WO2022153397A1 - Composition, composition fusible sous l'effet de la lumière et composé - Google Patents

Composition, composition fusible sous l'effet de la lumière et composé Download PDF

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Publication number
WO2022153397A1
WO2022153397A1 PCT/JP2021/000843 JP2021000843W WO2022153397A1 WO 2022153397 A1 WO2022153397 A1 WO 2022153397A1 JP 2021000843 W JP2021000843 W JP 2021000843W WO 2022153397 A1 WO2022153397 A1 WO 2022153397A1
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WIPO (PCT)
Prior art keywords
compound
photoradical generator
intramolecular cleavage
cleavage type
hydroxy
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PCT/JP2021/000843
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English (en)
Japanese (ja)
Inventor
祐樹 宮本
博司 大▲崎▼
尚 熊木
Original Assignee
昭和電工マテリアルズ株式会社
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Application filed by 昭和電工マテリアルズ株式会社 filed Critical 昭和電工マテリアルズ株式会社
Priority to JP2022574913A priority Critical patent/JPWO2022153397A1/ja
Priority to PCT/JP2021/000843 priority patent/WO2022153397A1/fr
Priority to TW111101275A priority patent/TW202237671A/zh
Publication of WO2022153397A1 publication Critical patent/WO2022153397A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers

Definitions

  • the present invention relates to compositions, photomeltable compositions and compounds.
  • Patent Document 1 describes a photocurable resin composition containing a compound (A) having a photopolymerizable functional group and an oil gelling agent (B), which has a shear rate of 1.0 s- at 25 ° C.
  • a photocurable resin composition having a viscosity at 1 of 30 to 1000 Pa ⁇ s is disclosed.
  • One aspect of the present invention is to provide a new composition having excellent photocurability.
  • 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 vinyl oxy groups, and an intramolecular cleavage type photoradical generator.
  • the intramolecular cleavage type photoradical generator is the first intramolecular cleavage type photoradical generator having an absorption coefficient of 1.0 ⁇ 102 or more at the first wavelength, and the absorption coefficient at the first wavelength is 1. It may include a second intramolecular cleavage type photoradical generator of 0 ⁇ 10 2 or more.
  • the first intramolecular cleavage photoradical generators are 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, and 2,4,6-trimethylbenzoyl-diphenyl-phosphine. At least one selected from the group consisting of oxides, the second intramolecular cleavage type photoradical generator is 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane.
  • the first intramolecular cleavage photoradical generator is bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide
  • the second intramolecular cleavage photoradical 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-Propane-1-one, Anisoin, 2,2-Dimethoxy-1,2-diphenylethane-1-one, 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane Selected from the group consisting of -1-one and 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl ⁇ -2-methyl-prop
  • the disulfide compound may have a structural unit represented by the following formula (1).
  • A represents a polyether group.
  • composition may be used as an adhesive.
  • One aspect of the present invention is light, which comprises a photoreaction product of a disulfide compound having two or more disulfide bonds, a vinyl ether compound having two or more vinyloxy groups, and an intramolecular cleavage type photoradical generator. With respect to the meltable composition.
  • One aspect of the present invention relates to a compound having a disulfide bond and a structure represented by the following formula (A). [In formula (A), * indicates a bond. ]
  • the compound may be a compound having a structure represented by the following formula (B).
  • n represents an integer of 1 or more
  • A represents a polyether group
  • * represents a bond
  • a plurality of A's may be the same or different from each other.
  • the compound may further have a structure represented by the following formula (C). [In formula (C), * indicates a bond. ]
  • One aspect of the present invention relates to a photomeltable composition containing the above-mentioned compound and an intramolecular cleavage type photoradical generator.
  • process is included in this term not only as an independent process but also as long as the desired action of the process is achieved even if it cannot be clearly distinguished from other processes. Is done. Further, the numerical range indicated by using "-" indicates a range including the numerical values before and after "-" as the minimum value and the maximum value, respectively.
  • each component in the composition refers to the content of each component in the composition when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified. Means the total amount. Further, the exemplary materials may be used alone or in combination of two or more unless otherwise specified.
  • the upper limit value or the lower limit value of the numerical range of one step may be replaced with the upper limit value or the lower limit value of the numerical range of another step.
  • 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" may include either A or B, or both.
  • composition of one embodiment contains a disulfide compound having two or more disulfide bonds, a vinyl ether compound having two or more vinyl oxy groups, and an intramolecular cleavage type photoradical generator. Since the composition has a property of being cured by light irradiation, it can also be called a photocurable composition.
  • composition photocures is not clear, but it is inferred as follows, for example. However, the mechanism is not limited to this.
  • a composition containing a disulfide compound, a vinyl ether compound and an intramolecular cleavage type photoradical generator By irradiating a composition containing a disulfide compound, a vinyl ether compound and an intramolecular cleavage type photoradical generator with light, a carbon-carbon double bond of a vinyloxy group causes an insertion reaction with respect to the disulfide bond to form a disulfide compound. It is considered that photocuring occurs when the vinyl ether compound forms a bond to increase the molecular weight.
  • the thiol group in the disulfide compound and the vinyloxy group in the vinyl ether compound can be subjected to an enthiol reaction in addition to the insertion reaction of the carbon-carbon double bond of the vinyloxy group to the disulfide bond. It is considered that the increase in molecular weight progresses.
  • the cured product of the composition of one embodiment contains a photoreaction product exhibiting photomeltability. Therefore, the cured product of the composition can be photomelted by irradiating with light in the presence of an intramolecular cleavage type photoradical generator.
  • the mechanism by which the cured product of the composition is photomelted is not clear, but the following mechanism can be considered, for example. However, it is not limited to these mechanisms.
  • the disulfide bond in the cured product is decomposed (cleaved) and a chile radical is generated.
  • the chile radical reacts with the intramolecular cleavage type photoradical generator, and the chile radical is capped by the photoradical generator.
  • photoinduced radicals caused by an intramolecular cleavage type photoradical generator react directly with a disulfide bond to form a photoinduced radical-thioether bond and generate a chile radical, which is different from the chile radical. It is also conceivable that the compound itself having a disulfide bond has a low molecular weight and the photocured product is softened. It can be said that the reaction in which the disulfide bond is cleaved is an irreversible reaction.
  • 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.
  • the molecular weight of the disulfide compound may be 200 to 10,000,000, 200 to 3,000,000, 500 to 1,000,000, or 1000 to 10000.
  • the number average molecular weight of the disulfide compound may be 200 to 10,000,000, 200 to 3,000,000, 500 to 1,000,000, or 1000 to 10000.
  • the number average molecular weight is a polystyrene-equivalent value using a calibration curve made of standard polystyrene by gel permeation chromatography (GPC).
  • 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.
  • the disulfide compound may be a compound having a linear molecular chain and a terminal group and having a disulfide bond in the molecular chain (for example, a polymer or an oligomer).
  • the disulfide compound may be, for example, a compound having a structural unit represented by the following formula (1).
  • a cured product of the composition having better photomeltability can be formed.
  • A represents a divalent organic group.
  • the disulfide compound having the structural unit represented by the formula (1) can react with, for example, a first precursor compound having a disulfide bond and having two first groups with the first group. It may be a reaction product with a second precursor compound having a second 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 end such as polyalkylene glycol diglycidyl ether, and silicones.
  • Examples of the diol compound include polyalkylene glycols such as polyethylene glycol and polypropylene glycol.
  • 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 group represented by -A 1 -OA 2 -OA 3- .
  • Each of A 1 to A 3 may be an alkylene group independently, 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- and the like.
  • the disulfide compound may be, for example, a compound represented by the following formula (1A).
  • n represents an integer of 1 or more
  • A has the same meaning as above
  • X 1 and X 2 represent terminal groups.
  • a plurality of A's may be the same or different from each other.
  • Examples of the terminal group represented by X 1 and X 2 include a thiol group, a hydroxy group, a cyclic ether, a carboxyl group, and an unsaturated double bond.
  • X 1 and X 2 may be the same or different from each other.
  • n is an integer of 1 or more, and may be, for example, an integer of 2 or more and 500 or less, or 10 or more and 100 or less.
  • the disulfide compound for example, a compound obtained by synthesis such as a reaction product of the first precursor compound and the second precursor compound described above may be used, and the thiocol LP series (having a disulfide bond) may be used. Commercially available products such as dithiol and Toray Fine Chemicals Co., Ltd. may be used. One type of disulfide compound may be used alone, or two or more types may be used in combination.
  • 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 95% by mass or less, based on the total mass of the composition. , 90% by mass or less, or 85% by mass or less.
  • the vinyl ether compound one type may be used alone, or two or more types may be used in combination.
  • 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 is preferably 2.
  • the molecular weight of the vinyl ether compound may be, for example, 100 or more, 150 or more, 1000 or less, and 300 or less.
  • 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 be 10 or less or 20 or less.
  • the linking group may be, for example, a polyoxyalkylene group (polyoxyethylene group or the like), an alkylene group, a cycloalkylene group, or a combination of these groups.
  • vinyl ether compound examples include diethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, and 1,4-butanediol divinyl ether.
  • 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, based on the total mass of the composition. It may be 0.0% by mass or less, 10.0% by mass or less, or 5.0% by mass or less.
  • 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.
  • An intramolecular cleavage type photoradical generator is a compound in which the substance itself is photocleaved by irradiation with light to generate two radicals.
  • a compound used as an intramolecular cleavage type photoradical polymerization initiator can be used as the intramolecular cleavage type photoradical generator.
  • Examples of the intramolecular cleavage type photoradical generator include a benzyl ketal photoradical generator, an ⁇ -aminoalkylphenone photoradical generator, an ⁇ -hydroxyalkylphenone photoradical generator, and an ⁇ -hydroxyacetophenone photoradical generator. Examples thereof include a generator and an acylphosphine oxide-based photoradical generator. As the intramolecular cleavage type photoradical generator, one type may be used alone, or two or more types may be used in combination.
  • Examples of the benzyl ketal-based photoradical generator include 2,2-dimethoxy-1,2-diphenylethane-1-one (Omnirad 651).
  • Examples of the ⁇ -aminoalkylphenone-based photoradical generator include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (Omnirad369) and 2-methyl-1- [4- (methylthio). ) Phenyl] -2-morpholinopropan-1-one (Omnirad907), 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-moriphorin-4-yl-phenyl) -butane-1- On (Omnirad379EG) and the like can be mentioned.
  • Examples of the ⁇ -hydroxyalkylphenone-based photoradical generator include 1-hydroxy-cyclohexyl-phenyl-ketone (Omnirad 184).
  • acylphosphine oxide-based photoradical generator examples include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (OmniradTPO H), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Omnirad819), and the like. Can be mentioned.
  • the intramolecular cleavage type photoradical generator has an absorption coefficient at the first wavelength of 1.0 ⁇ 102 or more , and the first intramolecular cleavage type photoradical generator has an absorption coefficient at the first wavelength.
  • 1.0 ⁇ 102 may contain a second intramolecular cleavage photoradical generator.
  • the extinction coefficient in the present specification is a value (unit: mL / g ⁇ cm) measured in methanol or acetonitrile.
  • the cured product obtained by irradiating the cured product with the first light containing the light of the first wavelength is the first.
  • the cured product can be melted by irradiating with a second light containing light having a wavelength different from the wavelength (second wavelength).
  • the second light may include light having a second wavelength on the shorter wavelength side than the first wavelength.
  • the first wavelength may be, for example, 447 nm nm or 405 nm. If the first wavelength is 447 nm, the second wavelength may be 405 nm or 365 nm. If the first wavelength is 405 nm, the second wavelength may be 365 nm.
  • Examples of the intramolecular cleavage type photoradical generator having an extinction coefficient of 1.0 ⁇ 102 or more at a wavelength of 447 nm include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Omnirad819). Be done.
  • Examples of the intramolecular cleavage type photoradical generator having an extinction coefficient of less than 1.0 ⁇ 102 at a wavelength of 447 nm and an extinction coefficient of 1.0 ⁇ 102 or more at a wavelength of 405 nm include 2 -benzyl- 2 .
  • -Dimethylamino-1- (4-morpholinophenyl) -butanone-1 (Omnirad 369)
  • 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide Omnirad TPO H
  • Examples of the intramolecular cleavage type photoradical generator having an absorption coefficient at a wavelength of 447 nm and an absorption coefficient at a wavelength of 405 nm of less than 1.0 ⁇ 102 are 1-hydroxy-cyclohexyl-phenyl-ketone (Omnirad184) and 2-hydroxy-.
  • the composition of one embodiment comprises a first intramolecular cleavage type photoradical generator having an extinction coefficient of 1.0 ⁇ 102 or more at a wavelength of 447 nm and an extinction coefficient of less than 1.0 ⁇ 102 at a wavelength of 447 nm. It may contain a second intramolecular cleavage type photoradical generator.
  • the first intramolecular cleavage photoradical generator is bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide
  • the second intramolecular cleavage photoradical generator is 2.
  • compositions of the other embodiments include a first intramolecular cleavage type photoradical generator having an extinction coefficient of 1.0 ⁇ 10 2 or more at a wavelength of 405 nm and an extinction coefficient of 1.0 ⁇ 10 2 at a wavelength of 405 nm. It may include a second intramolecular cleavage photoradical generator, which is less than.
  • the first intramolecular cleavage type photoradical generator is 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1
  • the second intramolecular cleavage type light Radical generators are 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, anisoin, 2,2-dimethoxy-1,2-diphenylethane-1-.
  • the first intramolecular cleavage photoradical generator is 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide
  • the second intramolecular cleavage photoradical generator is 1-hydroxy-cyclohexyl.
  • Suitable combinations of the first and second intramolecular cleavage photoradical generators include, for example, 2,4,6-trimethylbenzoyl-diphenyl-phosphenyl oxide (OmniradTPO H) and 1-hydroxy-cyclohexyl-phenyl-.
  • the total content of the intramolecular cleavage type photoradical generator may be 5% by mass or more, 10% by mass or more, and 30% by mass or less, or 20% by mass or less, based on the total mass of the composition. It's okay.
  • the content of the first intramolecular cleavage type photoradical generator may be 0.8% by mass or more, 1.0% by mass or more, and 1.5% by mass or less, based on the total mass of the composition. , Or 2.0% by mass or less.
  • 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 photoradical generator may be, for example, 5 or more, or 6.6 or more. It may be 12.5 or less, or 10 or less.
  • 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 photoradical generator may be, for example, 5 or more, or 6.6 or more. It may be 12.5 or less, or 10 or less.
  • the content of the second intramolecular cleavage type photoradical generator may be 5% by mass or more, 10% by mass or more, and 30% by mass or less, or 20% by mass or less, based on the total mass of the composition. May be.
  • 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 photoradical generator is, for example, 0.2 or more, or 0.33 or more. It may be 0.7 or less, or 1 or less.
  • the ratio (B / C2) of the number of moles (B / C2) of the vinyl ether compound to the number of moles (C2) of the second intramolecular cleavage type photoradical generator is, for example, 0.2 or more, or 0.33 or more. It may be 0.7 or less, or 1 or less.
  • the composition may further contain components (other components) other than the disulfide compound, the vinyl ether compound, and the intramolecular cleavage type photoradical generator.
  • Other components include, for example, plasticizers, tackifiers such as tackfire, antioxidants, leuco dyes, sensitizers, adhesion improvers such as coupling agents, polymerization inhibitors, light stabilizers, and defoamers.
  • Additives such as foaming agents, fillers, chain transfer agents, thixotropy-imparting agents, flame retardants, mold release agents, surfactants, lubricants, and antistatic agents can be mentioned.
  • Known additives 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, and 5% by mass or less based on the total amount of the composition.
  • 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 Examples described below.
  • 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 photoradical generator, and a component to be added as needed.
  • Mixing and kneading can be carried out by appropriately combining a disperser such as a normal stirrer, a raft machine, a triple roll, a ball mill, and a bead mill.
  • composition of one embodiment can be used for applications such as adhesives, temporary fixing materials, photoresists, resins for 3D printers, resins for molding materials, and the like.
  • the cured product of the composition of one embodiment comprises a photoreaction product of a disulfide compound and a vinyl ether compound.
  • the cured product may contain an intramolecular cleavage type photoradical generator.
  • a cured product containing a photoreaction product of a disulfide compound and a vinyl ether compound and an intramolecular cleavage type photoradical generator has a property of being melted by light irradiation, and thus can be said to be a photomeltable composition.
  • the cured product may have various shapes.
  • Examples of the shape of the cured product include a film shape (film shape) and a block shape.
  • the cured product formed in the form of a film (film form) can be used as a resin film.
  • the cured product formed in a block shape can be used as a resin block.
  • the method for forming a film-like (film-like) or block-like cured product is not particularly limited, and a known method can be applied.
  • the storage elastic modulus of the cured product at 25 ° C. may be 16000 Pa or more, 5000 Pa or more, or 100,000 Pa or more.
  • the storage elastic modulus of the cured product of the composition at 25 ° C. is not particularly limited, but may be, for example, 1000 MPa or less. In the present specification, the storage elastic modulus at 25 ° C. means a value measured by the method described in Examples.
  • the elastic 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 elastic modulus of the cured product of the composition at 25 ° C. is not particularly limited, but may be, for example, 1000 MPa or less.
  • the modulus of loss of elasticity at 25 ° C. means a value measured by the method described in the examples.
  • the loss tangent (tan ⁇ ) of the cured product at 25 ° C. is 1.5 or less, 1.2 or less, 1 from the viewpoint of slight adhesiveness or non-adhesiveness, thickening, slitting workability, punching workability, workability, etc. It may be 0.1 or less, or 1.0 or less.
  • the loss tangent at 25 ° C. means a value measured by the method described in the examples.
  • 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 the disulfide compound with the vinyl ether compound.
  • the light for forming the cured product may be, for example, ultraviolet light or visible light.
  • the wavelength of the curing light may be appropriately selected depending on, for example, the type of the intramolecular cleavage type photoradical generator 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.
  • Light irradiation can be performed using, for example, a light irradiation device under the condition that the irradiation amount is 100 mJ / cm 2 or more.
  • the irradiation amount can be appropriately set according to, for example, the wavelength of light for curing.
  • the irradiation amount may 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. good.
  • Irradiation amount means the product of illuminance and irradiation time (seconds).
  • Examples of the light source for irradiating ultraviolet light or visible light include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, and an LED lamp.
  • the light irradiation may be performed directly on the composition or may be performed through glass or the like.
  • the compound of one embodiment (hereinafter, also referred to as “the compound”) has a disulfide bond and a structure represented by the following formula (A).
  • the present compound is prepared by a method comprising irradiating a composition containing a disulfide compound, a vinyl ether compound, and an intramolecular cleavage type photoradical generator with light to cause the disulfide compound and the vinyl ether compound to react with each other.
  • a composition containing a disulfide compound, a vinyl ether compound, and an intramolecular cleavage type photoradical generator with light to cause the disulfide compound and the vinyl ether compound to react with each other.
  • the disulfide compound, vinyl ether compound and intramolecular cleavage type photoradical generator may be those described above.
  • the light irradiation condition the above-mentioned conditions can be used.
  • the structure represented by the above formula (A) is not limited to this, but the carbon-carbon double bond in the vinyloxy group causes an insertion reaction with respect to the disulfide bond due to the reaction between the disulfide compound and the vinyl ether compound. It is presumed that it will be formed.
  • the compound may have a structure represented by the following formula (B).
  • n represents an integer of 1 or more
  • A represents a polyether group
  • * represents a bond
  • a plurality of A's may be the same or different from each other.
  • a and n may have the same meaning as A and n described above.
  • the 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 the formula (B).
  • the compound may further have a structure represented by the following formula (C).
  • the present compound 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 present compound. It is presumed that the structure represented by the above formula (C) is formed by an enthiol reaction between a thiol group and a vinyloxy group in a vinyl ether compound.
  • the photomeltable composition of one embodiment contains a photoreaction product of a sulfide compound and a vinyl ether compound and an intramolecular cleavage type photoradical generator.
  • the photomeltable composition of another embodiment contains the compound and an intramolecular cleavage type photoradical generator.
  • the photomeltable composition comprises, for example, a composition containing a sulfide compound, a vinyl ether compound, and first and second intramolecular cleavage type photoradical generators, and a first light containing light having a first wavelength.
  • a cured product (photomeltable composition) containing a photoreaction product of the sulfide compound and the vinyl ether compound and a second intramolecular cleavage type photoradical generator by irradiating and reacting the sulfide compound and the vinyl ether compound. can be manufactured by methods involving the formation of radicals.
  • the method for producing a photomelt product of one embodiment is to irradiate a photomeltable composition containing the above-mentioned photoreaction product and an intramolecular cleavage type photoradical generator with light to form a photomelt product. Includes steps.
  • the method for producing a photomelt product of another embodiment includes a step of irradiating a photomeltable composition containing the present compound and an intramolecular cleavage type photoradical generator with light to form a photomelt product. ..
  • the light for forming the melt may be, for example, ultraviolet light or visible light.
  • the wavelength of the light for melting may be appropriately selected depending on, for example, the type of the intramolecular cleavage type photoradical generator 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.
  • the light irradiation can be performed using, for example, a light irradiation device under the condition of an irradiation amount of more than 3000 mJ / cm 2 .
  • the irradiation amount can be appropriately set according to, for example, the wavelength of light for curing.
  • the irradiation amount may be, for example, 15,000 mJ / cm 2 or more, 20000 mJ / cm 2 or more, or 25000 mJ / cm 2 or more, 100,000 mJ / cm 2 or less, 50,000 mJ / cm 2 or less, or 35,000 mJ / cm 2 or less. good.
  • the complex viscosity of the photomelt 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.
  • the adhesive body of the present 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 photomeltable composition described above.
  • first and second adherends examples include polyolefin resin, polyamide resin, ABS (acrylonitrile butadiene styrene) resin, PC (polycarbonate) resin, PET (polyethylene terephthalate) resin, and PPS (polyphenylene).
  • Sulfide) Resins plastics such as acrylic resins; steel, stainless steel, metals (aluminum, copper, nickel, chromium, etc.) alone or alloys of these metals, glass, silicon wafers and other inorganic materials; wood; rubber and the like.
  • first adherend and the second adherend include a material in which the plastic and the inorganic material are composited.
  • the adhesive body is, for example, in a state where the composition of the present embodiment is in contact with the first adherend and the second adherend, and the composition is irradiated with the first light to form the first adherend. It can be produced by a method that includes the step of forming an adhesive layer that adheres the body and the second adherend to each other.
  • the first light can be appropriately set according to, for example, the type of intramolecular cleavage type photoradical generator.
  • the first light irradiation condition may be the above-mentioned condition.
  • the adhesive layer of the adherend is irradiated with a second light to separate the first adherend and the second adherend. Be prepared. Since the adhesive layer contains the photomeltable composition, the photomeltable composition can be melted and the adherends can be easily separated from each other by irradiating with light.
  • the second light can be appropriately set according to, for example, the type of the intramolecular cleavage type photoradical generator.
  • the second light irradiation condition may be the above-mentioned condition.
  • component (A) a compound having two or more of the following disulfide bonds was prepared.
  • Thiocol LP-55 Polysulfide, manufactured by Toray Fine Chemicals, Inc., number average molecular weight (Mn): 3767.8
  • DEGDVE diethylene glycol divinyl ether, manufactured by Nippon Carbide Industries, Ltd., molecular weight: 158.2
  • TEGDVE Triethylene glycol divinyl ether, manufactured by Nippon Carbide Industries, Ltd., molecular weight: 202.28)
  • CHDVE 1,4-Cyclohexanedimethanol divinyl ether, manufactured by Nippon Carbide Industries, Ltd., molecular weight: 196.29
  • BDVE 1,4-butanediol divinyl ether, manufactured by Nippon Carbide Industries, Ltd., molecular weight: 142.2
  • Dialyl phthalate diallyl phthalate, manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight: 246.26)
  • Funkrill FA-124AS butanediol diacrylate, manufactured by Showa Denko Materials Co., Ltd., molecular weight: 198
  • the following photoradical generator was prepared as the component (C).
  • 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-trimethylbenzoyludiphenylphosphine oxide, manufactured by IGM Resins B.V., molecular weight: 348)
  • Omnirad-369 (2-benzyl-2- (dimethylamino) -4'-morpholinobtyrophenone, manufactured by IGM Resins BV, molecular weight: 366.5
  • Omnirad-184 (1-Hydroxycyclohexyl-phenylketon, manufactured by IGM Resins VV, molecular weight: 204.3
  • Omnirad-1173 (2-hydroxy-2-methyl-1-phenylpropanone, manufactured by IGM Resins B.V., molecular weight: 164.2
  • Examples 1-1 to 1 are obtained by adding the components and amounts (unit: parts by mass) shown in Tables 1 to 2 to a 100 mL flask and stirring with a mechanical stirrer at 100 ° C. for 1 hour to dissolve and mix each component.
  • the compositions of -2, 2-1 to 2-4, 2-6 to 2-8 and Comparative Examples 1 to 4 were obtained.
  • Example 2-5 Add the components and amounts (unit: parts by mass) shown in Table 2 other than Omnirad-1173 to a 100 mL flask, stir with a mechanical stirrer at 100 ° C. for 1 hour to dissolve and mix each component, and then show Table 1 at room temperature.
  • the composition of Example 2-5 was obtained by adding the above-mentioned amount of Omnirad-1173 and stirring for 1 hour.
  • Table 1 shows the measurement results of the complex viscosity at 25 ° C. before and after the light irradiation, the storage elastic modulus, the loss elastic modulus, and the loss tangent at 25 ° C. after the light irradiation of the first wavelength.
  • Touch test 1 Evaluation of photocurability When the sample after irradiation with the first wavelength is touched, if there is no resin transfer on the finger with an elastic or adhesive body, "A", a finger with a high-viscosity liquid. When there was a resin transfer on the finger, it was evaluated as “B”, and when there was a resin transfer on the finger with a liquid, it was evaluated as "C”.
  • Touch test 2 Evaluation of photomeltability When the sample after irradiation with the second wavelength is touched, if there is a resin transfer on the finger with a liquid, "A” (photomeltable), elastic body or fine When it was sticky and there was no resin transfer on the finger, it was evaluated as “C” (no photomeltability).
  • 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.
  • Table 2 shows the evaluation results of the photocurability and photomeltability of the compositions of Examples 2-1 to 2-8.
  • compositions of Examples 2-1 to 2-7 could be photocured with a smaller irradiation amount than the compositions of Example 2-8.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition contenant un composé disulfure présentant au moins deux liaisons disulfures, un composé éther vinylique présentant au moins deux groupes vinyloxy, ainsi qu'un générateur photoradicalaire de type à clivage intramoléculaire.
PCT/JP2021/000843 2021-01-13 2021-01-13 Composition, composition fusible sous l'effet de la lumière et composé WO2022153397A1 (fr)

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WO2024005154A1 (fr) * 2022-06-30 2024-01-04 株式会社レゾナック Composition, composition fusible sous l'effet de la lumière et composé
WO2024058117A1 (fr) * 2022-09-12 2024-03-21 株式会社レゾナック Matériau de résine, et composition de résine

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024005154A1 (fr) * 2022-06-30 2024-01-04 株式会社レゾナック Composition, composition fusible sous l'effet de la lumière et composé
WO2024058117A1 (fr) * 2022-09-12 2024-03-21 株式会社レゾナック Matériau de résine, et composition de résine

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