Composition, Photodegradable Composition, and Compound

Abstract

The present invention pertains to a composition containing a disulfide compound having two or more disulfide bonds, a vinyl ether compound having two or more vinyloxy groups, and an intramolecular cleavage type photo-radical generator.

Description

Technical Field

[0001] The present invention relates to a composition, a photo-dissolvable composition, and a compound.

Background Art

[0002] Photocurable resin compositions that cure upon light irradiation have been considered for various applications. Various photocurable resin compositions have been proposed so far. For example, Patent Document 1 discloses a photocurable resin composition containing a compound (A) having a photopolymerizable functional group and an oil gelling agent (B), wherein the viscosity at a shear rate of 1.0 s-1 at 25°C is 30 to 1000 Pa·s.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] One aspect of the present invention aims to provide a new composition having excellent photocurability.

Means for Solving the Problems

[0005] One aspect of the present invention relates to a composition containing a disulfide compound having two or more disulfide bonds, a vinyl ether compound having two or more vinyloxy groups, and an intramolecular cleavage type photo radical generator.

[0006] The intramolecular cleavage type photo radical generator may include a first intramolecular cleavage type photo radical generator having a molar extinction coefficient of 1.0×10 2 or more at a first wavelength, and a second intramolecular cleavage type photo radical generator having a molar extinction coefficient of 1.0×10 2 or more at the first wavelength.

[0007] The first intramolecular cleavage type photo radical generator is at least one selected from the group consisting of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and the second intramolecular cleavage type photo radical generator may be at least one selected from the group consisting of 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, anisoin, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one.

[0008] The first intramolecular cleavage type photo radical generator is bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and the second intramolecular cleavage type photo radical generator may be at least one selected from the group consisting of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, anisoin, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one.

[0009] The disulfide compound may have a structural unit represented by the following formula (1).

Chemical formula

[0010] The above-described composition may be used as an adhesive.

[0011] One aspect of the present invention relates to a photo-melting composition containing a photo-reaction product of a disulfide compound having two or more disulfide bonds and a vinyl ether compound having two or more vinyloxy groups, and an intramolecular cleavage type photo radical generator.

[0012] One aspect of the present invention relates to a compound having a disulfide bond and a structure represented by the following formula (A). [Chemical formula] [In formula (A), * represents a bond.]

[0013] The above compound may be a compound having a structure represented by the following formula (B). [Chemical formula] [In formula (B), n represents an integer of 1 or more, A represents a polyether group, * represents a bond, and a plurality of A's may be the same as or different from each other.]

[0014] The above compound may further have a structure represented by the following formula (C). [Chemical formula] [In formula (C), * represents a bond.]

[0015] One aspect of the present invention relates to a photo-melting composition containing the above-described compound and an intramolecular cleavage type photo radical generator. [Advantages of the Invention]

[0016] According to one aspect of the present invention, it is possible to provide a new composition having excellent photocurability. [Modes for Carrying Out the Invention]

[0017] Hereinafter, some embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

[0018] In this specification, the term "step" includes not only an independent step but also a step in which, even if it cannot be clearly distinguished from other steps, as long as the intended action of the step is achieved. Also, the numerical range indicated by "~" indicates a range including the numerical values described before and after "~" as the minimum value and the maximum value, respectively.

[0019] In this specification, the content of each component in the composition means the total amount of the plurality of substances corresponding to each component in the composition when there are a plurality of substances corresponding to each component in the composition, unless otherwise specified. Also, the exemplary materials may be used alone or in combination of two or more, unless otherwise specified.

[0020] In the numerical ranges described step by step in this specification, the upper limit value or the lower limit value of the numerical range at a certain step may be replaced with the upper limit value or the lower limit value of the numerical range at other steps. Also, in the numerical ranges described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples. "A or B" means that either A or B may be included, or both may be included.

[0021] 〔Composition〕 The composition of one embodiment contains a disulfide compound having two or more disulfide bonds, a vinyl ether compound having two or more vinyloxy groups, and an intramolecular cleavage type photo radical generator. Since the composition has the property of curing by light irradiation, it can also be called a photocurable composition.

[0022] Although the mechanism by which the composition photocures is not clear, it is speculated as follows, for example. However, the mechanism is not limited to this. In a composition containing a disulfide compound, a vinyl ether compound, and an intramolecular cleavage type photo radical generator, when irradiated with light, the carbon-carbon double bond of the vinyloxy group undergoes an insertion reaction with respect to the disulfide bond, and the disulfide compound and the vinyl ether compound form a bond and increase in molecular weight, thereby photocuring is considered. When the disulfide compound further has a thiol group, in addition to the insertion reaction of the carbon-carbon double bond of the vinyloxy group with respect to the disulfide bond, it is considered that the molecular weight increase also proceeds by the enethiol reaction between the thiol group in the disulfide compound and the vinyloxy group in the vinyl ether compound.

[0023] The cured product of the composition of one embodiment contains a photoreaction product exhibiting photo-melting properties. Therefore, the cured product of the composition can be photo-melted by irradiating with light in the presence of an intramolecular cleavage type photo radical generator. Although the mechanism by which the cured product of the composition photo-melts is not clear, for example, the following mechanisms are conceivable. However, it is not limited to these mechanisms. By photoreacting the disulfide compound and the vinyl ether compound in the composition, a cured product containing a compound having a disulfide bond can be formed. When the cured product of the composition is irradiated with light, the disulfide bond in the cured product decomposes (cleaves) to generate a thyl radical. At this time, if an intramolecular cleavage type photo radical generator is present in the cured product, the thyl radical reacts with the intramolecular cleavage type photo radical generator, and the thyl radical is capped by the photo radical generator. Thus, a mechanism is considered in which the compound having a disulfide bond decreases in molecular weight and the cured product photo-melts. As another mechanism, a photo-induced radical caused by the intramolecular cleavage type photo radical generator directly reacts with the disulfide bond, formation of a photo-induced radical-thioether bond and generation of a thyl radical occur, the thyl radical reacts with another photo-induced radical, and a mechanism in which the compound itself having a disulfide bond decreases in molecular weight and the photocured product softens is also considered. It can be said that the reaction in which the disulfide bond cleaves is an irreversible reaction.

[0024] <Disulfide compound> A disulfide compound is a compound having two or more disulfide bonds. The number of disulfide bonds per molecule of the disulfide compound may be, for example, 1 to 1000, or 4 to 50.

[0025] The molecular weight of the disulfide compound may be 200 to 10000000, 200 to 3000000, 500 to 1000000, or 1000 to 10000.

[0026] The number average molecular weight of the disulfide compound may be 200 to 10000000, 200 to 3000000, 500 to 1000000, or 1000 to 10000. The number average molecular weight is a polystyrene conversion value using a calibration curve with standard polystyrene by gel permeation chromatography (GPC).

[0027] The disulfide compound may have one or more (for example, two or more) thiol groups (-SH). The disulfide compound may be a compound having two thiol groups.

[0028] The disulfide compound may be a compound (for example, a polymer or an oligomer) having a linear molecular chain and end groups and having a disulfide bond in the molecular chain.

[0029] The disulfide compound may be, for example, a compound having a structural unit represented by the following formula (1). In this case, a cured product of a composition having more excellent photolytic properties can be formed.

Chemical formula

[0030] The disulfide compound having the structural unit represented by the formula (1) may be, for example, a reaction product of a first precursor compound having a disulfide bond and two first groups, and a second precursor compound having a second group capable of reacting with the first group. The first group may be, for example, a carboxy group. Examples of the first precursor compound include dithiodipropionic acid. The second group may be, for example, a hydroxy group or an epoxy group. The second precursor compound may be a compound having two or more second groups, or may be a compound having two second groups. Examples of the second precursor compound include diol compounds such as diol oligomers and diol polymers, compounds having an epoxy group at the terminal such as polyalkylene glycol diglycidyl ether, and silicone. Examples of the diol compound include polyalkylene glycols such as polyethylene glycol and polypropylene glycol.

[0031] A may be a polyether group. The polyether group represented by A may be, for example, a polyoxyalkylene group. The polyether group represented by A may be, for example, -A 1 -O-A 2 -O-A 3 - represented group. A 1 ~A 3 may each independently be an alkylene group, and may be an alkylene group having 1 to 2 carbon atoms (for example, a methylene group or an ethylene group). Examples of the polyether group represented by A include -CH 2 CH 2 -O-CH 2 -O-CH 2 CH 2 - etc.

[0032] The disulfide compound may be, for example, a compound represented by the following formula (1A).

Chemical formula

[0033] As the disulfide compound, for example, a compound obtained by synthesis such as a reaction product of the above-described first precursor compound and the second precursor compound may be used, or a commercially available product such as the Thiolcol LP series (dithiol having a disulfide bond, manufactured by Toray Fine Chemical Co., Ltd.) may be used. The disulfide compound may be used alone or in combination of two or more.

[0034] The content of the disulfide compound may be 50% by mass or more, 60% by mass or more, 70% by mass or more, 75% by mass or more, or 80% by mass or more, and may be 95% by mass or less, 90% by mass or less, or 85% by mass or less based on the total mass of the composition.

[0035] <Vinyl ether compound> The vinyl ether compound is a compound having two or more vinyloxy groups (H 2 C=CH-O-). The vinyl ether compound may be used alone or in combination of two or more.

[0036] The number of vinyloxy groups per molecule of the vinyl ether compound may be, for example, 2 to 8, may be 2 to 4, and preferably 2.

[0037] The molecular weight of the vinyl ether compound may be, for example, 100 or more, may be 150 or more, may be 1000 or less, and may be 300 or less.

[0038] The vinyl ether compound may be, for example, a compound composed of two vinyloxy groups and a linking group that links the vinyloxy groups together. That is, the vinyl ether compound may be a compound represented by formula (2): H 2 C=CH-O-Z-O-CH=CH 2 wherein in formula (2), Z represents a linking group. The linking group represented by Z may be, for example, a substituted or unsubstituted divalent hydrocarbon group. The number of carbon atoms of the hydrocarbon group in the linking group may be, for example, 1 or more, or 3 or more, and may also be 10 or less or 20 or less. The linking group may be, for example, a polyoxyalkylene group (such as a polyoxyethylene group), an alkylene group, a cycloalkylene group, or a combination of these groups.

[0039] Examples of the vinyl ether compound include diethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, and 1,4-butanediol divinyl ether.

[0040] The content of the vinyl ether compound may be 1.0% by mass or more, 1.5% by mass or more, 2.0% by mass or more, or 2.5% by mass or more, and may be 20.0% by mass or less, 10.0% by mass or less, or 5.0% by mass or less, based on the total mass of the composition.

[0041] The ratio (B / A) of the number of moles (B) of the vinyl ether compound to the number of moles (A) of the disulfide compound may be 0.5 or more, or 1 or more, and may be 3 or less, or 4 or less.

[0042] <Intramolecular cleavage type photo radical generator> The intramolecular cleavage type photo radical generator is a compound that undergoes photo cleavage by irradiation with light to generate two radicals. As the intramolecular cleavage type photo radical generator, a compound that has been used as an intramolecular cleavage type photo radical polymerization initiator can be used.

[0043] Examples of the intramolecular cleavage type photo radical generator include, for example, benzyl ketal type photo radical generators, α-aminoalkylphenone type photo radical generators, α-hydroxyalkylphenone type photo radical generators, α-hydroxyacetophenone type photo radical generators, and acylphosphine oxide type photo radical generators. The intramolecular cleavage type photo radical generator may be used alone or in combination of two or more.

[0044] Examples of the benzyl ketal type photo radical generator include 2,2-dimethoxy-1,2-diphenylethane-1-one (Omnirad651) and the like.

[0045] Examples of the α-aminoalkylphenone type photo radical generator include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (Omnirad369), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (Omnirad907), 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butanone-1 (Omnirad379EG) and the like.

[0046] Examples of the α-hydroxyalkylphenone type photo radical generator include 1-hydroxy-cyclohexyl-phenyl-ketone (Omnirad184) and the like.

[0047] Examples of the α-hydroxyacetophenone type photo radical generator include 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one (Omnirad127), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Omnirad1173), anisoin and the like.

[0048] Examples of acylphosphine oxide-based photo radical generators include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Omnirad TPO H), bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Omnirad 819), and the like.

[0049] The intramolecular cleavage type photo radical generator may contain a first intramolecular cleavage type photo radical generator having a molar absorption coefficient at the first wavelength of 1.0×10 2 or more, and a second intramolecular cleavage type photo radical generator having a molar absorption coefficient at the first wavelength of less than 1.0×10 2 . The molar absorption coefficient in this specification is a value measured in methanol or acetonitrile (unit: mL / g·cm).

[0050] When the composition contains the first and second intramolecular cleavage type photo radical generators, the cured product obtained by irradiating the first light containing the light of the first wavelength can be melted by irradiating the second light containing the light of a wavelength (second wavelength) different from the first wavelength. The second light may contain light of a second wavelength that is shorter than the first wavelength.

[0051] The first wavelength may be, for example, 447 nm or 405 nm. When the first wavelength is 447 nm, the second wavelength may be 405 nm or 365 nm. When the first wavelength is 405 nm, the second wavelength may be 365 nm.

[0052] Examples of the intramolecular cleavage type photo radical generator having a molar absorption coefficient at a wavelength of 447 nm of 1.0×10 2 or more include bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Omnirad 819).

[0053] Examples of the intramolecular cleavage type photo radical generator having a molar absorption coefficient at a wavelength of 447 nm of less than 1.0×10 2 and a molar absorption coefficient at a wavelength of 405 nm of 1.0×10 2Examples of the intramolecular cleavage type photo radical generator include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (Omnirad 369) and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Omnirad TPO H).

[0054] The absorption coefficient at a wavelength of 447 nm and the absorption coefficient at a wavelength of 405 nm are 1.0×10 2 Examples of the intramolecular cleavage type photo radical generator with an absorption coefficient less than 1.0×10 include 1-hydroxy-cyclohexyl-phenyl-ketone (Omnirad 184), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Omnirad 1173), anisoin, 2,2-dimethoxy-1,2-diphenylethane-1-one (Omnirad 651), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (Omnirad 907), and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one (Omnirad 127).

[0055] The composition of one embodiment has an absorption coefficient at a wavelength of 447 nm of 1.0×10 2 or more, a first intramolecular cleavage type photo radical generator, and an absorption coefficient at a wavelength of 447 nm of 1.0×10 2It may contain a second intramolecular cleavage type photo radical generator that is less than. For example, the first intramolecular cleavage type photo radical generator is bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and the second intramolecular cleavage type photo radical generator is 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, anisoin, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, or 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one.

[0056] The composition of other embodiments has an extinction coefficient at a wavelength of 405 nm of 1.0×10 2 or more, a first intramolecular cleavage type photo radical generator, and an extinction coefficient at a wavelength of 405 nm of 1.0×10 2 It may contain a second intramolecular cleavage type photo radical generator that is less than.

[0057] For example, the first intramolecular cleavage type photo radical generator is 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and the second intramolecular cleavage type photo radical generator may be 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, anisoin, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, or 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one. The first intramolecular cleavage type photo radical generator is 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and the second intramolecular cleavage type photo radical generator may be 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, anisoin, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, or 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one.

[0058] Suitable combinations of the first and second intramolecular cleavage type photo radical generators include, for example, the combination of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Omnirad TPO H) and 1-hydroxy-cyclohexyl-phenyl-ketone (Omnirad 184) or anisoin, the combination of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (Omnirad 369) and 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Omnirad 1173), and the combination of bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Omnirad 819) and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Omnirad TPO H).

[0059] The total content of the intramolecular cleavage type photo radical generator may be 5% by mass or more, or 10% by mass or more, and may be 30% by mass or less, or 20% by mass or less, based on the total mass of the composition.

[0060] The content of the first intramolecular cleavage type photo radical generator may be 0.8% by mass or more, or 1.0% by mass or more, and may be 1.5% by mass or less, or 2.0% by mass or less, based on the total mass of the composition.

[0061] The ratio (A / C1) of the number of moles (A) of the disulfide compound to the number of moles (C1) of the first intramolecular cleavage type photo radical generator may be, for example, 5 or more, or 6.6 or more, and may be 12.5 or less, or 10 or less.

[0062] The ratio (B / C1) of the number of moles (B) of the vinyl ether compound to the number of moles (C1) of the first intramolecular cleavage type photo radical generator may be, for example, 5 or more, or 6.6 or more, and may be 12.5 or less, or 10 or less.

[0063] The content of the second intramolecular cleavage type photo radical generator may be 5% by mass or more, or 10% by mass or more, and may be 30% by mass or less, or 20% by mass or less, based on the total mass of the composition.

[0064] The ratio (A / C2) of the number of moles (A) of the disulfide compound to the number of moles (C2) of the second intramolecular cleavage type photo radical generator may be, for example, 0.2 or more, or 0.33 or more, and may be 0.7 or less, or 1 or less.

[0065] The ratio (B / C2) of the number of moles (B) of the vinyl ether compound to the number of moles (C2) of the second intramolecular cleavage type photo radical generator may be, for example, 0.2 or more, or 0.33 or more, and may be 0.7 or less, or 1 or less.

[0066] The composition may further contain components other than the disulfide compound, the vinyl ether compound, and the intramolecular cleavage type photo radical generator (other components). Examples of the other components include additives such as plasticizers, tackifiers such as tackifiers, antioxidants, leuco dyes, sensitizers, adhesion improvers such as coupling agents, polymerization inhibitors, light stabilizers, defoamers, fillers, chain transfer agents, thixotropy imparting agents, flame retardants, mold release agents, surfactants, lubricants, and antistatic agents. Known ones can be used as these additives. The total content of the other components may be 50% by mass or less, 20% by mass or less, or 5% by mass or less based on the total amount of the composition.

[0067] The complex viscosity of the composition at 25 ° C. may be, for example, 300 Pa·s or less, or 100 Pa·s or less, and may be 1 Pa·s or more, or 5 Pa·s or more. The complex viscosity at 25 ° C. is measured by the method described in the examples below.

[0068] <Method for producing the composition> The composition can be produced, for example, by a method comprising a step of mixing or kneading a disulfide compound, a vinyl ether compound, an intramolecular cleavage type photo radical generator, and components added as necessary. Mixing and kneading can be appropriately performed in combination with dispersers such as ordinary stirrers, kneaders, three-roll mills, ball mills, and bead mills.

[0069] <Use> The composition of one embodiment can be used for applications such as adhesives, temporary fixing materials, photoresists, resins for 3D printers, and resins for molding materials.

[0070] 〔Cured product〕 The cured product of the composition of one embodiment contains a photoreaction product of a disulfide compound and a vinyl ether compound. The cured product may contain an intramolecular cleavage type photo radical generator. Since the cured product containing the photoreaction product of the disulfide compound and the vinyl ether compound and the intramolecular cleavage type photo radical generator has the property of melting upon light irradiation, it can also be referred to as a photo-melting composition.

[0071] The cured product may have various shapes. Examples of the shape of the cured product include a film shape (film-like) and a block shape. For example, a cured product formed in a film shape (film-like) can be used as a resin film. A cured product formed in a block shape can be used as a resin block. The method for forming a cured product in a film shape (film-like) or a block shape is not particularly limited, and known methods can be applied.

[0072] The storage modulus of the cured product at 25°C may be 16,000 Pa or more, 5,000 Pa or more, or 100,000 Pa or more. The storage modulus of the cured product of the composition is not particularly limited, but may be, for example, 1,000 MPa or less. In this specification, the storage modulus at 25°C means the value measured by the method described in the examples.

[0073] The loss modulus of the cured product at 25°C may be 15,000 Pa or more, 25,000 Pa or more, or 35,000 Pa or more. The loss modulus of the cured product of the composition is not particularly limited, but may be, for example, 1,000 MPa or less. In this specification, the loss modulus at 25°C means the value measured by the method described in the examples.

[0074] The loss tangent (tanδ) of the cured product at 25°C may be 1.5 or less, 1.2 or less, 1.1 or less, or 1.0 or less from the viewpoints of micro-adhesiveness or non-adhesiveness, thickening property, slit processability, punching processability, workability, etc. In this specification, the loss tangent at 25°C means the value measured by the method described in the examples.

[0075] <Method for producing a cured product> The cured product of the composition of one embodiment can be produced by a method including a step of irradiating the composition with light to react a disulfide compound and a vinyl ether compound.

[0076] The light (light for curing) when forming the cured product may be, for example, ultraviolet light or visible light. The wavelength of the light for curing may be appropriately selected according to, for example, the type of the intramolecular cleavage type photo radical generator used. The wavelength of the light for curing may be, for example, 150 to 830 nm. The light for curing may contain, for example, light with a wavelength of 447 nm, a wavelength of 405 nm, or a wavelength of 365 nm.

[0077] The light irradiation can be carried out, for example, using a light irradiation device, with an irradiation amount of 100 mJ / cm 2 or more under the above conditions. The irradiation amount can be appropriately set according to, for example, the wavelength of the light for curing. The irradiation amount can be, for example, 1000 mJ / cm 2 or more, 2000 mJ / cm 2 or more, or 2500 mJ / cm 2 or more, and may be 10000 mJ / cm 2 or less, 5000 mJ / cm 2 or less, or 3500 mJ / cm 2 or less.

[0078] The irradiation amount means the product of the illuminance and the irradiation time (seconds). Examples of the light source for ultraviolet light or visible light irradiation include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, an LED lamp, etc. The light irradiation may be carried out directly on the composition or through glass or the like.

[0079] 〔The compound of this case〕 The compound of one embodiment (hereinafter also referred to as "the compound of this case") has a disulfide bond and a structure represented by the following formula (A).

Chemical formula

[0080] The present compound can be produced by a method including irradiating a composition containing a disulfide compound, a vinyl ether compound, and an intramolecular cleavage type photo radical generator with light to react the disulfide compound with the vinyl ether compound. The disulfide compound, the vinyl ether compound, and the intramolecular cleavage type photo radical generator may be those described above. As the light irradiation conditions, the above-described conditions can be used.

[0081] The production of the present compound is confirmed by NMR, IR, GC-MS, etc.

[0082] The structure represented by the above formula (A) is not limited thereto, but is presumed to be formed by an insertion reaction of the carbon-carbon double bond in the vinyloxy group with respect to the disulfide bond by the reaction of the disulfide compound and the vinyl ether compound.

[0083] The present compound may have a structure represented by the following formula (B).

Chemical formula

[0084] The present compound may have a linking group represented by Z in the above formula (2). The linking group may be bonded to the oxygen atom in formula (B).

[0085] The present compound may further have a structure represented by the following formula (C).

Chemical formula

[0086] The compound of the present invention further having the structure represented by the above formula (C) can be obtained, for example, by using a disulfide compound having two thiol groups in the method for producing the compound of the present invention. The structure represented by the above formula (C) is presumed to be formed by an enethiol reaction between a thiol group and a vinyloxy group in a vinyl ether compound.

[0087] [Photodegradable Composition] A photodegradable composition according to one embodiment contains a photochemical reaction product of a sulfide compound and a vinyl ether compound, and an intramolecular cleavage type photo radical generator. A photodegradable composition according to another embodiment contains the compound of the present invention and an intramolecular cleavage type photo radical generator.

[0088] The photodegradable composition can be produced, for example, by irradiating a composition containing a sulfide compound, a vinyl ether compound, a first and a second intramolecular cleavage type photo radical generator with a first light containing light of a first wavelength to react the sulfide compound and the vinyl ether compound, thereby forming a cured product (photodegradable composition) containing a photochemical reaction product of the sulfide compound and the vinyl ether compound and a second intramolecular cleavage type photo radical generator.

[0089] [Method for Producing Photodegradable Product] A method for producing a photodegradable product according to one embodiment includes a step of irradiating a photodegradable composition containing the above-described photochemical reaction product and an intramolecular cleavage type photo radical generator with light to form a photodegradable product. A method for producing a photodegradable product according to another embodiment includes a step of irradiating a photodegradable composition containing the compound of the present invention and an intramolecular cleavage type photo radical generator with light to form a photodegradable product.

[0090] The light (melting light) for forming the melt may be, for example, ultraviolet light or visible light. The wavelength of the melting light may be appropriately selected according to, for example, the type of the intramolecular cleavage type photo radical generator used. The wavelength of the melting light may be, for example, 150 to 830 nm. The melting light may contain, for example, light having a wavelength of 405 nm or 365 nm.

[0091] The light irradiation can be performed, for example, using a light irradiation device, under conditions of an irradiation amount of 3000 mJ / cm 2 or more. The irradiation amount can be appropriately set according to, for example, the wavelength of the light for curing, etc. The irradiation amount is, for example, 15000 mJ / cm 2 or more, 20000 mJ / cm 2 or more, or 25000 mJ / cm 2 or more, and may be 100000 mJ / cm 2 or less, 50000 mJ / cm 2 or less, or 35000 mJ / cm 2 or less.

[0092] The complex viscosity of the photo-melted product at 25 °C may be, for example, 1000 Pa·s or less, or 500 Pa·s or less, and may be 10 Pa·s or more, or 1 Pa·s or more.

[0093] 〔Adherend〕 The adherend of this embodiment includes a first adherend, a second adherend, and an adhesive layer that adheres the first adherend and the second adherend to each other. The adhesive layer contains the photo-melting composition described above.

[0094] Examples of the first adherend and the second adherend include plastics such as polyolefin resin, polyamide resin, ABS (acrylonitrile-butadiene-styrene) resin, PC (polycarbonate) resin, PET (polyethylene terephthalate) resin, PPS (polyphenylene sulfide) resin, and acrylic resin; inorganic materials such as steel, stainless steel, a single metal (aluminum, copper, nickel, chromium, etc.) or an alloy of these metals, glass, and silicon wafer; wood; rubber, etc. Further, examples of the first adherend and the second adherend also include a material in which the above plastic and the above inorganic material are combined.

[0095] The adherend can be produced, for example, by a method including a step of irradiating a composition with first light in a state where the composition of the present embodiment is in contact with a first adherend and a second adherend to form an adhesive layer that adheres the first adherend and the second adherend to each other. The first light can be appropriately set according to, for example, the type of the intramolecular cleavage type photo radical generator. The irradiation conditions of the first light may be the conditions described above.

[0096] 〔Method for Separating Adherends〕 A method for separating adherends according to an embodiment includes a step of irradiating the adhesive layer of the adherend with second light to separate the first adherend and the second adherend. Since the adhesive layer contains a photo-melting composition, by irradiating light, the photo-melting composition can be melted to easily separate the adherends from each other. The second light can be appropriately set according to, for example, the type of the intramolecular cleavage type photo radical generator. The irradiation conditions of the second light may be the conditions described above.

Examples

[0097] Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

[0098] (A) As a component, a compound having two or more disulfide bonds shown below was prepared. Thiocol LP-55 (polysulfide, manufactured by Toray Fine Chemical Co., Ltd., number average molecular weight (Mn): 3677.8)

[0099] (B) As a component, a compound having a carbon-carbon double bond shown below was prepared. DEGDVE (diethylene glycol divinyl ether, manufactured by Nippon Carbide Industries Co., Ltd., molecular weight: 158.2) TEGDVE (triethylene glycol divinyl ether, manufactured by Nippon Carbide Industries Co., Ltd., molecular weight: 202.28) CHDVE (1,4-cyclohexanedimethanol divinyl ether, manufactured by Nippon Carbide Industries Co., Ltd., molecular weight: 196.29) BDVE (1,4-butanediol divinyl ether, manufactured by Nippon Carbide Industries Co., Ltd., molecular weight: 142.2) Diallyl phthalate (diallyl phthalate, manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight: 246.26) Funacryl FA-124AS (butanediol diacrylate, manufactured by Showa Denko Materials Co., Ltd., molecular weight: 198)

[0100] (C) As a component, the following photoinitiators were prepared. (Intramolecular cleavage type photoinitiator) Omnirad-819 (bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, manufactured by IGM Resins B.V., molecular weight: 418.5) Omnirad-TPO H (2,4,6-trimethylbenzoyl-diphenylphosphine oxide, manufactured by IGM Resins B.V., molecular weight: 348) Omnirad-369 (2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone, manufactured by IGM Resins B.V., molecular weight: 366.5) Omnirad-184 (1-hydroxycyclohexyl-phenyl ketone, manufactured by IGM Resins B.V., molecular weight: 204.3) Omnirad-1173 (2-hydroxy-2-methyl-1-phenylpropanone, manufactured by IGM Resins B.V., molecular weight: 164.2) A1010 (anisoin, manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight: 272.3) (Hydrogen abstraction type photoinitiator) Benzyl (benzyl, manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight: 210.23)

[0101] Preparation of the composition (Examples 1-1 to 1-2, 2-1 to 2-4, 2-6 to 2-8, Comparative Examples 1 to 4) The components and amounts (unit: parts by mass) shown in Tables 1 to 2 were added to a 100 mL flask and stirred with a mechanical stirrer at 100 °C for 1 hour to dissolve and mix the components, thereby obtaining the compositions of Examples 1-1 to 1-2, 2-1 to 2-4, 2-6 to 2-8, and Comparative Examples 1 to 4.

[0102] (Example 2-5) The components and amounts (unit: parts by mass) shown in Table 2 other than Omnirad-1173 were added to a 100 mL flask and stirred with a mechanical stirrer at 100 °C for 1 hour to dissolve and mix the components. Then, the amount of Omnirad-1173 shown in Table 1 was added at room temperature and stirred for 1 hour, thereby obtaining the composition of Example 2-5.

[0103] Evaluation of photocuring and meltability Using a viscoelasticity measuring device (manufactured by TA Instruments, trade name: DHR-2), the change in storage modulus at 25 °C with respect to the light irradiation time was measured by irradiating the evaluation sample with ultraviolet light from the bottom surface with light transmissivity. For light irradiation, LED lamps (manufactured by Panasonic Device SUNX Co., Ltd., trade names: Aicure UJ30 / ANUJ6186 and ANUJ6189) were used for 365 nm and 405 nm, and an LED lamp (manufactured by CCS Co., Ltd., trade name: HLV2-22BL447-3W) was used for 447 nm. The exposure was performed at the wavelengths and exposure amounts shown in Table 1 as the first wavelength. Then, the exposure was performed at the wavelengths and exposure amounts shown in Table 1 as the second wavelength. Table 1 shows the measurement results of complex viscosity at 25 °C before light irradiation, after irradiation with the second wavelength, storage modulus, loss modulus, and loss tangent at 25 °C after irradiation with the first wavelength.

[0104] Touch test 1: Evaluation of photocurability When touching the sample after irradiation with the first wavelength, if there was no transfer of resin to the finger with an elastomer or adhesive, it was evaluated as "A", if there was transfer of resin to the finger with a highly viscous liquid, it was evaluated as "B", and if there was transfer of resin to the finger with a liquid, it was evaluated as "C".

[0105] Touch test 2: Evaluation of photomeltability When touching the sample after the second wavelength irradiation, if there is resin transfer to the finger with a liquid, it was evaluated as "A" (with photo - meltability), and if there is no resin transfer to the finger due to an elastomer or slight adhesion, it was evaluated as "C" (without photo - meltability).

[0106] Table 1 shows the evaluation results of the photocurability of the compositions of Examples 1 - 1 to 1 - 2 and Comparative Examples 1 to 4.

[0107] Table 2 shows the evaluation results of the photocurability and photo - meltability of the compositions of Examples 2 - 1 to 2 - 8.

[0108]

Table 1

[0109] As shown in Table 1, it was shown that the compositions of the examples containing a disulfide compound, a vinyl ether compound, and an intramolecular cleavage type photo - radical generator had excellent curability.

[0110]

Table 2

[0111] As shown in Table 2, the compositions of Examples 2 - 1 to 2 - 7 were able to be photocured with a smaller irradiation dose compared to the composition of Example 2 - 8. With the compositions of the examples, it was possible to photo - melt the cured product after light irradiation.

Claims

[

1. ] A disulfide compound having two or more disulfide bonds, a vinyl ether compound having two or more vinyloxy groups, and an intramolecular cleavage type photo radical generator, and the intramolecular cleavage type photo radical generator includes a first intramolecular cleavage type photo radical generator and a second intramolecular cleavage type photo radical generator, the first intramolecular cleavage type photo radical generator is at least one selected from the group consisting of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, the second intramolecular cleavage type photo radical generator is at least one selected from the group consisting of 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, anisoin, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one, a composition. [

2. ] A disulfide compound having two or more disulfide bonds, a vinyl ether compound having two or more vinyloxy groups, and an intramolecular cleavage type photo radical generator, and the intramolecular cleavage type photo radical generator includes a first intramolecular cleavage type photo radical generator and a second intramolecular cleavage type photo radical generator, the first intramolecular cleavage type photo radical generator is bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, The composition, wherein the second intramolecular cleavage type photo radical generator is at least one selected from the group consisting of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, anisoin, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one.

3. The composition according to claim 1 or 2, wherein the disulfide compound has a structural unit represented by the following formula (1). 【Chemical 1】 [In formula (1), A represents a polyether group. ]

4. The composition according to claim 1 or 2, which is used as an adhesive.

5. A photo-melting composition containing a photo reaction product of a disulfide compound having two or more disulfide bonds and a vinyl ether compound having two or more vinyloxy groups, and an intramolecular cleavage type photo radical generator.

6. A photo-melting composition containing a compound having a disulfide bond and a structure represented by the following formula (A), and an intramolecular cleavage type photo radical generator. 【Chemical 2】 [In formula (A), * represents a bond. ]

7. The photo-melting composition according to claim 6, which has a structure represented by the following formula (B). [Chemical Formula 3] [In formula (B), n represents an integer of 1 or more, A represents a polyether group, * represents a bond, and a plurality of As may be the same or different from each other. ]

8. The photo-melting composition according to claim 6 or 7, which further has a structure represented by the following formula (C). 【Chemical Formula 4】 [In formula (C), * represents a bond. ]

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