Composition, photo-meltable composition, and compound

Abstract

The present invention relates to a composition containing a disulfide having two or more disulfide bonds, an allyl compound having two or more allyl groups, and an intramolecular cleavage-type photo-radical initiator.

Description

Technical Field

[0001] The invention relates to a composition, a photofusible composition and a compound. Background Art

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

[0003] Previous technical literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Publication No. 2018-30898 Summary of the invention

[0006] Technical issues to be solved by the invention

[0007] The storage stability of the photocurable composition in a mixed state of all components has room for improvement. In order to obtain stability for a certain period of time, it is necessary to consider a method of storage at low temperature or mixing immediately before use.

[0008] An object of the present invention is to provide a composition that can be handled as a one-liquid mixture having excellent photocurability and good storage stability.

[0009] Means for solving technical problems

[0010] The present invention relates to the following [1] to

[10] in several aspects. [1]

[0012] A composition comprises: a disulfide having two or more disulfide bonds, an allyl compound having two or more allyl groups, and an intramolecular cleavage type photo-radical initiator. [2]

[0014] The composition according to [1], wherein the intramolecular cleavage type photo-radical initiator comprises: an absorption coefficient at the first wavelength of 1.0×10 2 The first intramolecular cleavage type photoradical initiator and the absorption coefficient at the first wavelength are less than 1.0×10 2 The second intramolecular cleavage type photo-radical initiator. [3]

[0016] The composition according to [2], wherein the first intramolecular cleavage type photoradical initiator 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 photoradical initiator is at least one selected from the group consisting of 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, anisoin, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propane-1-one. [4]

[0018] The composition according to any one of [1] to [3], wherein the disulfide compound has a structural unit represented by the following formula (1).

[0019]

[0020] [In formula (1), A represents a polyether group.] [5]

[0022] The composition according to any one of [1] to [4], which is used for an adhesive. [6]

[0024] A photofusible composition comprises: a photoreaction product of a disulfide having two or more disulfide bonds and an allyl compound having two or more allyl groups, and an intramolecular cleavage type photo-radical initiator. [7]

[0026] A compound having a disulfide bond and a structure represented by the following formula (A).

[0027]

[0028] [In formula (A), * represents a bonding bond.] [8]

[0030] The compound according to [7], which has a structure represented by the following formula (B).

[0031]

[0032] [In formula (B), n represents an integer greater than 1, A represents a polyether group, * represents a bonding bond, and a plurality of A's may be the same or different.] [9]

[0034] The compound according to [7] or [8], further having a structure represented by the following formula (C).

[0035]

[0036] [In formula (C), * represents a bonding bond.]

[10]

[0038] A photofusible composition comprising: the compound described in any one of [7] to [9] and an intramolecular cleavage-type photoradical initiator.

[0039] Effects of the Invention

[0040] According to the present invention, there is provided a composition which can be handled as a one-liquid mixture having excellent photocurability and good storage stability. DETAILED DESCRIPTION

[0041] Several embodiments of the present invention are described in detail below, but the present invention is not limited to the following embodiments.

[0042] In this specification, the term "process" includes not only independent processes, but also processes that cannot be clearly distinguished from other processes as long as the intended effect of the process is achieved. In addition, a numerical range expressed using "to" indicates a range that includes the numerical values ​​recorded before and after "to" as the minimum and maximum values, respectively.

[0043] In addition, in this specification, when there are multiple substances corresponding to each component in the composition, the content of each component in the composition refers to the total amount of the multiple substances present in the composition unless otherwise specified. In addition, the exemplified materials may be used alone or in combination of two or more unless otherwise specified.

[0044] Furthermore, in the numerical ranges recorded in stages in this specification, the upper limit or lower limit of the numerical range in a certain stage may also be replaced by the upper limit or lower limit of the numerical range in other stages. Furthermore, in the numerical ranges recorded in this specification, the upper limit or lower limit of the numerical range may be replaced by the values ​​shown in the embodiments. "A or B" may include either A or B, or both.

[0045] 〔Composition〕

[0046] The composition of one embodiment contains a disulfide having two or more disulfide bonds, an allyl compound having two or more allyl groups, and an intramolecular cleavage type photoradical initiator. Since the composition has the property of being cured by light irradiation, it can also be called a photocurable composition.

[0047] The mechanism of photocuring of the composition is not clear, but it can be inferred, for example, as follows. However, the mechanism is not limited to this. It is believed that by irradiating the composition containing a disulfide, an allyl compound, and an intramolecular cleavage type photoradical initiator with light, the carbon-carbon double bond of the allyl group causes an insertion reaction with respect to the disulfide bond, and the disulfide forms a bond with the allyl compound and is high in molecular weight, thereby photocuring. It is believed that the molecular weight is also high by the reaction of the ene thiol of the allyl group in the disulfide and the allyl group in the allyl compound with the insertion reaction of the carbon-carbon double bond of the allyl group.

[0048] The cured product of the composition of one embodiment includes a photoreaction product showing photofusibility. Therefore, the cured product of the composition can be photomelted by light irradiation in the presence of an intramolecular cleavage type photoradical initiator. The mechanism of photomelting of the cured product of the composition is not clear, but the following mechanism can be considered, for example. However, it is not limited to these mechanisms. By photoreacting a disulfide with an allyl compound in the composition, a cured product containing a compound having a disulfide bond can be formed. The disulfide bond in the cured product is decomposed (cleaved) by light irradiation of the cured product of the composition, and thiol radicals are generated. At this time, if there is an intramolecular cleavage type photoradical initiator in the cured product, the thiol radical reacts with the intramolecular cleavage type photoradical initiator, and the thiol radical is capped by the photoradical initiator. Thus, it can be considered that the compound having a disulfide bond is low in molecular weight to make the cured product photomelted. As another mechanism, the following mechanism can also be considered: the photoinduced radicals generated by the intramolecular cleavage type photoradical initiator directly react with the disulfide bond, resulting in the formation of a photoinduced radical-thioether bond and the generation of a thiol radical, and the thiol radical reacts with another photoinduced radical, and the compound having a disulfide bond itself is reduced in molecular weight, thereby softening the photocured material. It can be said that the reaction of disulfide bond cleavage is an irreversible reaction.

[0049] <Disulfide>

[0050] A disulfide is a compound having two or more disulfide bonds. The number of disulfide bonds per disulfide molecule may be, for example, 1 to 1000 or 4 to 50.

[0051] The molecular weight of the disulfide may be 200-10,000,000, 200-3,000,000, 500-1,000,000, or 1,000-10,000.

[0052] The number average molecular weight of the disulfide may be 200 to 10,000,000, 200 to 3,000,000, 500 to 1,000,000, or 1,000 to 10,000. The number average molecular weight is a polystyrene conversion value obtained by gel permeation chromatography (GPC) using a calibration curve based on standard polystyrene.

[0053] The disulfide may have one or more (eg, two or more) thiol groups (—SH). The disulfide may be a compound having two thiol groups.

[0054] The disulfide may be a compound (for example, a polymer or an oligomer) having a linear molecular chain and a terminal group and having a disulfide bond in the molecular chain.

[0055] The disulfide may be, for example, a compound having a structural unit represented by the following formula (1). In this case, a cured product of the composition having more excellent optical solubility can be formed.

[0056]

[0057] In formula (1), A represents a divalent organic group.

[0058] The disulfide having a structural unit represented by 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 that can react with the first group. The first group may be, for example, a carboxyl group. As the first precursor compound, for example, dithiodipropionic acid may be cited. The second group may be, for example, a hydroxyl group or an epoxy group. The second precursor compound may be a compound having two or more second groups or a compound having two second groups. As the second precursor compound, diol compounds such as diol oligomers and diol polymers, compounds having an epoxy group at the end such as polyalkylene glycol diglycidyl ether, silicone, etc. may be cited. As the diol compound, for example, polyalkylene glycols such as polyethylene glycol and polypropylene glycol may be cited.

[0059] 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 polyoxyalkylene group represented by -A 1 -OA 2 -OA 3 - represents a group. 1 ~A 3 Each of them independently may be an alkylene group, or 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 -CH2CH2-O-CH2-O-CH2CH2- and the like.

[0060] The disulfide compound may be, for example, a compound represented by the following formula (1A).

[0061]

[0062] In formula (1A), n represents an integer greater than 1, A represents the same meaning as above, and X 1 and X 2 A represents a terminal group. A plurality of A's may be the same or different from each other. 1 and X 2 Examples of the terminal group represented by X include a thiol group, a hydroxyl group, a cyclic ether, a carboxyl group, and an unsaturated double bond. 1 and X 2 They may be the same as or different from each other. n is an integer of 1 or more, for example, an integer of 2 or more and 500 or an integer of 10 or more and 100 or less.

[0063] As the disulfide, for example, a compound obtained by synthesis such as a reaction product of the first precursor compound and the second precursor compound can be used, or commercially available products such as Thiokol LP series (dithiol having a disulfide bond, manufactured by TORAY FINE CHEMICALS CO., LTD.) can be used. The disulfide can be used alone or in combination of two or more.

[0064] The content of the disulfide may be 50 mass % or more, 60 mass % or more, 70 mass % or more, 75 mass % or more, or 80 mass % or less, or 95 mass % or less, 90 mass % or less, or 87 mass % or less, based on the total mass of the composition.

[0065] <Allyl compounds>

[0066] The allyl compound is a compound having two or more allyl groups (H2C=CH-CH2-). The allyl compound may be used alone or in combination of two or more.

[0067] The number of allyl groups per molecule of the allyl compound may be, for example, 2 to 8, 2 to 4, and preferably 2 to 3. From the viewpoint of further improving the storage modulus during photocuring, the allyl compound may contain a diallyl compound having two allyl groups and a triallyl compound having three allyl groups.

[0068] The molecular weight of the allyl compound may be, for example, 100 or more, or 150 or more, or 1000 or less, or 300 or less.

[0069] The allyl compound may contain, for example, a diallyl compound formed by two allyl groups and a linking group linking the allyl groups. That is, the allyl compound may contain a diallyl compound represented by the formula (2): H2C=CH-CH2-Z-CH2-CH=CH2. In the 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 less or 10 or less than 20. The linking group may contain, for example, an arylene group, an ester bond, an alkenylene group, a polyoxyalkylene group (polyoxyethylene, etc.), an alkylene group, a cycloalkylene group, or a combination of these groups.

[0070] The diallyl compound may be represented by the formula (2a): H2C=CH-CH2-Z 1 -Z 3 -Z 2 -CH2-CH=CH2 represented by the compound. 1 , Z 2 and Z 3 Z represent connecting groups respectively. 1 and Z 2 Z may be independently a single bond or an ester bond. 3 It may be a substituted or unsubstituted divalent hydrocarbon group, for example, a phenylene group (-C6H4-) or an alkenylene group (-CH=CH-).

[0071] Examples of the diallyl compound include diallyl isophthalate, diallyl terephthalate, diallyl fumarate, and diallyl maleate.

[0072] The allyl compound may include, for example, a triallyl compound consisting of three allyl groups and a linking group linking the three allyl groups. Examples of the triallyl compound include triallyl isocyanurate.

[0073] Based on the total mass of the composition, the content of the allyl compound can be 1.0 mass % or more, 1.5 mass % or more, 2.0 mass % or more, 2.5 mass % or more, 3.0 mass % or more, 3.5 mass % or more, 4.0 mass % or more, 4.5 mass % or more, 5.0 mass % or more, or it can be 20.0 mass % or less, 15.0 mass % or less, 10.0 mass % or less, 8.0 mass % or less, 6.0 mass % or less, or 5.0 mass % or less.

[0074] The ratio (B / A) of the number of moles of the allyl compound (B) to the number of moles of the disulfide (A) may be 0.5 or more or 1 or 3 or less or 4 or less.

[0075] When the disulfide contains a thiol group, the ratio (D / C) of the total molar number of allyl groups in the allyl compound (D) to the total molar number of thiol groups in the disulfide (C) may be 0.5 or more, or 1.5 or less, or 1.1 or less.

[0076] <Intramolecular cleavage type photoradical initiator>

[0077] The intramolecular cleavage type photoradical initiator is a compound that generates two radicals by photolysis upon irradiation with light. As the intramolecular cleavage type photoradical initiator, a compound used as an intramolecular cleavage type photoradical polymerization initiator can be used.

[0078] Examples of the intramolecular cleavage type photoradical initiator include benzyl ketal photoradical initiators, α-aminoalkylphenone photoradical initiators, α-hydroxyalkylphenone photoradical initiators, α-hydroxyacetophenone photoradical initiators, and acylphosphine oxide photoradical initiators. The intramolecular cleavage type photoradical initiators may be used alone or in combination of two or more.

[0079] Examples of the benzyl ketal-based photoradical initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one (Omnirad 651) and the like.

[0080] Examples of α-aminoalkylphenone-based photoradical initiators include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (Omnirad369), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one (Omnirad907), and 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one (Omnirad379EG).

[0081] Examples of the α-hydroxyalkylphenone-based photoradical initiator include 1-hydroxy-cyclohexyl-phenyl-ketone (Omnirad 184) and the like.

[0082] Examples of the α-hydroxyacetophenone-based photoradical initiator include 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propane-1-one (Omnirad127), 2-hydroxy-2-methyl-1-phenyl-propane-1-one (Omnirad1173), and anisoin.

[0083] Examples of the acylphosphine oxide-based photoradical initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Omnirad TPO H) and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Omnirad 819).

[0084] The intramolecular cleavage type photoradical initiator may contain a photosensitive 2 The first intramolecular cleavage type photoradical initiator and the absorption coefficient at the first wavelength are less than 1.0×10 2 The absorption coefficient in this specification is a value measured in methanol or acetonitrile (unit: mL / g·cm).

[0085] When the composition contains the first and second intramolecular cleavage type photoradical initiators, the cured product obtained by irradiating the cured product with the first light containing the first wavelength can be melted by irradiating the cured product with the second light containing the light of the second wavelength different from the first wavelength. The second light can contain the light of the second wavelength located on the shorter wavelength side than the first wavelength.

[0086] The first wavelength, for example, may be 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.

[0087] The absorption coefficient at a wavelength of 447 nm is 1.0×10 2 Examples of the intramolecular cleavage-type photoradical initiator include bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Omnirad 819).

[0088] The absorption coefficient at a wavelength of 447 nm is less than 1.0×10 2 The absorption coefficient at a wavelength of 405 nm is 1.0×10 2 Examples of the intramolecular cleavage type photoradical initiator include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (Omnirad 369) and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Omnirad TPO H).

[0089] The absorption coefficient at a wavelength of 447 nm and the absorption coefficient at a wavelength of 405 nm are less than 1.0×10 2Examples of intramolecular cleavage type photoradical initiators include 1-hydroxy-cyclohexyl-phenyl-ketone (Omnirad184), 2-hydroxy-2-methyl-1-phenyl-propane-1-one (Omnirad1173), anisoin, 2,2-dimethoxy-1,2-diphenylethane-1-one (Omnirad651), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one (Omnirad907) and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propane-1-one (Omnirad127).

[0090] The composition of one embodiment may include a 2 The first intramolecular cleavage type photo-radical initiator and the absorption coefficient at a wavelength of 447 nm are less than 1.0×10 2 For example, the first intramolecular cleavage type photoradical initiator may be bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and the second intramolecular cleavage type photoradical initiator may be 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-propane-1-one, anisoin, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one or 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propane-1-one.

[0091] The composition of another embodiment may include a luminescent material having an absorption coefficient of 1.0×10 2 The first intramolecular cleavage type photo-radical initiator and the absorption coefficient at a wavelength of 405 nm are less than 1.0×10 2 The second intramolecular cleavage type photo-radical initiator.

[0092] For example, the first intramolecular cleavage type photoradical initiator can be 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and the second intramolecular cleavage type photoradical initiator can be 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, anisoin, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one or 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propane-1-one. The first intramolecular cleavage type photoradical initiator can be 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and the second intramolecular cleavage type photoradical initiator can be 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, anisoin, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one or 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propane-1-one.

[0093] Preferred combinations of the first and second intramolecular cleavage type photoradical initiators include, for example, a combination of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Omnirad TPO H) and 2-hydroxy-2-methyl-1-phenyl-propane-1-one (Omnirad 1173), 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Omnirad TPO H) and 1-hydroxy-cyclohexyl-phenyl-ketone (Omnirad184) or anisole, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (Omnirad369) and 2-hydroxy-2-methyl-1-phenyl-propane-1-one (Omnirad1173), bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Omnirad819) and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (OmniradTPO H).

[0094] Based on the total mass of the composition, the total content of the intramolecular cleavage type photoradical initiator can be 5 mass% or more, 7 mass% or more, or 9 mass% or less, or 30 mass% or less, 20 mass% or less, 15 mass% or less, or 12 mass% or less.

[0095] Based on the total mass of the composition, the content of the first intramolecular cleavage-type photoradical initiator can be greater than 0.8 mass%, greater than 1.0 mass%, greater than 1.5 mass% or greater than 2.0 mass%, or less than 5.0 mass%, less than 4.0 mass%, less than 3.0 mass%, less than 2.0 mass% or less than 1.8 mass%.

[0096] The ratio (A / C1) of the molar number of disulfide (A) to the molar number of the first intramolecular cleavage-type photoradical initiator (C1) can be, for example, greater than 2, greater than 3, greater than 4 or greater than 5, or less than 12, less than 10, less than 8, less than 6 or less than 4.

[0097] The ratio (B / C1) of the molar number of the allyl compound (B) to the molar number of the first intramolecular cleavage-type photoradical initiator (C1) can be, for example, greater than 1, greater than 2, greater than 3, greater than 4 or greater than 5, or less than 12, less than 10, less than 8, less than 6 or less than 5.

[0098] Based on the total mass of the composition, the content of the second intramolecular cleavage-type photoradical initiator can be greater than 3 mass%, greater than 4 mass%, greater than 5 mass%, greater than 6 mass% or greater than 7 mass%, or can be less than 30 mass%, less than 20 mass%, less than 15 mass%, less than 10 mass% or less than 8 mass%.

[0099] The ratio (A / C2) of the molar number of disulfide (A) to the molar number of the second intramolecular cleavage-type photoradical initiator (C2) can be, for example, greater than 0.20, greater than 0.25, greater than 0.30, greater than 0.35 or greater than 0.45, or less than 1.0, less than 0.80, less than 0.70 or less than 0.60.

[0100] The ratio (B / C2) of the molar number of the allyl compound (B) to the molar number of the second intramolecular cleavage-type photoradical initiator (C2) can be, for example, greater than 0.20, greater than 0.25, greater than 0.30, greater than 0.35, greater than 0.40 or greater than 0.45, or less than 1.0, less than 0.80, less than 0.70 or less than 0.60.

[0101] Composition can also include components (other components) other than disulfide, allyl compound and intramolecular cleavage type photo-radical initiator. As other components, for example, can enumerate the adhesiveness imparting agent such as plasticizer, tackifier, antioxidant, leuco dye, sensitizer, coupling agent and other adhesion improvers, inhibitor, light stabilizer, defoamer, filler, chain transfer agent, thixotropy imparting agent, flame retardant, release agent, surfactant, lubricant, antistatic agent and other additives. These additives can use known additives. Based on the total amount of composition, the total amount of the content of other components can be less than 50 mass %, less than 20 mass % or less than 5 mass %.

[0102] <Method for producing composition>

[0103] The composition can be produced, for example, by a method comprising the following steps: mixing or kneading the disulfide, the allyl compound, the intramolecular cleavage type photo-radical initiator, and the components added as needed. The mixing and kneading can be carried out by appropriately combining a conventional dispersing machine such as a stirrer, a pestle, a three-roll mill, a ball mill, a bead mill, etc.

[0104] <Application>

[0105] The composition of one embodiment can be used for applications such as an adhesive, a temporary fixing material, a photoresist, a resin for a 3D printer, and a resin for a molding material.

[0106] 〔Cured product〕

[0107] The cured product of the composition of one embodiment includes a photoreaction product of a disulfide and an allyl compound. The cured product may include an intramolecular cleavage type photoradical initiator. The cured product including the photoreaction product of a disulfide and an allyl compound and the intramolecular cleavage type photoradical initiator has the property of melting by light irradiation, and therefore can also be called a photofusible composition.

[0108] The solidified material may have various shapes. The shape of the solidified material may be, for example, a film-like shape or a block-like shape. For example, a solidified material formed into a film-like shape may be used as a resin film. A solidified material formed into a block-like shape may be used as a resin block. The method for forming a film-like or block-like solidified material is not particularly limited, and a known method may be applied.

[0109] The storage modulus of the cured product at 25° C. may be 10,000 Pa or more, 30,000 Pa or more, 50,000 Pa or more, 70,000 Pa or more, 110,000 Pa or more, 130,000 Pa or more, or 150,000 Pa or more. The storage modulus of the cured product at 25° C. is not particularly limited, and may be, for example, 10 MPa or less. The method for measuring the storage modulus at 25° C. is described in the Examples.

[0110] <Method for producing cured product>

[0111] The cured product of the composition of one embodiment can be produced by a method including the step of irradiating the composition with light to react the disulfide and the allyl compound.

[0112] The light (curing light) used when forming the cured product may be, for example, ultraviolet light or visible light. The wavelength of the curing light may be appropriately selected, for example, according to the type of intramolecular cleavage type photoradical initiator used. The wavelength of the curing light may be, for example, 150 to 830 nm. The curing light may include, for example, light having a wavelength of 447 nm, a wavelength of 405 nm, or a wavelength of 365 nm.

[0113] Light irradiation can be performed, for example, using a light irradiation device at an irradiation dose of 100 mJ / cm 2 The irradiation dose can be appropriately set according to the wavelength of the curing light, for example. The irradiation dose can be, for example, 1000 mJ / cm 2 Above, 2000mJ / cm 2 Above, 2500mJ / cm 2 Above, 5000mJ / cm 2 Above, 10000mJ / cm 2 Above or 15000mJ / cm 2 Above, it can also be 50000mJ / cm 2 Below, 35000mJ / cm 2 Below, 25000mJ / cm 2 Below, 10000mJ / cm 2 Below, 5000mJ / cm 2 Below or 3500mJ / cm 2 the following.

[0114] The irradiation amount refers to the product of the illuminance and the irradiation time (seconds). In addition, as a light source for ultraviolet light or visible light irradiation, for example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, an LED lamp, etc. can be cited. The light irradiation can be performed directly on the composition or through glass, etc.

[0115] [Compounds in this case]

[0116] The compound of one embodiment (hereinafter also referred to as “the compound of the present invention”) has a disulfide bond and a structure represented by the following formula (A).

[0117]

[0118] The compound of the present invention can be prepared by a method comprising the following steps: irradiating a composition comprising a disulfide, an allyl compound and an intramolecular cleavage type photo-radical initiator with light to react the disulfide with the allyl compound. The disulfide, the allyl compound and the intramolecular cleavage type photo-radical initiator can be as described above. The light irradiation conditions can use the above conditions.

[0119] The production of the compound of the present invention was confirmed by NMR, IR, GC-MS and the like.

[0120] The structure represented by the above formula (A) is not limited thereto, but it is presumed that it is formed by the reaction of a disulfide with an allyl compound, whereby a carbon-carbon double bond in the allyl group undergoes an insertion reaction into a disulfide bond.

[0121] The compound of the present invention may have a structure represented by the following formula (B).

[0122]

[0123] In formula (B), n represents an integer greater than 1, A represents a polyether group, * represents a bonding bond, and a plurality of A's may be the same or different. A and n may have the same meanings as those described above.

[0124] The compound of the present invention 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).

[0125] The compound of the present invention may also have a structure represented by the following formula (C).

[0126]

[0127] The compound of the present invention having a structure represented by the above formula (C) can be obtained, for example, by using a disulfide having two thiol groups in the method for producing the compound of the present invention. It can be inferred that the structure represented by the above formula (C) is formed by the reaction of the thiol group with the ene thiol of the allyl group in the allyl compound.

[0128] [Photofusible composition]

[0129] An optically fusible composition of one embodiment contains a photoreaction product of a sulfur compound and an allyl compound and an intramolecular cleavage type optical radical initiator. An optically fusible composition of another embodiment contains the compound of the present invention and an intramolecular cleavage type optical radical initiator.

[0130] The photofusible composition can be manufactured, for example, by a method comprising the following steps: irradiating a composition comprising a sulfur compound, an allyl compound, and a first and a second intramolecular cleavage-type photoradical initiator with a first light comprising a first wavelength, and causing the sulfur compound and the allyl compound to react to form a cured product (photofusible composition) comprising a photoreaction product of the sulfur compound and the allyl compound and the second intramolecular cleavage-type photoradical initiator.

[0131] [Method for producing photo-melted material]

[0132] The method for producing a photofusible product in one embodiment includes the step of irradiating a photofusible composition containing the photoreaction product and an intramolecular cleavage type photoradical initiator with light to form a photofusible product. The method for producing a photofusible product in another embodiment includes the step of irradiating a photofusible composition containing the compound of the present invention and an intramolecular cleavage type photoradical initiator with light to form a photofusible product.

[0133] The light used to form the melt (melting light) may be, for example, ultraviolet light or visible light. The wavelength of the melting light may be appropriately selected, for example, according to the type of intramolecular cleavage type photoradical initiator used. The wavelength of the melting light may be, for example, 150 to 830 nm. The melting light may include, for example, light having a wavelength of 405 nm or a wavelength of 365 nm.

[0134] Light irradiation can be performed, for example, using a light irradiation device at an irradiation dose exceeding 3000 mJ / cm 2 The irradiation amount can be appropriately set according to the wavelength of the curing light, for example. The irradiation amount can be, for example, 15000 mJ / cm 2 Above, 20000mJ / cm 2 Above or 25000mJ / cm 2 Above, it can also be 100000mJ / cm 2 Below, 50000mJ / cm 2 Below or 35000mJ / cm 2 the following.

[0135] 〔Adhesion〕

[0136] The adherend of the present embodiment comprises a first adherend, a second adherend, and an adhesive layer for bonding the first adherend and the second adherend to each other. The adhesive layer contains the optically fusible composition described above.

[0137] As the first adherend and the second adherend, for example, 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 can be cited; inorganic materials such as steel, stainless steel, metal (aluminum, copper, nickel, chromium, etc.) monomers or alloys of these metals, glass, and silicon wafers; wood; rubber, etc. In addition, as the first adherend and the second adherend, materials in which the above plastics and the above inorganic materials are composited can also be cited.

[0138] Adherent for example can be manufactured by the method comprising the following operation: under the state that the composition of present embodiment is contacted with the 1st adherend and the 2nd adherend, composition is irradiated the 1st light, thereby forms the adhesive layer that the 1st adherend and the 2nd adherend are bonded to each other. The 1st light, for example, can be suitably set according to the kind of intramolecular cleavage type photo-radical initiator etc. The irradiation condition of the 1st light can be above-mentioned condition.

[0139] [Method for separating the bonded body]

[0140] The method for separating an adherend of one embodiment comprises a step of irradiating the adhesive layer of the adherend with a second light to separate the first adherend and the second adherend. The adhesive layer contains a light-fusible composition, so the light-fusible composition is melted by irradiating light so that the adherends can be easily separated from each other. The second light can be appropriately set according to the type of intramolecular cleavage type photo-radical initiator, etc. The irradiation conditions of the second light can be the above-mentioned conditions.

[0141] Example

[0142] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

[0143] As the component (A), the following compounds having two or more disulfide bonds were prepared.

[0144] Thiokol LP-55 (polysulfide, manufactured by TORAY FINE CHEMICALS CO., LTD., number average molecular weight (Mn): 3677.8)

[0145] As the component (B), the following compounds having a carbon-carbon double bond were prepared.

[0146] DAIP (diallyl isophthalate, manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 246.26)

[0147] TAIC (triallyl isocyanurate, manufactured by SHINRYO CORPORATION, molecular weight 249)

[0148] DEGDVE (diethylene glycol divinyl ether, manufactured by Nippon Carbide Industries Co., Inc., molecular weight: 158.2)

[0149] TEGDVE (triethylene glycol divinyl ether, manufactured by Nippon Carbide Industries Co., Inc., molecular weight: 202.28)

[0150] As the component (C), the photoradical initiator shown below was prepared.

[0151] (Intramolecular cleavage type photoradical initiator)

[0152] Omnirad-TPO H (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, manufactured by IGM Resins BV, molecular weight: 348)

[0153] Omnirad-1173 (2-hydroxy-2-methyl-1-phenylpropanone, manufactured by IGM Resins BV, molecular weight: 164.2)

[0154] Preparation of composition

[0155] The components and amounts (unit: parts by mass) described in Table 1 were added to a 100 mL flask, and stirred at 100° C. for 1 hour with a mechanical stirrer to dissolve and mix the components, thereby obtaining compositions of Examples 1 and 2 and Comparative Examples 1 and 2.

[0156] Evaluation of light curing / melting properties

[0157] Using a viscoelasticity measuring device (manufactured by TA Instruments, trade name: DHR-2), the evaluation sample was irradiated with ultraviolet light from the light-transmitting bottom surface, and the change in storage modulus with respect to light irradiation time at 25°C was measured. For light irradiation, an LED lamp (manufactured by Panasonic Industrial Devices SUNX Co., Ltd., trade name: Ai cure UJ30 / ANUJ6186 and ANUJ6189) was used, with an exposure amount of 20,000 mJ / cm as the first wavelength. 2 , and then as the second wavelength with an exposure of 30000mJ / cm 2The exposure was performed. Table 1 shows the measurement results of the storage modulus after irradiation with the first wavelength and the second wavelength. Furthermore, the same measurement was performed after each composition before photocuring was stored at 40°C for one week. The results are shown in Table 1. The first wavelength is 405 nm. The second wavelength is 365 nm.

[0158] [Table 1]

[0159]

[0160] As shown in Table 1, the storage modulus after irradiation with the first wavelength of Comparative Examples 1 and 2 using vinyl ether compounds significantly decreased compared to the initial value after storage at 40°C for one week. On the other hand, the storage modulus after irradiation with the first wavelength of Examples 1 and 2 using allyl compounds was maintained after storage at 40°C for one week.

Claims

1. A composition comprising: Disulfides having more than two disulfide bonds; Allyl compounds having two or more allyl groups; and Intramolecular cleavage type photoradical initiator.

2. The composition according to claim 1, wherein The intramolecular cleavage type photo-radical initiator comprises: The absorption coefficient at the first wavelength is 1.0×10 2 The first intramolecular cleavage type photo-radical initiator described above; and The absorption coefficient at the first wavelength is less than 1.0×10 2 The second intramolecular cleavage type photo-radical initiator.

3. The composition according to claim 2, wherein The first intramolecular cleavage type photo-radical initiator 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 photoradical initiator is at least one selected from the group consisting of 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, anisoin, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propane-1-one.

4. The composition according to any one of claims 1 to 3, wherein The disulfide has a structural unit represented by the following formula (1), In formula (1), A represents a polyether group.

5. The composition according to any one of claims 1 to 3, which is used in an adhesive.

6. A photofusible composition comprising: a photoreaction product of a disulfide having two or more disulfide bonds and an allyl compound having two or more allyl groups; and an intramolecular cleavage-type photoradical initiator.

7. A compound having a disulfide bond and a structure represented by the following formula (A), In formula (A), * represents a bond.

8. The compound according to claim 7, which has a structure represented by the following formula (B), In the formula (B), n represents an integer of 1 or greater, A represents a polyether group, and * represents a bonding bond. A plurality of A's may be the same as or different from each other.

9. The compound according to claim 7 or 8, which further has a structure represented by the following formula (C), In formula (C), * represents a bond.

10. A photofusible composition comprising: the compound according to claim 7 or 8 and an intramolecular cleavage type photo-radical initiator.

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