapentane is converted to a mercapto group, and 1-mercapto-5-phenyl-3-thiapentane is obtained as a hydrocarbon thiol group-containing thiol.

[0145]

[0146] 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.

[0147] <Epichlorohydrin Reaction Step> Next, in this method, the hydrocarbon thio group-containing thiol is reacted with epichlorohydrin (epichlorohydrin reaction step).

[0148] More specifically, in this step, a hydrocarbon thio group-containing thiol is reacted with epichlorohydrin. The method for reacting the hydrocarbon thio group-containing thiol with epichlorohydrin is not particularly limited. For example, the hydrocarbon thio group-containing thiol and epichlorohydrin are mixed in a predetermined ratio in the presence of a known basic compound (e.g., sodium hydroxide).

[0149] In the epichlorohydrin reaction step, the mixing ratio of the hydrocarbon thio group-containing thiol per 1 mol of epichlorohydrin is, for example, 2.0 mol or more, preferably 2.0 to 5.0 mol, and more preferably 2.0 to 3.0 mol.

[0150] The reaction conditions are not particularly limited and are appropriately set depending on the purpose and application. 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.

[0151] In this reaction, a solvent is added as needed. Examples of the solvent include water and known organic solvents, and water is preferred. The blending ratio of the solvent is appropriately determined depending on the purpose and application.

[0152] In this reaction, a known basic compound (e.g., sodium hydroxide) is preferably added. The mixing ratio of the basic compound is appropriately set depending on the purpose and application.

[0153] In the epichlorohydrin reaction step, for example, a basic compound dissociates a proton from the mercapto group of the hydrocarbon thio group-containing thiol to generate a nucleophile. The nucleophile derived from the hydrocarbon thio group-containing thiol then undergoes a nucleophilic substitution reaction with epichlorohydrin. This reaction opens the oxirane ring of epichlorohydrin to produce 2-propanol. Furthermore, both terminals of the 2-propanol are modified with the hydrocarbon thio group-containing thiol. As a result, a modified product in which both terminals of 2-propanol are modified with the hydrocarbon thio group-containing thiol (hereinafter referred to as a "2-propanol modified product") is obtained.

[0154] More specifically, when the hydrocarbon thiol group-containing thiol represented by the above formula (2-1) reacts with epichlorohydrin, the 2-propanol modified product is represented by, for example, the following formula (7).

[0155]

[0156] (In formula (7), 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

[0157] In the above formula (7), preferably, R １ represents a phenyl group or a 2-ethylphenyl group, and more preferably represents a 2-ethylphenyl group. ２ indicates a hydrogen atom.

[0158] In the above formula (7), R １ represents a 2-ethylphenyl group, and all R ２ When represents a hydrogen atom, the modified 2-propanol is represented, for example, by the following formula (7-1): The modified 2-propanol represented by the following formula (7-1) is 8-hydroxy-1,15-diphenyl-3,6,10,13-tetrathiapentadecane.

[0159]

[0160] 8-Hydroxy-1,15-diphenyl-3,6,10,13-tetrathiapentadecane is produced, for example, by the following method. That is, in this method, as shown in the following formula (8), two molecules of 1-mercapto-5-phenyl-3-thiapentane are reacted with one molecule of epichlorohydrin in the presence of a basic compound. As a result, 8-hydroxy-1,15-diphenyl-3,6,10,13-tetrathiapentadecane is obtained as a 2-propanol-modified product.

[0161]

[0162] The method for obtaining the modified 2-propanol is not limited to the above, and may be appropriately selected depending on the purpose and application.

[0163] <(Meth)acryloyl Group Forming Step> Next, in this method, the hydroxyl groups of the 2-propanol modified product are modified into (meth)acryloyloxy groups ((meth)acryloyl group forming step).

[0164] More specifically, in this step, the 2-propanol modified product is reacted with a modifying agent for forming a (meth)acryloyl group (hereinafter referred to as a second modifying agent).

[0165] The second modifying agent is a compound that modifies a hydroxyl group to form a (meth)acryloyloxy group.

[0166] 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.

[0167] 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.

[0168] 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.

[0169] 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 specifically, 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 basic compounds include sodium hydroxide, potassium hydroxide, triethylamine, and pyridine. These can be used alone or in combination of two or more.

[0170] 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.

[0171] The blending ratio of the second modifying agent to the modified 2-propanol is not particularly limited and is set appropriately depending on the type of the second modifying agent.

[0172] For example, when the second modifying agent contains a (meth)acrylic acid halide, the 2-propanol modified product 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 hydroxyl groups of the 2-propanol modified product is, for example, 0.8 to 1.5 moles, preferably 0.9 to 1.3 moles.

[0173] For example, when the second modifying agent contains (meth)acrylic anhydride, the 2-propanol modified product and (meth)acrylic anhydride are mixed and subjected to 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 hydroxyl groups of the 2-propanol modified product is, for example, 0.8 to 1.5 moles, preferably 0.9 to 1.3 moles.

[0174] When the second modifying agent contains (meth)acrylic acid and a dehydrating condensing agent, the 2-propanol modified product and (meth)acrylic acid undergo a condensation reaction in the presence of the dehydrating 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 hydroxyl groups of the 2-propanol modified product is, for example, 0.8 to 1.5 moles, preferably 0.9 to 1.3 moles.

[0175] Furthermore, when the second modifying agent contains a propionic acid derivative and a basic compound, the 2-propanol modified product 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 2-propanol modified product and the propionic acid derivative are first subjected to a condensation reaction. Next, the halogen of the reaction product (condensate) is treated (elimination treatment) with a basic compound to form an ethylenically unsaturated bond. This results in the formation of a (meth)acryloyloxy 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 hydroxyl groups of the 2-propanol modified product is, for example, 0.8 to 1.5 moles, preferably 0.9 to 1.3 moles.

[0176] The reaction conditions for the 2-propanol modified product 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 2-propanol modified product and the second modifying agent, if necessary. The type and amount of the solvent are appropriately determined. A known catalyst can be added to the reaction between the 2-propanol modified product and the second modifying agent, if necessary. The type and amount of the catalyst are appropriately selected depending on the type of the 2-propanol modified product and the type of the second modifying agent.

[0177] The reaction of the 2-propanol modified product with the second modifying agent modifies the hydroxyl groups of the 2-propanol modified product to give (meth)acryloyloxy groups. More specifically, the reaction of the 2-propanol modified product represented by the above formula (7) with the second modifying agent gives the compound represented by the above formula (1-1-1).

[0178] More specifically, when the 2-propanol modified product is 8-hydroxy-1,15-diphenyl-3,6,10,13-tetrathiapentadecane (the above formula (7-1)), 3-chloropropionic acid chloride (3CPC) and triethylamine are preferably used as the second modifying agent. In such a case, as shown in the following formula (9), the hydroxyl groups of the 2-propanol modified product are modified with the second modifying agent (e.g., 3CPC and TEA) to form (meth)acryloyloxy groups. As a result, 8-acryloyloxy-1,15-diphenyl-3,6,10,13-tetrathiapentadecane (PE-ECHA-A, the above formula (1-1-1-1-2)) is obtained.

[0179]

[0180] As described above, first, a hydrocarbon thio group-containing thiol is prepared (preparation step), then the hydrocarbon thio group-containing thiol and epichlorohydrin are reacted to produce a 2-propanol modified product (epichlorohydrin reaction step), and then the hydroxyl groups of the 2-propanol modified product are modified to (meth)acryloyloxy groups ((meth)acryloyl group formation step), thereby obtaining the compound represented by the above formula (1).

[0181] <Modifications> The method for obtaining the compound represented by the above formula (1) is not limited to the above, and may be any method for obtaining the compound represented by the above formula (1) １ , R ２ , R ３ , X, m and n, an appropriate method is selected.

[0182] For example, when X represents a sulfur atom in the above formula (1), the hydroxyl group of the 2-propanol modified product is converted to a mercapto group to obtain a 2-propanethiol modified product, and the 2-propanethiol modified product is then reacted with the second modifying agent to modify the mercapto group to a (meth)acryloylthio group. As a result, a compound represented by the above formula (1) (wherein X represents a sulfur atom) is obtained. Note that the method for obtaining the 2-propanethiol modified product is not particularly limited. For example, the 2-propanol modified product is reacted with thiourea to produce an isothiuronium salt, and the isothiuronium salt is then hydrolyzed.

[0183] Furthermore, when n and / or m in the above formula (1) represent an integer of 2 or greater, for example, in the above preparation step, a thioalkylene unit can be introduced into the above hydrocarbon thio group-containing thiol by a known method, and then the hydrocarbon thio group-containing thiol into which the thioalkylene unit has been introduced can be subjected to the epichlorohydrin reaction step and the (meth)acryloyl group formation step.

[0184] 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.

[0185] 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.

[0186] The monomer component contains the compound represented by the above formula (1) as an essential component.

[0187] 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).

[0188] Examples of the copolymerizable monomer include monofunctional copolymerizable monomers and polyfunctional copolymerizable monomers.

[0189] Examples of the monofunctional copolymerizable monomer include monofunctional (meth)acrylates.

[0190] 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.

[0191] 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.

[0192] 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.

[0193] 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.

[0194] 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.

[0195] 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.

[0196] 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.

[0197] 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.

[0198] Additionally, examples of monofunctional copolymerizable monomers include styrene, α-methylstyrene, vinyltoluene, vinylbiphenyl, and divinylbenzene.

[0199] The monofunctional copolymerizable monomers can be used alone or in combination of two or more kinds.

[0200] Examples of the polyfunctional copolymerizable monomer include polyfunctional (meth)acrylates.

[0201] Examples of polyfunctional (meth)acrylates include bifunctional (meth)acrylates and trifunctional or higher functional (meth)acrylates.

[0202] 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.

[0203] 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.

[0204] 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.

[0205] The polyfunctional copolymerizable monomers can be used alone or in combination of two or more kinds.

[0206] 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.

[0207] 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.

[0208] 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.

[0209] 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 1 to 40 mol%, more preferably 5 to 20 mol%.

[0210] 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%.

[0211] 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.

[0212] 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.

[0213] 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.

[0214] 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.

[0215] 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 ２The 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.

[0216] 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.

[0217] By the irradiation of active energy rays and / or heating, the monomer component undergoes radical polymerization (photoradical polymerization and / or thermal radical polymerization), resulting in a cured resin having adhesive properties, i.e., a pressure-sensitive adhesive.

[0218] More specifically, when the monomer component contains the compound represented by the above formula (1) but does not contain a copolymerizable monomer, the compound represented by the above formula (1) is homopolymerized by the above radical polymerization to obtain a homopolymer. That is, the PSA contains, for example, a homopolymer of the compound represented by the above formula (1), and preferably consists of a homopolymer of the compound represented by the above formula (1).

[0219] In such a case, the content of the structural unit derived from the compound represented by the above formula (1) is, for example, 100 mass % relative to the total amount of the pressure-sensitive adhesive.

[0220] Furthermore, when the monomer component contains the compound represented by the above formula (1) and a copolymerizable monomer, the compound represented by the above formula (1) and the copolymerizable monomer are copolymerized by the above radical polymerization to obtain a copolymer. The pressure-sensitive adhesive contains, for example, a copolymer of the compound represented by the above formula (1) and the copolymerizable monomer, and preferably consists of a copolymer of the compound represented by the above formula (1) and the copolymerizable monomer.

[0221] In such a case, the content of the structural unit derived from the compound represented by the formula (1) is, for example, 50% by mass or more and less than 100% by mass, preferably 70% by mass or more and 99% by mass or less, more preferably 90% by mass or more and 95% by mass or less, relative to the total amount of the adhesive. Also, the content of the structural unit derived from the copolymerizable monomer is, for example, more than 0% by mass and 50% by mass or less, preferably 1% by mass or more and 30% by mass or less, more preferably 5% by mass or more and 10% by mass or less, relative to the total amount of the adhesive.

[0222] The pressure-sensitive adhesive has a weight average molecular weight (Mw) of, for example, 10,000 to 500,000, preferably 20,000 to 450,000, and more preferably 30,000 to 400,000.

[0223] The pressure-sensitive adhesive has a number average molecular weight (Mn) of, for example, 5,000 to 200,000, preferably 5,000 to 150,000, or more preferably 9,000 to 100,000.

[0224] The pressure-sensitive adhesive has a dispersity (Mw / Mn) of, for example, 1.1 to 10.0, preferably 1.5 to 9.0, or more preferably 2.0 to 8.0.

[0225] 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.

[0226] Furthermore, the above-mentioned pressure-sensitive adhesive may be crosslinked if necessary. That is, the pressure-sensitive adhesive may be a crosslinked pressure-sensitive adhesive. The method for obtaining the crosslinked pressure-sensitive adhesive is not particularly limited. For example, when the copolymerizable monomer contains a hydroxyl group-containing mono(meth)acrylate, the pressure-sensitive adhesive obtained by the above reaction contains a hydroxyl group. In such a case, for example, the pressure-sensitive adhesive can be crosslinked using a crosslinking agent capable of reacting with a hydroxyl group.

[0227] Preferably, the pressure-sensitive adhesive is crosslinked with a crosslinking agent, in other words, the pressure-sensitive adhesive contains structural units derived from the crosslinking agent.

[0228] 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 pressure-sensitive adhesive, for example, to urethane-crosslink the pressure-sensitive adhesive.

[0229] Examples of isocyanate crosslinking agents include polyisocyanates. That is, the adhesive preferably has structural units derived from polyisocyanates. Examples of polyisocyanates include linear aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and araliphatic polyisocyanates. Examples of linear aliphatic polyisocyanates include pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), and derivatives thereof. Examples of alicyclic polyisocyanates include isophorone diisocyanate (IPDI), norbornene diisocyanate (NBDI), hydrogenated diphenylmethane diisocyanate (HDI), and derivatives thereof. １２ MDI), hydrogenated xylylene diisocyanate (H ６ Examples 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.

[0230] The method for crosslinking the PSA with the crosslinking agent is not particularly limited. For example, first, a PSA having a hydroxyl group is dissolved in a known solvent (e.g., toluene) to prepare a PSA solution (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 solids concentration of the resin varnish is, for example, 10 to 50% by mass, preferably 20 to 40% by mass.

[0231] 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 pressure-sensitive adhesive.

[0232] 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.

[0233] 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 pressure-sensitive adhesive.

[0234] 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.

[0235] 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%.

[0236] 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 adhesive.

[0237] 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.

[0238] In this way, the adhesive can be crosslinked.

[0239] The crosslinking agent is not limited to the above, and for example, the above-mentioned polyfunctional copolymerizable monomers can also be used as the crosslinking agent.

[0240] The shape of the pressure-sensitive adhesive is not particularly limited and can be appropriately set depending on the purpose and use.The shape of the pressure-sensitive adhesive can be, for example, a film, a sheet, a flat plate, a net, a mesh, a block, a sphere, or a polyhedron.Preferably, the pressure-sensitive adhesive has a film shape.In other words, the pressure-sensitive adhesive can preferably be an adhesive film.

[0241] The pressure-sensitive adhesive contains a structural unit derived from the compound represented by formula (1). Therefore, the pressure-sensitive adhesive has relatively excellent adhesion and a relatively excellent refractive index. That is, the pressure-sensitive adhesive has a relatively excellent refractive index. In other words, the pressure-sensitive adhesive contains a structural unit derived from the compound represented by formula (1), and therefore has a relatively excellent refractive index.

[0242] More specifically, the adhesive has a relatively high refractive index because it has a structural unit derived from the compound represented by formula (1). The refractive index of the adhesive is, for example, 1.59 or more, preferably 1.60 or more, and more preferably 1.62 or more. The refractive index of the 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.

[0243] Furthermore, since the pressure-sensitive adhesive has a structural unit derived from the compound represented by the above formula (1), it has relatively high flexibility. 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 0.030 MPa or more. 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.

[0244] 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.

[0245] 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.

[0246] 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.

[0247] 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).

[0248] 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).

[0249] 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).

[0250] 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).

[0251] 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.

[0252] 5. Effects The above-mentioned pressure-sensitive adhesive has a relatively excellent refractive index because it has a structural unit derived from the compound represented by formula (1). Furthermore, the above-mentioned pressure-sensitive adhesive composition has a relatively excellent refractive index because it contains the above-mentioned pressure-sensitive adhesive. Furthermore, the above-mentioned compound is a novel compound, and a pressure-sensitive adhesive and a pressure-sensitive adhesive composition can be produced. Therefore, the above-mentioned pressure-sensitive adhesive, pressure-sensitive adhesive composition, and compound are suitable for use in various industrial fields.

[0253] More specifically, the pressure-sensitive adhesive and pressure-sensitive adhesive composition described above are suitable for use in various industrial fields as pressure-sensitive adhesives and pressure-sensitive adhesive compositions that can adhere to various adherends, including, but not limited to, paper, cloth, leather, resin sheets, rubber sheets, foams, metals, glass, and wood.

[0254] 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 and pressure-sensitive adhesive composition are 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.

[0255] 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.

[0256] Furthermore, the pressure-sensitive adhesive and pressure-sensitive adhesive composition have an excellent refractive index because they contain structural units derived from the compound represented by formula (1). Furthermore, the pressure-sensitive adhesive and pressure-sensitive adhesive composition have relatively excellent flexibility because they contain structural units derived from the compound represented by formula (1). Therefore, the pressure-sensitive adhesive and pressure-sensitive adhesive composition are suitable for use in the optical field. In other words, the pressure-sensitive adhesive and pressure-sensitive adhesive composition are preferably optical components. More specifically, the pressure-sensitive adhesive and pressure-sensitive adhesive composition are preferably optical pressure-sensitive adhesives and optical pressure-sensitive adhesive compositions.

[0257] Examples of applications of the optical pressure-sensitive adhesive and the optical pressure-sensitive adhesive composition include displays, anti-reflection films (e.g., anti-reflection films attached to displays), film mirrors, optical waveguides (e.g., sheet-like optical waveguides and optical waveguide films), and optical connectors, and particularly preferably, displays.

[0258] More specifically, optical pressure-sensitive adhesives and optical pressure-sensitive adhesive compositions are preferably used in the assembly of various devices for optical applications. Examples of such devices include electronic devices, light-emitting devices, lighting devices, optical devices, display devices, and operating devices. More specifically, LED devices, organic EL devices, displays, touch panels, optical information processing devices, lenses, and optical fibers are examples. In particular, in recent years, bendable and / or flexible displays have been put into 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, and 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.

[0259] 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.

[0260] Furthermore, the above-mentioned adhesive and adhesive composition have a relatively excellent refractive index and flexibility, and are therefore suitable for use in touch panels that require shock absorption properties.

[0261] 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.

[0262] 1. Compound (Polymerizable Monomer) Production Example 1 (1) Synthesis of PE-ECHA-A 8-Acryloyloxy-1,15-diphenyl-3,6,10,13-tetrathiapentadecane (PE-ECHA-A) was synthesized by the following method.

[0263] That is, a hydrocarbon thio group-containing thiol was prepared (preparation step) as shown in Synthesis Step 1 and Synthesis Step 2 below. 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, a hydrocarbon thio group-containing thiol was produced by reacting the hydrocarbon thio group-containing alcohol with thiourea. Next, as shown in Synthesis Step 3 below, two molecules of the hydrocarbon thio group-containing thiol were reacted with one molecule of epichlorohydrin to produce a 2-propanol modified product (epichlorohydrin reaction step). Thereafter, as shown in Synthesis Step 4 below, the 2-propanol modified product was reacted with a second modifying agent to produce a compound containing a (meth)acryloyl group ((meth)acryloyl group formation step).

[0264] (Synthesis Step 1: Synthesis of 1-hydroxy-5-phenyl-3-thiapentane) 67.6 g (865 mmol) of 2-mercaptoethanol and 150 mL of ethyl acetate (solvent) were placed in a four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet line, and a dropping funnel, and the mixture was mixed.

[0265] Next, while stirring the content of the flask, 92.8 g (891 mmol) of styrene (first modifier, vinyl compound) and 0.71 g (4.3 mmol) of AIBN (azobisisobutyronitrile, radical initiator) were slowly added to the flask to obtain a homogeneous solution.

[0266] 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.

[0267] 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.

[0268] Stirring was stopped and the mixture was allowed to stand for 1 hour. Thereafter, the organic layer was separated from the contents of the flask. The obtained organic layer was then 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.

[0269] The obtained 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.

[0270] 1-hydroxy-5-phenyl-3-thiapentane is as follows: １ H-NMR (400MHz, CDCl ３ ) was identified.

[0271] 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)

[0272] ​(Synthesis Step 2: Synthesis of 1-mercapto-5-phenyl-3-thiapentane) Into a four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet line, and a dropping funnel, 50.0 g (274 mol) of 1-hydroxy-5-phenyl-3-thiapentane and 40 mL of water were charged and mixed.

[0273] 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 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.

[0274] 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 charged into the flask.

[0275] 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.

[0276] 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.

[0277] Then, stirring was stopped and the solution was allowed to stand for 1 hour. The organic layer was then separated from the solution and 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.

[0278] 1-mercapto-5-phenyl-3-thiapentane is as follows: １ H-NMR (400MHz, CDCl ３ ) was identified.

[0279] 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)

[0280] (Synthesis Step 3: Synthesis of 8-hydroxy-1,15-diphenyl-3,6,10,13-tetrathiapentadecane) In a four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet line, and a dropping funnel, 10.1 g (252 mmol) of sodium hydroxide was dissolved in 90 g of water. Next, 50.0 g (252 mmol) of 1-mercapto-5-phenyl-3-thiapentane as a hydrocarbon thio group-containing thiol was added to the flask and dissolved with stirring.

[0281] Next, the temperature of the solution was adjusted to be maintained at 20°C to 30°C, and 10.5 g (113 mmol) of epichlorohydrin was slowly added to the flask while stirring the contents of the flask, and the contents of the flask were stirred at room temperature until epichlorohydrin disappeared.

[0282] Next, 100 mL of toluene and 100 mL of a 10% aqueous sodium hydroxide solution were added to the flask, and the contents of the flask were stirred for 1 hour. Next, stirring was stopped and the contents were allowed to stand for 1 hour. 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 the toluene (solvent). As a result, 57.1 g of a crude product containing 8-hydroxy-1,15-diphenyl-3,6,10,13-tetrathiapentadecane as a 2-propanol modified product was obtained.

[0283] The resulting crude product was then purified by silica gel column chromatography (developing solvent: hexane / toluene=1 / 1 (volume ratio)) to obtain 50.1 g of 8-hydroxy-1,15-diphenyl-3,6,10,13-tetrathiapentadecane.

[0284] 8-hydroxy-1,15-diphenyl-3,6,10,13-tetrathiapentadecane is as follows: １ H-NMR (400MHz, CDCl ３ ) was identified.

[0285] ​１ H-NMR (400MHz, CDCl ３ ): δ7.34-7.27 (m, 4H) δ7.25-7.18 (m, 6H) δ3.85-3.77 (m, 1H) δ2.92-2.61 (m, 20H) δ1.27 (br, 1H)

[0286] (Synthesis Step 4: Synthesis of 8-acryloyloxy-1,15-diphenyl-3,6,10,13-tetrathiapentadecane (PE-ECHA-A)) 20.0 g (44.2 mmol) of 8-hydroxy-1,15-diphenyl-3,6,10,13-tetrathiapentadecane and 100 mL of dichloromethane (solvent) were placed in a four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet line, and a dropping funnel, and these were dissolved therein.

[0287] Then, 6.73 g (53.0 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 8-hydroxy-1,15-diphenyl-3,6,10,13-tetrathiapentadecane disappeared.

[0288] Next, 100 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.

[0289] 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 6.44 g (63.6 mmol) of triethylamine was then added while adjusting the reaction temperature to maintain it at 5 to 15°C.

[0290] 200 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, the stirring was stopped and the contents of the flask were allowed to stand for 1 hour.

[0291] 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 21.8 g of a crude product containing 8-acryloyloxy-1,15-diphenyl-3,6,10,13-tetrathiapentadecane.

[0292] The resulting crude product was then purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate=20 / 1) to obtain 19.3 g of 8-acryloyloxy-1,15-diphenyl-3,6,10,13-tetrathiapentadecane.

[0293] In addition, PE-ECHA-A is as follows: １ H-NMR (400MHz, CDCl ３ ) was identified. １ H-NMR (400MHz, CDCl ３ ): δ7.34-7.27 (m, 4H) δ7.25-7.18 (m, 6H) δ6.42 (dd, J=1.2Hz, 17.2Hz, 1H) δ6.11 (dd, J=10.4Hz, 17.2Hz, 1H) δ5.86 (dd, J=1.2Hz, 10.4Hz, 1H) δ5.11 (quin, J=6.0Hz, 1H) δ2.95-2.70 (m, 20H)

[0294] (2) Evaluation of Physical Properties <Refractive Index nD and Abbe Number> The refractive index and Abbe number of PE-ECHA-A were measured in accordance with ASTM D 542. The results are shown in Table 1.

[0295] More specifically, the refractive index of PE-ECHA-A 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.

[0296] 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

[0297] <Viscosity> The viscosity of PE-ECHA-A 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.

[0298] Production Example 2 (1) Synthesis of Ph-ECHA-A 5-Acryloyloxy-1,9-bis(phenylthio)-3,7-dithianonane (Ph-ECHA-A) was synthesized by the following method.

[0299] More specifically, a hydrocarbon thio group-containing thiol was prepared (preparation step) as shown in the following synthesis step 1. Next, as shown in the following synthesis step 2, two molecules of the hydrocarbon thio group-containing thiol were reacted with one molecule of epichlorohydrin to produce a 2-propanol modified product (epichlorohydrin reaction step). Thereafter, as shown in the following synthesis step 3, the 2-propanol modified product was reacted with a second modifying agent to produce a compound containing a (meth)acryloyl group ((meth)acryloyl group formation step).

[0300] (Synthesis Step 1: Synthesis of 2-(phenylthio)-ethane-1-thiol) Into a four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet line, and a dropping funnel, 29.0 g (188 mol) of 2-(phenylthio)ethanol (commercially available product) and 10 mL of water were charged and mixed.

[0301] 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. In other words, the hydrocarbon thio group-containing alcohol and thiourea were reacted to obtain an isothiuronium salt. The temperature of the solution was then lowered to 60°C. Next, while stirring the solution in the flask, 100 mL of toluene was slowly added to the flask.

[0302] 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.

[0303] 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.

[0304] 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.

[0305] 2-(phenylthio)-ethane-1-thiol is as follows: １ H-NMR (400MHz, CDCl ３ ) was identified.

[0306] 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)

[0307] (Synthesis Step 2: Synthesis of 5-hydroxy-1,9-bis(phenylthio)-3,7-dithianonane) In a four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet line, and a dropping funnel, 5.87 g (147 mmol) of sodium hydroxide was dissolved in 50 g of water. Next, 25.0 g (147 mmol) of 2-(phenylthio)-ethane-1-thiol as a hydrocarbon thio group-containing thiol was added to the flask and dissolved with stirring.

[0308] Next, the temperature of the solution was adjusted to be maintained at 20°C to 30°C, and 6.1 g (66.1 mmol) of epichlorohydrin was slowly added to the flask while stirring the contents of the flask, and the contents of the flask were stirred at room temperature until epichlorohydrin disappeared.

[0309] ​Next, 100 mL of toluene and 100 mL of a 10% aqueous sodium hydroxide solution were added to the flask, and the contents of the flask were stirred for 1 hour. Next, stirring was stopped and the contents were allowed to stand for 1 hour. 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 the toluene (solvent). As a result, 32.1 g of a crude product containing 5-hydroxy-1,9-bis(phenylthio)-3,7-dithianonane as a 2-propanol modified product was obtained.

[0310] The resulting crude product was then purified by silica gel column chromatography (developing solvent: hexane / toluene=1 / 1 (volume ratio)) to obtain 25.4 g of 5-hydroxy-1,9-bis(phenylthio)-3,7-dithianonane.

[0311] 5-hydroxy-1,9-bis(phenylthio)-3,7-dithianonane is as follows: １ H-NMR (400MHz, CDCl ３ ) was identified.

[0312] １ H-NMR (400MHz, CDCl ３ ): δ7.45-7.19 (m, 10H) δ3.85-3.77 (m, 1H) δ3.15-3.10 (m, 4H) δ2.92-2.61 (m, 8H) δ1.27 (br, 1H)

[0313] (Synthesis Step 3: Synthesis of 5-acryloyloxy-1,9-bis(phenylthio)-3,7-dithianonane (Ph-ECHA-A)) Into a four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet line, and a dropping funnel, 20.0 g (50.4 mmol) of 5-hydroxy-1,9-bis(phenylthio)-3,7-dithianonane and 100 mL of dichloromethane (solvent) were placed and dissolved.

[0314] Then, 7.68 g (60.5 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 5-hydroxy-1,9-bis(phenylthio)-3,7-dithianonane disappeared. ​

[0315] Next, 100 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.

[0316] 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 7.35 g (72.6 mmol) of triethylamine was then added while adjusting the reaction temperature to maintain it at 5 to 15°C.

[0317] 200 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, the stirring was stopped and the contents of the flask were allowed to stand for 1 hour.

[0318] 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 21.8 g of a crude product containing Ph-ECHA-A.

[0319] The crude product was then purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate=20 / 1) to obtain 19.8 g of Ph-ECHA-A.

[0320] Ph-ECHA-A is as follows: １ H-NMR (400MHz, CDCl ３ ) was identified.

[0321] １ H-NMR (400MHz, CDCl ３ ): δ7.45-7.19 (m, 10H) δ6.42 (dd, J=1.2Hz, 17.2Hz, 1H) δ6.11 (dd, J=10.4Hz, 17.2Hz, 1H) δ5.86 (dd, J=1.2Hz, 10.4Hz, 1H) δ5.11 (quin, J=6.0Hz, 1H) δ3.15-3.10 (m, 4H) δ2.95-2.61 (m, 8H)

[0322] ​(2) Evaluation of Physical Properties The refractive index and Abbe number of Ph-ECHA-A were measured in the same manner as in Production Example 1. The results are shown in Table 1. The viscosity of Ph-ECHA-A was also measured in the same manner as in Production Example 1. The results are shown in Table 1.

[0323] Comparative Production Example 1 (1) Synthesis of Et-ECHA-A 8-Acryloyloxy-3,6,10,13-tetrathiapentadecane (Et-ECHA-A) was synthesized by the following method.

[0324] That is, a hydrocarbon thio group-containing alcohol 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 the following synthesis step 3, two molecules of a hydrocarbon thio group-containing thiol were reacted with one molecule of epichlorohydrin to produce a 2-propanol modified product (epichlorohydrin reaction step). Thereafter, as shown in the following synthesis step 4, the 2-propanol modified product was reacted with a second modifying agent to produce a compound containing a (meth)acryloyl group ((meth)acryloyl group formation step).

[0325] (Synthesis Step 1: Synthesis of 1-hydroxy-3-thiapentane) 100.0 g (1280 mmol) of 2-mercaptoethanol and 200 mL of pure 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.

[0326] Then, while stirring the contents of the flask, 51.2 g (1280 mmol) of sodium hydroxide was slowly added to the flask to obtain a homogeneous solution.

[0327] Next, the temperature of the solution was adjusted to be maintained at 20° C. to 30° C., and 133.3 g (1,280 mmol) of bromoethane was slowly added to the flask while stirring the contents of the flask, and the contents of the flask were stirred at room temperature until the bromoethane disappeared. Next, 200 mL of toluene was added, and the mixture was stirred for 1 hour.

[0328] The stirring was stopped and the mixture was allowed to stand for 1 hour. Thereafter, the organic layer was separated from the contents of the flask. The obtained organic layer was then concentrated under reduced pressure to obtain 109.1 g of 1-hydroxy-3-thiapentane as a hydrocarbon thio group-containing alcohol.

[0329] 1-hydroxy-3-thiapentane is as follows: １ H-NMR (400MHz, CDCl ３ ) was identified.

[0330] １ H-NMR (400MHz, CDCl ３ ): δ3.73 (tt, J=6.0, 6.0Hz, 2H) δ2.75 (t, J=6.0Hz, 2H) δ2.56 (q, J=7.6Hz, 2H) δ2.15 (t, J=6.0Hz, 1H) δ1.27 (t, J=7.6Hz, 3H)

[0331] (Synthesis Step 2: Synthesis of 1-mercapto-3-thiapentane) Into a four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet line and a dropping funnel, 50.0 g (471 mol) of 1-hydroxy-3-thiapentane and 100 mL of water were charged and mixed.

[0332] Next, while stirring the contents of the flask, 52.5 g of 36% hydrochloric acid (hydrohalic acid) and 37.6 g (494 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.

[0333] 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 charged into the flask.

[0334] 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, 37.0 g 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 potassium hydroxide. ​

[0335] The temperature of the solution was then lowered to room temperature, and 500 mL of 1N hydrochloric acid was added to the flask, followed by stirring for 1 hour.

[0336] Then, stirring was stopped and the solution was allowed to stand for 1 hour. The organic layer was then separated from the solution and concentrated under reduced pressure. As a result, 36.6 g of 1-mercapto-3-thiapentane was obtained as a hydrocarbon thio group-containing thiol.

[0337] 1-mercapto-3-thiapentane is as follows: １ H-NMR (400MHz, CDCl ３ ) was identified.

[0338] １ H-NMR (400MHz, CDCl ３ ): δ2.80-2.70 (m, 4H) δ2.57 (q, J=7.2Hz, 2H) δ1.74 (t, J=8.0Hz, 1H) δ1.27 (t, J=7.2Hz, 3H)

[0339] (Synthesis Step 3: Synthesis of 8-hydroxy-3,6,10,13-tetrathiapentadecane) In a four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet line, and a dropping funnel, 11.8 g (295 mmol) of sodium hydroxide was dissolved in 90 g of water. Then, 32.8 g (268 mmol) of 1-mercapto-3-thiapentane as a hydrocarbon thio group-containing thiol was added and dissolved with stirring.

[0340] Next, the temperature of the solution was adjusted to be maintained at 20°C to 30°C, and 9.9 g (107 mmol) of epichlorohydrin was slowly added to the flask while stirring the contents of the flask, and the contents of the flask were stirred at room temperature until epichlorohydrin disappeared.

[0341] ​Next, 100 mL of toluene and 100 mL of a 10% aqueous sodium hydroxide solution were added to the flask, and the contents of the flask were stirred for 1 hour. Next, stirring was stopped and the contents were allowed to stand for 1 hour. 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 the toluene (solvent). As a result of the above, 26.3 g of a crude product containing 8-hydroxy-3,6,10,13-tetrathiapentadecane was obtained.

[0342] The resulting crude product was then purified by silica gel column chromatography (developing solvent: hexane / toluene=1 / 1 (volume ratio)) to obtain 25.6 g of 8-hydroxy-3,6,10,13-tetrathiapentadecane.

[0343] 8-hydroxy-3,6,10,13-tetrathiapentadecane is as follows: １ H-NMR (400MHz, CDCl ３ ) was identified.

[0344] １ H-NMR (400MHz, CDCl ３ ): δ3.88-3.79 (m, 1H) δ2.91 (d, J=3.2Hz, 1H) δ2.84-2.64 (m, 12H) δ2.58 (q, J=7.6Hz, 4H) δ1.27 (t, J=7.6Hz, 6H)

[0345] (Synthesis Step 4: Synthesis of 8-acryloyloxy-3,6,10,13-tetrathiapentadecane (Et-ECHA-A)) Into a four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet line, and a dropping funnel, 21.5 g (71.7 mmol) of 8-hydroxy-3,6,10,13-tetrathiapentadecane and 100 mL of dichloromethane (solvent) were placed and dissolved.

[0346] Then, 9.10 g (71.7 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 8-hydroxy-3,6,10,13-tetrathiapentadecane disappeared.

[0347] ​Next, 100 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.

[0348] 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 8.7 g (86.0 mmol) of triethylamine was then added while adjusting the reaction temperature to maintain it at 5 to 15°C.

[0349] 200 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, the stirring was stopped and the contents of the flask were allowed to stand for 1 hour.

[0350] 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 19.5 g of a crude product containing Et-ECHA-A.

[0351] The resulting crude product was then purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate=20 / 1) to obtain 18.1 g of Et-ECHA-A.

[0352] Et-ECHA-A is as follows: １ H-NMR (400MHz, CDCl ３ ) was identified. １ H-NMR (400MHz, CDCl ３ ): δ6.44 (dd, J=1.6Hz, 17.2Hz, 2H) δ6.13 (dd, J=10.4Hz, 17.2Hz, 2H) δ5.89 (dd, J=1.6Hz, 10.4Hz, 2H) δ5.13 (quin, J=6.0Hz, 1H) δ2.97-2.72 (m, 12H) δ2.58 (q, J=7.6Hz, 4H) δ1.27 (t, J=7.6Hz, 6H)

[0353] (2) Evaluation of Physical Properties The refractive index and Abbe number of Et-ECHA-A were measured in the same manner as in Production Example 1. The results are shown in Table 1. The viscosity of Et-ECHA-A was measured in the same manner as in Production Example 1. The results are shown in Table 1.

[0354] 2. Pressure-sensitive adhesive (homopolymer) Examples 1 and 2 and Comparative Example 1 According to the formulations shown in Table 2, 1.0 g (100 parts by mass) of the compounds (polymerizable monomers) obtained in Production Examples 1 and 2 and Production Comparative Example 1 were placed in a brown test tube. 4.0 g of toluene and 50.0 mg (0.5 parts by mass) of AIBN were also placed in the test tube. The contents of the test tubes were then mixed to obtain polymerizable compositions.

[0355] Next, the polymerizable composition was degassed and the reaction system was substituted with nitrogen by a freeze vacuum degassing method using liquid nitrogen.

[0356] 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.

[0357] (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.

[0358] (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

[0359] <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 Production Example 1. The results are shown in Table 2.

[0360] <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.

[0361] 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

[0362] 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.

[0363] 3. Pressure-Sensitive Adhesive (Copolymer) Examples 3-4 and Comparative Example 2 (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 Production Examples 1-2 and Production 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.

[0364] Next, the polymerizable composition was degassed and the reaction system was substituted with nitrogen by a freeze vacuum degassing method using liquid nitrogen.

[0365] 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.

[0366] (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.

[0367] 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.

[0368] (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.

[0369] 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.

[0370] 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.

[0371] 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.

[0372] 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).

[0373] 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.

[0374] (4) 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.

[0375] The refractive index and Abbe number of the adhesive were measured in the same manner as in Production Example 1. The results are shown in Table 3.

[0376] <Storage Modulus 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.

[0377] A plurality of adhesives were laminated to obtain a sample having a thickness of about 0.5 mm.

[0378] 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.

[0379] <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).

[0380] 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.

[0381] 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).

[0382] 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.

[0383] 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.

[0384] 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.

[0385] <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.

[0386] 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

[0387] After the weather resistance test, the peel strength and yellowness index (b ＊ The results are shown in Table 3.

[0388] <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.

[0389] Temperature: 85°C Humidity: 20% Test time: 100 hours

[0390] After the heat resistance test, the peel strength and yellowness index (b ＊ The viscosity (A) and haze (H) values ​​were measured by the methods described above. The results are shown in Table 3. 4. Pressure-sensitive adhesive compositions Examples 5 to 7 (1) Preparation of resin varnish According to the formulation shown in Table 4, the compound (polymerizable monomer) obtained in Production Example 1 and 4-hydroxybutyl acrylate (copolymerizable monomer, 4HBA) were polymerized to obtain a pressure-sensitive adhesive. Next, according to the formulation shown in Table 4, additives were added to the pressure-sensitive adhesive. A resin varnish (solid concentration 40%) was obtained in the same manner as in Example 3, except for the above.

[0391] The following ultraviolet absorbers and light stabilizers were used as additives.

[0392] 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 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.

[0393] (2) Preparation of Paint A paint having a solid content concentration of 25% by mass was obtained in the same manner as in Example 3, except that a resin varnish containing the above additives was used.

[0394] (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 a crosslinked adhesive, and an adhesive composition containing the adhesive and the additives was obtained in the same manner as in Example 3, except that the resin varnish was used. A laminate (GP-1) was also produced in the same manner as in Example 3, except that the adhesive composition was used to bond the film. Table 4 shows the formulation of Example 3, along with the formulations of Examples 5 to 7.

[0395] (2) Evaluation of Physical Properties <Weather Resistance Test (2)> The laminates (GP-1) of Examples 3 and 5 to 7 were evaluated under conditions stricter than those of the above weather resistance test.

[0396] More specifically, the laminates (GP-1) of Examples 3 and 5 to 7 were exposed to light under the following conditions using a solar simulator.

[0397] Device name: UVACUBE400 / SOL500 (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

[0398] After the weather resistance test, the peel strength and yellowness index (b ＊ The results are shown in Table 4.

[0399]

[0400]

[0401]

[0402]

[0403] Details of the abbreviations in the table are as follows: PE-ECHA-A: 8-acryloyloxy-1,15-diphenyl-3,6,10,13-tetrathiapentadecane Ph-ECHA-A: 5-acryloyloxy-1,9-bis(phenylthio)-3,7-dithianonane Et-ECHA-A: 8-acryloyloxy-3,6,10,13-tetrathiapentadecane 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 PA144: Hindered amine 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

[0404] 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.

[0405] The pressure-sensitive adhesive, pressure-sensitive adhesive composition and 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 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; m represents an integer of 1 or more; n represents an integer of 1 or more; and X represents a sulfur atom or an oxygen atom.

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

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

4. The pressure-sensitive adhesive according to claim 1, further comprising structural units derived from a crosslinking agent.

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

6. The adhesive of claim 1, which is an adhesive film.

7. A pressure-sensitive adhesive composition comprising 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 less than or equal to parts by mass.

8. A compound represented by the following formula (1'): (In formula (1′), R ３ represents a hydrogen atom or a methyl group; m represents an integer of 1 or more; and n represents an integer of 1 or more.

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