WO2022080409A1 - Ester compound, method for synthesizing ester compound, and resin composition - Google Patents

Ester compound, method for synthesizing ester compound, and resin composition Download PDF

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Publication number
WO2022080409A1
WO2022080409A1 PCT/JP2021/037891 JP2021037891W WO2022080409A1 WO 2022080409 A1 WO2022080409 A1 WO 2022080409A1 JP 2021037891 W JP2021037891 W JP 2021037891W WO 2022080409 A1 WO2022080409 A1 WO 2022080409A1
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Prior art keywords
ester compound
polyol
resin composition
ester
disulfide bond
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PCT/JP2021/037891
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French (fr)
Japanese (ja)
Inventor
圭市 坂本
祐樹 宮本
哲也 今井
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昭和電工マテリアルズ株式会社
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Priority to JP2022557044A priority Critical patent/JPWO2022080409A1/ja
Publication of WO2022080409A1 publication Critical patent/WO2022080409A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/22—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/22—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and doubly-bound oxygen atoms bound to the same carbon skeleton
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/52—Polythioethers
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48—Polymers modified by chemical after-treatment

Definitions

  • the present disclosure relates to an ester compound, a method for synthesizing an ester compound, and a resin composition.
  • Patent Document 1 discloses an image forming apparatus including a recording member having a photosoftening resin layer made of a photosoftening resin.
  • One aspect of the present disclosure relates to an ester compound which is a transesterification reaction product of a dicarboxylic acid ester having a disulfide bond and a polyol, having a disulfide bond in the molecular chain and having a hydroxy group at the terminal.
  • an ester compound having a disulfide bond in the molecular chain and having a hydroxy group at the terminal is obtained by a transesterification reaction between a disulfide acid ester having a disulfide bond and a polyol.
  • a transesterification reaction between a disulfide acid ester having a disulfide bond and a polyol.
  • Another aspect of the present disclosure relates to a resin composition containing the above ester compound and a photoradical generator.
  • a novel ester compound having photosoftness a method for synthesizing the ester compound, and a resin composition softened by light irradiation are provided.
  • photosoftness means that the viscosity is lowered, the elastic modulus is lowered, the loss tangent (tan ⁇ ) is increased, the hardness is lowered, and the like by light irradiation.
  • process is included in this term not only as an independent process but also as long as the intended action of the process is achieved even if it cannot be clearly distinguished from other processes. Is done.
  • 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.
  • 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.
  • the upper limit value and the lower limit value described individually can be arbitrarily combined.
  • each component in the composition is the total amount of the plurality of substances present in the composition when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified.
  • the exemplary materials may be used alone or in combination of two or more unless otherwise specified.
  • a or B may include either A or B, and may include both.
  • the ester compound according to the present embodiment is a transesterification product of a dicarboxylic acid ester having a disulfide bond and a polyol, and is a photosoftening resin having a disulfide bond in the molecular chain and a hydroxy group at the terminal. ..
  • Such an ester compound can be obtained by transesterifying a dicarboxylic acid ester having a disulfide bond with a polyol.
  • the ester compound according to the present embodiment is different from the compound having at least a hydroxy group and a disulfide bond by the Michael addition reaction in that it does not have a thioether bond. Further, in the transesterification reaction, the molecular weight can be easily controlled as compared with the Michael addition reaction, and the desired ester compound can be stably obtained.
  • the hydroxyl value of the ester compound may be 20 to 150 mgKOH / g, 20 to 140 mgKOH / g, or 25 to 120 mgKOH / g.
  • the hydroxyl value can be measured according to JIS K0070.
  • the dicarboxylic acid ester having a disulfide bond is a compound having a disulfide bond capable of generating a thiyl radical by light irradiation and an alkyl ester group capable of transesterification reaction.
  • a compound having a structure represented by the following formula (1) can be used as the dicarboxylic acid ester having a disulfide bond.
  • R 1 and R 2 independently represent an alkyl group having 1 to 4 carbon atoms
  • R 3 and R 4 independently represent an alkylene group having 1 to 10 carbon atoms, respectively.
  • R 1 and R 2 are preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group, and further preferably a methyl group, from the viewpoint that the transesterification reaction can easily proceed.
  • R 3 and R 4 may be an alkylene group having 1 to 8 carbon atoms, an alkylene group having 2 to 6 carbon atoms, or an alkylene group having 2 to 4 carbon atoms.
  • dicarboxylic acid ester having a disulfide bond examples include dimethyl 3,3'-dithiopropionate, dimethyl dithiodiacetate, and dimethyl 4,4'-dithiodibutyrate.
  • the dicarboxylic acid ester according to the present embodiment may contain at least one selected from the group consisting of dimethyl 3,3'-dithiopropionic acid, dimethyl dithiodiacetate, and dimethyl 4,4'-dithiodibutyrate.
  • the polyol can be used without particular limitation as long as it is a compound having two or more hydroxy groups.
  • the polyol may be a compound (diol) having two hydroxy groups.
  • examples of the polyol include a polyether polyol, a polyester polyol, a polycaprolactone polyol, a polycarbonate polyol, a polybutadiene polyol, and a bisphenol A / ethylene oxide-added diol.
  • the polyol according to the present embodiment may contain at least one selected from the group consisting of a polyether polyol, a polyester polyol, a polycaprolactone polyol, a polycarbonate polyol, a polybutadiene polyol, and a bisphenol A / ethylene oxide-added diol.
  • polyether polyol examples include polytetramethylene ether glycol, polyethylene glycol, and polypropylene glycol.
  • an ester compound having a disulfide bond in the molecular chain and a hydroxy group at the terminal is obtained by a transesterification reaction between a disulfide acid ester having a disulfide bond and a polyol. Can be done.
  • the mixing ratio of the dicarboxylic acid ester and the polyol when synthesizing the ester compound is such that the molar ratio of the alkyl ester group of the dicarboxylic acid ester is 0.5 to 0.9 with respect to 1 mol of the hydroxy group of the polyol. It is preferable to adjust in the range of mol. This makes it easier to obtain an ester compound having a hydroxy group at the end, and makes it easier to adjust the ratio and molecular weight of the disulfide bond of the ester compound.
  • a catalyst When synthesizing an ester compound, a catalyst may be used to promote the transesterification reaction.
  • the catalyst is not particularly limited as long as it is a compound generally used for the transesterification reaction.
  • the catalyst include catalysts such as titanium compounds and acetate compounds.
  • titanium compounds include titanium tetraisopropoxide.
  • the temperature and time of the transesterification reaction are not particularly limited, the temperature may be about 25 to 120 ° C., and the time of the transesterification reaction may be about 1 to 20 hours.
  • the resin composition according to the present embodiment contains the above-mentioned ester compound and a photoradical generator.
  • the photoradical generator may be a component that reacts with the chile radical generated or a component that generates a photoinduced radical when the resin composition is irradiated with light.
  • a photoradical polymerization initiator or the like can be used as the photoradical generator.
  • Examples of the photoradical generator include an intramolecular cleavage type photoradical polymerization initiator and a hydrogen abstraction type photoradical polymerization initiator.
  • Examples of the intramolecular cleavage type photoradical polymerization initiator include a benzyl ketal-based photoradical polymerization initiator; an ⁇ -hydroxyacetophenone-based photoradical polymerization initiator; a benzoin-based photoradical polymerization initiator; an aminoacetophenone-based photoradical polymerization initiator.
  • Oxymuketone-based photoradical polymerization initiators include a benzophenone-based photoradical polymerization initiator, a thioxanthone-based photoradical polymerization initiator, and an anthraquinone-based photoradical polymerization initiator.
  • the content of the photoradical generator may be 1 part by mass or more, 5 parts by mass or more, or 8 parts by mass or more, and 25 parts by mass or less, 20 parts by mass or less, or 15 parts by mass with respect to 100 parts by mass of the ester compound. It may be less than or equal to a mass part.
  • the resin composition according to this embodiment may further contain polyisocyanate.
  • the polyisocyanate can be used without particular limitation as long as it is a compound having two or more isocyanate groups.
  • the polyisocyanate may be a compound having two isocyanate groups (diisocyanate).
  • polyisocyanate examples include aromatic isocyanates such as diphenylmethane diisocyanate (4,4'-diphenylmethane diisocyanate), dimethyldiphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and p-phenylenedi isocyanate; and dicyclohexylmethane diisocyanate and isophorone diisocyanate.
  • aromatic isocyanates such as diphenylmethane diisocyanate (4,4'-diphenylmethane diisocyanate), dimethyldiphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and p-phenylenedi isocyanate
  • dicyclohexylmethane diisocyanate and isophorone diisocyanate examples include aromatic isocyanates such as diphenylmethane diisocyan
  • Alicyclic isocyanates aliphatic isocyanates such as hexamethylene diisocyanates; derivatives such as isocyanurates, biurets, allophanates, uretdiones, and polymerics derived from these isocyanates, and polynuclear bodies can be mentioned.
  • polyisocyanate one type may be used alone, or two or more types may be used in combination.
  • the content of the polyisocyanate may be 10 parts by mass or more, 15 parts by mass or more, or 20 parts by mass or more, and 50 parts by mass or less, 40 parts by mass or less, or 30 parts by mass with respect to 100 parts by mass of the ester compound. It may be as follows.
  • the resin composition may further contain other components other than the above-mentioned components.
  • Other components include, for example, thermosetting resins such as epoxy resins, adhesion improvers such as coupling agents, polymerization inhibitors, light stabilizers, defoamers, fillers, chain transfer agents, thixotropy-imparting agents, and difficult.
  • additives such as fueling agents, mold release agents, surfactants, lubricants, and antistatic agents.
  • known ones can be used.
  • the total content of the other components may be 0 to 95% by mass, 0.01 to 50% by mass, or 0.1 to 10% by mass based on the total amount of the resin composition.
  • the resin composition may be used as a varnish of the resin composition diluted with a solvent.
  • the solvent include aromatic hydrocarbons such as toluene, xylene, mesityrene, cumene, and p-simene; aliphatic hydrocarbons such as hexane and heptane; cyclic alkanes such as methylcyclohexane; tetrahydrofuran, 1,4-dioxane and the like.
  • Cyclic ethers such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone; esters such as methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, ⁇ -butyrolactone; Carbonated esters such as ethylene carbonate and propylene carbonate; amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone (NMP) can be mentioned.
  • the solvent one type may be used alone or two or more types may be used in combination.
  • the concentration of solid components in the varnish may be 10 to 80% by mass based on the total mass of the varnish.
  • the resin composition can be prepared, for example, by mixing or kneading an ester compound, a photoradical generator, and components added as needed. Mixing and kneading can be performed by appropriately combining a disperser such as a normal stirrer, a raft machine, a triple roll, a ball mill, and a bead mill.
  • a disperser such as a normal stirrer, a raft machine, a triple roll, a ball mill, and a bead mill.
  • the resin composition according to this embodiment can be formed into a film and used as a photosoftening resin film. Further, it can be formed into a block shape and used as a photosoftening resin block.
  • the method for forming the resin composition in the form of a film or a block is not particularly limited, and a known method can be applied.
  • the resin composition according to the present embodiment has a property that the disulfide bond (—S—S—) in the ester compound is cleaved by light irradiation, and the compound having the disulfide bond is reduced in molecular weight and softened.
  • the resin composition can also be softened to a liquid (liquid). Further, the resin composition has a property of being easily formed into a film shape or a block shape. By utilizing such properties, the resin composition according to the present embodiment can be applied to, for example, the use of a photoresist agent for photolithography, and is used as a photosensitive resin composition or a photosensitive resin film. be able to.
  • the photosensitive resin composition or the photosensitive resin film can be patterned by light irradiation (exposure), and can be further developed by washing with water after light irradiation (exposure).
  • the resin composition according to this embodiment can be suitably used for forming a pattern film.
  • the resin composition according to the present embodiment is also, for example, a softening agent or an easy peeling agent for a strong adhesive tape; a pressure-sensitive agent for a slightly adhesive or non-adhesive film; a coating material, a pressure-sensitive adhesive, or a partial softening agent for an adhesive; Partial softener of molding material; Ultra-low elastic film that can be punched by irradiating with light after punching; Moisture proofing agent; Capsule film that softens and dissolves by irradiating light; Thickener that reduces viscosity by irradiating light, etc. It can be applied to various uses.
  • a softened product of the resin composition By irradiating the resin composition according to the embodiment with light, a softened product of the resin composition can be obtained.
  • the light in the light irradiation is not particularly limited, but may be, for example, ultraviolet light or visible light.
  • the wavelength of light in light irradiation may be 150 to 830 nm.
  • the 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 means the product of the illuminance and the 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 photosoftening resin composition, or may be performed via glass or the like.
  • the light irradiation of the resin composition may be performed while heating.
  • the heating conditions may be, for example, 40 to 200 ° C.
  • Example 1 A flask equipped with a stirrer, a thermometer, a reflux condenser, decompression equipment, and a nitrogen inflow pipe was prepared. 800 parts by mass of polyethylene glycol (manufactured by Sanyo Chemical Industries, Ltd., trade name "PEG-400", molecular weight 400) and 238 parts by mass of dimethyl 3,3'-dithiodipropionate (manufactured by Fujifilm Waco Chemical Co., Ltd.) in a flask. The mixture was charged, bubbling with nitrogen inflow into the liquid phase, and stirred at 90 ° C. for 2 hours while reducing the pressure to 70 kPa.
  • polyethylene glycol manufactured by Sanyo Chemical Industries, Ltd., trade name "PEG-400", molecular weight 400
  • dimethyl 3,3'-dithiodipropionate manufactured by Fujifilm Waco Chemical Co., Ltd.
  • Example 2 2000 parts by mass of polyethylene glycol (manufactured by Sanyo Chemical Industries, Ltd., trade name "PEG-2000", molecular weight 2000) and 119 parts by mass of dimethyl 3,3'-dithiodipropionate are placed in the same flask as in Example 1 and liquid. The phase was bubbled by influx of nitrogen, and the mixture was stirred at 90 ° C. for 2 hours while reducing the pressure to 70 kPa. Next, 22 parts by mass of titanium tetraisopropoxide (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the transesterification reaction was carried out by stirring at 100 ° C. for 12 hours with the bubbling and depressurization unchanged. As a result, an ester compound B having a hydroxy group and a disulfide bond (hydroxyl value: 27 mgKOH / g) was obtained.
  • Example 4 A resin composition was prepared by mixing 100 parts by mass of ester compound B and 10 parts by mass of Omnirad TPO.
  • Example 5 After mixing 100 parts by mass of ester compound A, 25 parts by mass of diphenylmethane diisocyanate (manufactured by Tosoh Corporation, trade name "Millionate MT”), and 13 parts by mass of Omnirad TPO, it is cured at 80 ° C. for 24 hours to form a resin composition. I made a thing.
  • a resin composition was prepared by mixing 100 parts by mass of polyethylene glycol (manufactured by Sanyo Chemical Industries, Ltd., trade name "PEG-2000", molecular weight 2000) with 10 parts by mass of Omnirad TPO.
  • the resin composition was irradiated with light using a high-pressure mercury lamp at an illuminance of 100 mW and an integrated light amount of 2000 mJ / cm 2 .
  • the viscosity of the resin composition before and after light irradiation was measured at 25 ° C. or 60 ° C. using an E-type viscometer (TV-22, manufactured by Toki Sangyo Co., Ltd.). The results are shown in Table 1.

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The present disclosure pertains to: an ester compound that is a transesterification reactant between a polyol and a dicarboxylic acid ester having a disulfide bond and that has, in a molecule chain, a disulfide bond and has, at a terminal, a hydroxy group; a method for synthesizing said ester compound; and a resin composition containing said ester compound and a photo-radical generator.

Description

エステル化合物、エステル化合物の合成方法、及び樹脂組成物Ester compound, method for synthesizing ester compound, and resin composition
　本開示は、エステル化合物、エステル化合物の合成方法、及び樹脂組成物に関する。 The present disclosure relates to an ester compound, a method for synthesizing an ester compound, and a resin composition.
　光照射によって軟化する光軟化性組成物は、様々な用途に用いられている。例えば、特許文献１には、光軟化性樹脂から構成される光軟化樹脂層を有する記録部材を備える画像形成装置が開示されている。 The photosoftening composition, which is softened by light irradiation, is used for various purposes. For example, Patent Document 1 discloses an image forming apparatus including a recording member having a photosoftening resin layer made of a photosoftening resin.
特開平１１－１９０８８３号公報Japanese Unexamined Patent Publication No. 11-190883
　本開示は、光軟化性を有する新規なエステル化合物、該エステル化合物の合成方法、及び光照射によって軟化する樹脂組成物を提供することを目的とする。 It is an object of the present disclosure to provide a novel ester compound having photosoftness, a method for synthesizing the ester compound, and a resin composition that is softened by light irradiation.
　本開示の一側面は、ジスルフィド結合を有するジカルボン酸エステルと、ポリオールとのエステル交換反応物であり、分子鎖中にジスルフィド結合を有し、末端にヒドロキシ基を有する、エステル化合物に関する。 One aspect of the present disclosure relates to an ester compound which is a transesterification reaction product of a dicarboxylic acid ester having a disulfide bond and a polyol, having a disulfide bond in the molecular chain and having a hydroxy group at the terminal.
　本開示の他の一側面は、ジスルフィド結合を有するジカルボン酸エステルと、ポリオールとのエステル交換反応により、分子鎖中にジスルフィド結合を有し、末端にヒドロキシ基を有するエステル化合物を得る、エステル化合物の合成方法に関する。 Another aspect of the present disclosure is that an ester compound having a disulfide bond in the molecular chain and having a hydroxy group at the terminal is obtained by a transesterification reaction between a disulfide acid ester having a disulfide bond and a polyol. Regarding the synthesis method.
　本開示の他の一側面は、上記エステル化合物と、光ラジカル発生剤とを含有する、樹脂組成物に関する。 Another aspect of the present disclosure relates to a resin composition containing the above ester compound and a photoradical generator.
　本開示によれば、光軟化性を有する新規なエステル化合物、該エステル化合物の合成方法、及び光照射によって軟化する樹脂組成物が提供される。 According to the present disclosure, a novel ester compound having photosoftness, a method for synthesizing the ester compound, and a resin composition softened by light irradiation are provided.
　以下、本開示の実施形態について説明する。ただし、本開示は以下の実施形態に限定されるものではない。 Hereinafter, embodiments of the present disclosure will be described. However, the present disclosure is not limited to the following embodiments.
　本明細書において、「光軟化性」とは、光照射によって、粘度が低下する、弾性率が低下する、損失正接（ｔａｎδ）が上昇する、硬度が低下する等の性質を示すことをいう。本明細書において、「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の作用が達成されれば、本用語に含まれる。本明細書中、「～」を用いて示された数値範囲は、「～」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示す。本明細書中に段階的に記載されている数値範囲において、ある段階の数値範囲の上限値又は下限値は、他の段階の数値範囲の上限値又は下限値に置き換えてもよい。本明細書中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。また、個別に記載した上限値及び下限値は任意に組み合わせ可能である。 In the present specification, "photosoftness" means that the viscosity is lowered, the elastic modulus is lowered, the loss tangent (tan δ) is increased, the hardness is lowered, and the like by light irradiation. In the present specification, the term "process" is included in this term not only as an independent process but also as long as the intended action of the process is achieved even if it cannot be clearly distinguished from other processes. Is done. In the present specification, 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. In the numerical range described stepwise in the present specification, 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. In the numerical range described in the present specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples. In addition, the upper limit value and the lower limit value described individually can be arbitrarily combined.
　本明細書において、組成物中の各成分の含有量は、組成物中に各成分に該当する物質が複数存在する場合、特に断らない限り、組成物中に存在する当該複数の物質の合計量を意味する。また、例示材料は特に断らない限り単独で用いてもよいし、２種以上を組み合わせて用いてもよい。「Ａ又はＢ」とは、Ａ及びＢのどちらか一方を含んでいればよく、両方とも含んでいてもよい。 In the present specification, the content of each component in the composition is the total amount of the plurality of substances present in the composition when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified. Means. Further, the exemplary materials may be used alone or in combination of two or more unless otherwise specified. "A or B" may include either A or B, and may include both.
［エステル化合物］
　本実施形態に係るエステル化合物は、ジスルフィド結合を有するジカルボン酸エステルと、ポリオールとのエステル交換反応物であり、分子鎖中にジスルフィド結合を有し、末端にヒドロキシ基を有する光軟化性樹脂である。このようなエステル化合物は、ジスルフィド結合を有するジカルボン酸エステルと、ポリオールとをエステル交換反応させることで得ることができる。 [Ester compound]
The ester compound according to the present embodiment is a transesterification product of a dicarboxylic acid ester having a disulfide bond and a polyol, and is a photosoftening resin having a disulfide bond in the molecular chain and a hydroxy group at the terminal. .. Such an ester compound can be obtained by transesterifying a dicarboxylic acid ester having a disulfide bond with a polyol.
　ヒドロキシ基及びジスルフィド結合を有する化合物として、ジスルフィド結合を有するチオール化合物と、水酸基を有するアクリレート化合物とのマイケル付加反応により得られる化合物が知られている。マイケル付加反応によるヒドロキシ基及びジスルフィド結合を有する化合物は、チオール基に由来するチオエーテル結合を有している。これに対して、本実施形態に係るエステル化合物は、チオエーテル結合を有していない点で、少なくともマイケル付加反応によるヒドロキシ基及びジスルフィド結合を有する化合物と相違する。また、エステル交換反応は、マイケル付加反応と比較して、分子量の制御が容易であり、安定して目的とするエステル化合物を得ることができる。 As a compound having a hydroxy group and a disulfide bond, a compound obtained by a Michael addition reaction between a thiol compound having a disulfide bond and an acrylate compound having a hydroxyl group is known. The compound having a hydroxy group and a disulfide bond by the Michael addition reaction has a thioether bond derived from a thiol group. On the other hand, the ester compound according to the present embodiment is different from the compound having at least a hydroxy group and a disulfide bond by the Michael addition reaction in that it does not have a thioether bond. Further, in the transesterification reaction, the molecular weight can be easily controlled as compared with the Michael addition reaction, and the desired ester compound can be stably obtained.
　エステル化合物の水酸基価は、２０～１５０ｍｇＫＯＨ／ｇ、２０～１４０ｍｇＫＯＨ／ｇ、又は２５～１２０ｍｇＫＯＨ／ｇであってもよい。水酸基価は、ＪＩＳ　Ｋ００７０に準じて測定することができる。 The hydroxyl value of the ester compound may be 20 to 150 mgKOH / g, 20 to 140 mgKOH / g, or 25 to 120 mgKOH / g. The hydroxyl value can be measured according to JIS K0070.
（ジスルフィド結合を有するジカルボン酸エステル）
　ジスルフィド結合を有するジカルボン酸エステルは、光照射によってチイルラジカルを発生することが可能なジスルフィド結合と、エステル交換反応が可能なアルキルエステル基を有する化合物である。ジスルフィド結合を有するジカルボン酸エステルとしては、例えば、下記式（１）で表される構造を有する化合物を用いることができる。
　Ｒ１－Ｏ－Ｃ（＝Ｏ）－Ｒ３－Ｓ－Ｓ－Ｒ４－Ｃ（＝Ｏ）－Ｏ－Ｒ２　（１） (Dicarboxylic acid ester having a disulfide bond)
The dicarboxylic acid ester having a disulfide bond is a compound having a disulfide bond capable of generating a thiyl radical by light irradiation and an alkyl ester group capable of transesterification reaction. As the dicarboxylic acid ester having a disulfide bond, for example, a compound having a structure represented by the following formula (1) can be used.
R 1 -OC (= O) -R 3 -S-S-R 4 -C (= O) -OR 2 (1)
　式（１）中、Ｒ１及びＲ２は、それぞれ独立に炭素数１～４のアルキル基を示し、Ｒ３及びＲ４は、それぞれ独立に炭素数１～１０のアルキレン基を示す。Ｒ１及びＲ２は、エステル交換反応が進行し易い点から、炭素数１～３のアルキル基であることが好ましく、メチル基又はエチル基であることがより好ましく、メチル基であることが更に好ましい。Ｒ３及びＲ４は、炭素数１～８のアルキレン基、炭素数２～６のアルキレン基、又は炭素数２～４のアルキレン基であってよい。 In the formula (1), R 1 and R 2 independently represent an alkyl group having 1 to 4 carbon atoms, and R 3 and R 4 independently represent an alkylene group having 1 to 10 carbon atoms, respectively. R 1 and R 2 are preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group, and further preferably a methyl group, from the viewpoint that the transesterification reaction can easily proceed. preferable. R 3 and R 4 may be an alkylene group having 1 to 8 carbon atoms, an alkylene group having 2 to 6 carbon atoms, or an alkylene group having 2 to 4 carbon atoms.
　ジスルフィド結合を有するジカルボン酸エステルとしては、例えば、３，３’－ジチオプロピオン酸ジメチル、ジチオ二酢酸ジメチル、及び４，４’－ジチオ二酪酸ジメチルが挙げられる。本実施形態に係るジカルボン酸エステルは、３，３’－ジチオプロピオン酸ジメチル、ジチオ二酢酸ジメチル、及び４，４’－ジチオ二酪酸ジメチルからなる群より選ばれる少なくとも１種を含んでよい。 Examples of the dicarboxylic acid ester having a disulfide bond include dimethyl 3,3'-dithiopropionate, dimethyl dithiodiacetate, and dimethyl 4,4'-dithiodibutyrate. The dicarboxylic acid ester according to the present embodiment may contain at least one selected from the group consisting of dimethyl 3,3'-dithiopropionic acid, dimethyl dithiodiacetate, and dimethyl 4,4'-dithiodibutyrate.
（ポリオール）
　ポリオールは、ヒドロキシ基を２以上有する化合物であれば、特に制限なく用いることができる。ポリオールは、ヒドロキシ基を２つ有する化合物（ジオール）であってよい。ポリオールとしては、例えば、ポリエーテルポリオール、ポリエステルポリオール、ポリカプロラクトンポリオール、ポリカーボネートポリオール、ポリブタジエンポリオール、及びビスフェノールＡ・エチレンオキサイド付加ジオールが挙げられる。本実施形態に係るポリオールは、ポリエーテルポリオール、ポリエステルポリオール、ポリカプロラクトンポリオール、ポリカーボネートポリオール、ポリブタジエンポリオール、及びビスフェノールＡ・エチレンオキサイド付加ジオールからなる群より選ばれる少なくとも１種を含んでよい。 (Polyol)
The polyol can be used without particular limitation as long as it is a compound having two or more hydroxy groups. The polyol may be a compound (diol) having two hydroxy groups. Examples of the polyol include a polyether polyol, a polyester polyol, a polycaprolactone polyol, a polycarbonate polyol, a polybutadiene polyol, and a bisphenol A / ethylene oxide-added diol. The polyol according to the present embodiment may contain at least one selected from the group consisting of a polyether polyol, a polyester polyol, a polycaprolactone polyol, a polycarbonate polyol, a polybutadiene polyol, and a bisphenol A / ethylene oxide-added diol.
　ポリエーテルポリオールとしては、例えば、ポリテトラメチレンエーテルグリコール、ポリエチレングリコール、及びポリプロピレングリコールが挙げられる。 Examples of the polyether polyol include polytetramethylene ether glycol, polyethylene glycol, and polypropylene glycol.
　本実施形態に係るエステル化合物の合成方法では、ジスルフィド結合を有するジカルボン酸エステルと、ポリオールとのエステル交換反応により、分子鎖中にジスルフィド結合を有し、末端にヒドロキシ基を有するエステル化合物を得ることができる。 In the method for synthesizing an ester compound according to the present embodiment, an ester compound having a disulfide bond in the molecular chain and a hydroxy group at the terminal is obtained by a transesterification reaction between a disulfide acid ester having a disulfide bond and a polyol. Can be done.
　エステル化合物を合成する際のジカルボン酸エステルと、ポリオールとの配合割合は、ジカルボン酸エステルが有するアルキルエステル基のモル比が、ポリオールが有するヒドロキシ基が１モルに対して０．５～０．９モルの範囲で調整することが好ましい。これにより、ヒドロキシ基を末端に有するエステル化合物が得られ易くなり、エステル化合物が有するジスルフィド結合の割合及び分子量を調整し易くなる。 The mixing ratio of the dicarboxylic acid ester and the polyol when synthesizing the ester compound is such that the molar ratio of the alkyl ester group of the dicarboxylic acid ester is 0.5 to 0.9 with respect to 1 mol of the hydroxy group of the polyol. It is preferable to adjust in the range of mol. This makes it easier to obtain an ester compound having a hydroxy group at the end, and makes it easier to adjust the ratio and molecular weight of the disulfide bond of the ester compound.
　エステル化合物を合成する際には、触媒を用いてエステル交換反応を促進してもよい。触媒は、エステル交換反応に一般的に用いられる化合物であれば特に限定されない。触媒として、チタン化合物、酢酸塩化合物等の触媒が挙げられる、チタン化合物としては、例えば、チタンテトライソプロポキシドが挙げられる。 When synthesizing an ester compound, a catalyst may be used to promote the transesterification reaction. The catalyst is not particularly limited as long as it is a compound generally used for the transesterification reaction. Examples of the catalyst include catalysts such as titanium compounds and acetate compounds. Examples of titanium compounds include titanium tetraisopropoxide.
　エステル交換反応の温度及び時間は特に限定されず、温度は、２５～１２０℃程度であってよく、エステル交換反応の時間は、１～２０時間程度であってよい。 The temperature and time of the transesterification reaction are not particularly limited, the temperature may be about 25 to 120 ° C., and the time of the transesterification reaction may be about 1 to 20 hours.
［樹脂組成物］
　本実施形態に係る樹脂組成物は、上述したエステル化合物と、光ラジカル発生剤とを含有する。 [Resin composition]
The resin composition according to the present embodiment contains the above-mentioned ester compound and a photoradical generator.
（光ラジカル発生剤）
　光ラジカル発生剤は、樹脂組成物に光を照射したときに、発生するチイルラジカルと反応する成分又は光誘起ラジカルを発生する成分であり得る。光ラジカル発生剤としては、光ラジカル重合開始剤等を用いることができる。 (Photo radical generator)
The photoradical generator may be a component that reacts with the chile radical generated or a component that generates a photoinduced radical when the resin composition is irradiated with light. As the photoradical generator, a photoradical polymerization initiator or the like can be used.
　光ラジカル発生剤としては、例えば、分子内開裂型の光ラジカル重合開始剤及び水素引き抜き型の光ラジカル重合開始剤が挙げられる。分子内開裂型の光ラジカル重合開始剤としては、例えば、ベンジルケタール系光ラジカル重合開始剤；α－ヒドロキシアセトフェノン系光ラジカル重合開始剤；ベンゾイン系光ラジカル重合開始剤；アミノアセトフェノン系光ラジカル重合開始剤；オキシムケトン系光ラジカル重合開始剤；アシルホスフィンオキシド系光ラジカル重合開始剤；チタノセン系光ラジカル重合開始剤；チオ安息香酸Ｓ－フェニル重合開始剤；これらの高分子量誘導体が挙げられる。水素引き抜き型の光ラジカル重合開始剤としては、例えば、ベンゾフェノン系光ラジカル重合開始剤、チオキサントン系光ラジカル重合開始剤、及びアントラキノン系光ラジカル重合開始剤が挙げられる。 Examples of the photoradical generator include an intramolecular cleavage type photoradical polymerization initiator and a hydrogen abstraction type photoradical polymerization initiator. Examples of the intramolecular cleavage type photoradical polymerization initiator include a benzyl ketal-based photoradical polymerization initiator; an α-hydroxyacetophenone-based photoradical polymerization initiator; a benzoin-based photoradical polymerization initiator; an aminoacetophenone-based photoradical polymerization initiator. Agents; Oxymuketone-based photoradical polymerization initiators; Acylphosphine oxide-based photoradical polymerization initiators; Titanosene-based photoradical polymerization initiators; Thiobenzoic acid S-phenyl polymerization initiators; Examples of the hydrogen abstraction type photoradical polymerization initiator include a benzophenone-based photoradical polymerization initiator, a thioxanthone-based photoradical polymerization initiator, and an anthraquinone-based photoradical polymerization initiator.
　光ラジカル発生剤の含有量は、エステル化合物１００質量部に対して、１質量部以上、５質量部以上、又は８質量部以上であってよく、２５質量部以下、２０質量部以下、又は１５質量部以下であってよい。 The content of the photoradical generator may be 1 part by mass or more, 5 parts by mass or more, or 8 parts by mass or more, and 25 parts by mass or less, 20 parts by mass or less, or 15 parts by mass with respect to 100 parts by mass of the ester compound. It may be less than or equal to a mass part.
（ポリイソシアネート）
　本実施形態に係る樹脂組成物は、ポリイソシアネートを更に含有してもよい。ポリイソシアネートは、イソシアネート基を２以上有する化合物であれば、特に制限なく用いることができる。ポリイソシアネートは、イソシアネート基を２つ有する化合物（ジイソシアネート）であってよい。 (Polyisocyanate)
The resin composition according to this embodiment may further contain polyisocyanate. The polyisocyanate can be used without particular limitation as long as it is a compound having two or more isocyanate groups. The polyisocyanate may be a compound having two isocyanate groups (diisocyanate).
　ポリイソシアネートとしては、例えば、ジフェニルメタンジイソシアネート（４，４’－ジフェニルメタンジイソシアネート）、ジメチルジフェニルメタンジイソシアネート、トリレンジイソシアネート、キシリレンジイソシアネート、ｐ－フェニレンジイソシアネート等の芳香族イソシアネート；ジシクロヘキシルメタンジイソシアネート、イソフォロンジイソシアネート等の脂環族イソシアネート；ヘキサメチレンジイソシアネート等の脂肪族イソシアネート；これらイソシアネートから誘導されるイソシアヌレート、ビウレット、アロファネート、ウレトジオン、ポリメリック等の誘導体及び多核体が挙げられる。ポリイソシアネートは、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Examples of the polyisocyanate include aromatic isocyanates such as diphenylmethane diisocyanate (4,4'-diphenylmethane diisocyanate), dimethyldiphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and p-phenylenedi isocyanate; and dicyclohexylmethane diisocyanate and isophorone diisocyanate. Alicyclic isocyanates; aliphatic isocyanates such as hexamethylene diisocyanates; derivatives such as isocyanurates, biurets, allophanates, uretdiones, and polymerics derived from these isocyanates, and polynuclear bodies can be mentioned. As the polyisocyanate, one type may be used alone, or two or more types may be used in combination.
　ポリイソシアネートの含有量は、エステル化合物１００質量部に対して、１０質量部以上、１５質量部以上、又は２０質量部以上であってよく、５０質量部以下、４０質量部以下、又は３０質量部以下であってよい。 The content of the polyisocyanate may be 10 parts by mass or more, 15 parts by mass or more, or 20 parts by mass or more, and 50 parts by mass or less, 40 parts by mass or less, or 30 parts by mass with respect to 100 parts by mass of the ester compound. It may be as follows.
　樹脂組成物は、上述した成分以外のその他の成分を更に含有してもよい。その他の成分としては、例えば、エポキシ樹脂等の熱硬化性樹脂、カップリング剤等の密着性向上剤、重合禁止剤、光安定剤、消泡剤、フィラー、連鎖移動剤、チキソトロピー付与剤、難燃剤、離型剤、界面活性剤、滑剤、帯電防止剤等の添加剤が挙げられる。その他の成分は、公知のものを使用することができる。その他の成分の含有量の総量は、樹脂組成物の全量を基準として、０～９５質量％、０．０１～５０質量％、又は０．１～１０質量％であってよい。 The resin composition may further contain other components other than the above-mentioned components. Other components include, for example, thermosetting resins such as epoxy resins, adhesion improvers such as coupling agents, polymerization inhibitors, light stabilizers, defoamers, fillers, chain transfer agents, thixotropy-imparting agents, and difficult. Examples thereof include additives such as fueling agents, mold release agents, surfactants, lubricants, and antistatic agents. As other components, known ones can be used. The total content of the other components may be 0 to 95% by mass, 0.01 to 50% by mass, or 0.1 to 10% by mass based on the total amount of the resin composition.
　樹脂組成物は、溶剤で希釈された樹脂組成物のワニスとして用いてよい。溶剤としては、例えば、トルエン、キシレン、メシチレン、クメン、ｐ－シメン等の芳香族炭化水素；ヘキサン、ヘプタン等の脂肪族炭化水素；メチルシクロヘキサン等の環状アルカン；テトラヒドロフラン、１，４－ジオキサン等の環状エーテル；アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、４－ヒドロキシ－４－メチル－２－ペンタノン等のケトン；酢酸メチル、酢酸エチル、酢酸ブチル、乳酸メチル、乳酸エチル、γ－ブチロラクトン等のエステル；エチレンカーボネート、プロピレンカーボネート等の炭酸エステル；Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチル－２－ピロリドン（ＮＭＰ）等のアミドなどが挙げられる。溶剤は、１種を単独で又は２種以上を組み合わせて用いてもよい。 The resin composition may be used as a varnish of the resin composition diluted with a solvent. Examples of the solvent include aromatic hydrocarbons such as toluene, xylene, mesityrene, cumene, and p-simene; aliphatic hydrocarbons such as hexane and heptane; cyclic alkanes such as methylcyclohexane; tetrahydrofuran, 1,4-dioxane and the like. Cyclic ethers; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone; esters such as methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, γ-butyrolactone; Carbonated esters such as ethylene carbonate and propylene carbonate; amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone (NMP) can be mentioned. As the solvent, one type may be used alone or two or more types may be used in combination.
　ワニス中の固形成分濃度は、ワニスの全質量を基準として、１０～８０質量％であってよい。 The concentration of solid components in the varnish may be 10 to 80% by mass based on the total mass of the varnish.
　樹脂組成物は、例えば、エステル化合物及び光ラジカル発生剤、並びに必要に応じて添加される成分を混合又は混練することによって調製することができる。混合及び混練は、通常の撹拌機、らいかい機、三本ロール、ボールミル、ビーズミル等の分散機を適宜、組み合わせて行うことができる。 The resin composition can be prepared, for example, by mixing or kneading an ester compound, a photoradical generator, and components added as needed. Mixing and kneading can be performed by appropriately combining a disperser such as a normal stirrer, a raft machine, a triple roll, a ball mill, and a bead mill.
　本実施形態に係る樹脂組成物は、フィルム状に形成して、光軟化性の樹脂フィルムとして用いることができる。また、ブロック状に形成して、光軟化性の樹脂ブロックとして用いることができる。樹脂組成物をフィルム状又はブロック状に形成する方法は、特に制限されず、公知の方法を適用することができる。 The resin composition according to this embodiment can be formed into a film and used as a photosoftening resin film. Further, it can be formed into a block shape and used as a photosoftening resin block. The method for forming the resin composition in the form of a film or a block is not particularly limited, and a known method can be applied.
　本実施形態に係る樹脂組成物は、光照射によって、エステル化合物中のジスルフィド結合（－Ｓ－Ｓ－）が切断され、ジスルフィド結合を有する化合物が低分子量化して軟化する性質を有している。樹脂組成物は、液体（液状）まで軟化させることも可能である。また、樹脂組成物は、フィルム状又はブロック状に成形し易いという性質を有している。このような性質を利用することによって、本実施形態に係る樹脂組成物は、例えば、フォトリソグラフィーのフォトレジスト剤の用途に応用することができ、感光性樹脂組成物又は感光性樹脂フィルムとして使用することができる。感光性樹脂組成物又は感光性樹脂フィルムは、光照射（露光）によってパターニングが可能となり、さらには光照射（露光）後に水洗で現像が可能となる。本実施形態に係る樹脂組成物は、パターン膜の形成に好適に用いることができる。 The resin composition according to the present embodiment has a property that the disulfide bond (—S—S—) in the ester compound is cleaved by light irradiation, and the compound having the disulfide bond is reduced in molecular weight and softened. The resin composition can also be softened to a liquid (liquid). Further, the resin composition has a property of being easily formed into a film shape or a block shape. By utilizing such properties, the resin composition according to the present embodiment can be applied to, for example, the use of a photoresist agent for photolithography, and is used as a photosensitive resin composition or a photosensitive resin film. be able to. The photosensitive resin composition or the photosensitive resin film can be patterned by light irradiation (exposure), and can be further developed by washing with water after light irradiation (exposure). The resin composition according to this embodiment can be suitably used for forming a pattern film.
　本実施形態に係る樹脂組成物はまた、例えば、強粘着テープの軟化剤又は易剥離化剤；微粘着又は無粘着フィルムの粘着化剤；コーティング材、粘着剤、又は接着剤の部分軟化剤；成形材の部分軟化剤；打ち抜き後、光照射することで得られる打ち抜き加工可能な超低弾性フィルム；防湿剤；光照射によって軟化、溶解するカプセルの被膜；光照射によって減粘する増粘剤等の様々な用途に応用することができる。 The resin composition according to the present embodiment is also, for example, a softening agent or an easy peeling agent for a strong adhesive tape; a pressure-sensitive agent for a slightly adhesive or non-adhesive film; a coating material, a pressure-sensitive adhesive, or a partial softening agent for an adhesive; Partial softener of molding material; Ultra-low elastic film that can be punched by irradiating with light after punching; Moisture proofing agent; Capsule film that softens and dissolves by irradiating light; Thickener that reduces viscosity by irradiating light, etc. It can be applied to various uses.
　実施形態に係る樹脂組成物に光照射することで、樹脂組成物の軟化物を得ることができる。光照射における光は、特に制限されないが、例えば、紫外光又は可視光であってよい。光照射における光の波長は、１５０～８３０ｎｍであってよい。光照射は、例えば、光照射装置を用いて、照射量１００ｍＪ／ｃｍ２以上の条件で行うことができる。なお、照射量とは、照度と照射時間（秒）との積を意味する。また、紫外光又は可視光照射用の光源としては、例えば、低圧水銀灯、中圧水銀灯、高圧水銀灯、メタルハライドランプ、ＬＥＤランプ等が挙げられる。光照射は、光軟化性樹脂組成物に対して直接行ってもよく、ガラス等を介して行ってもよい。 By irradiating the resin composition according to the embodiment with light, a softened product of the resin composition can be obtained. The light in the light irradiation is not particularly limited, but may be, for example, ultraviolet light or visible light. The wavelength of light in light irradiation may be 150 to 830 nm. The 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 means the product of the illuminance and the 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 photosoftening resin composition, or may be performed via glass or the like.
　樹脂組成物の光照射は、加熱しながら行ってもよい。加熱条件は、例えば、４０～２００℃であってよい。 The light irradiation of the resin composition may be performed while heating. The heating conditions may be, for example, 40 to 200 ° C.
　以下、本開示について実施例を挙げてより具体的に説明する。ただし、本開示はこれら実施例に限定されるものではない。 Hereinafter, this disclosure will be described more specifically with reference to examples. However, the present disclosure is not limited to these examples.
［エステル化合物］
（実施例１）
　撹拌機、温度計、還流冷却器、減圧設備、及び窒素流入配管を装備したフラスコを準備した。ポリエチレングリコール（三洋化成株式会社製、商品名「ＰＥＧ－４００」、分子量４００）８００質量部及び３，３’－ジチオジプロピオン酸ジメチル（富士フイルムワコーケミカル株式会社製）２３８質量部をフラスコ内に仕込み、液相へ窒素流入にてバブリング、７０ｋＰａまで減圧しつつ９０℃で２時間撹拌した。次いで、チタンテトライソプロポキシド（富士フイルム和光純薬株式会社製）１０質量部を加え、バブリングと減圧はそのままで、１００℃で５時間撹拌してエステル交換反応を行った。これにより、ヒドロキシ基及びジスルフィド結合を有するエステル化合物Ａ（水酸基価：１０８ｍｇＫＯＨ／ｇ）を得た。 [Ester compound]
(Example 1)
A flask equipped with a stirrer, a thermometer, a reflux condenser, decompression equipment, and a nitrogen inflow pipe was prepared. 800 parts by mass of polyethylene glycol (manufactured by Sanyo Chemical Industries, Ltd., trade name "PEG-400", molecular weight 400) and 238 parts by mass of dimethyl 3,3'-dithiodipropionate (manufactured by Fujifilm Waco Chemical Co., Ltd.) in a flask. The mixture was charged, bubbling with nitrogen inflow into the liquid phase, and stirred at 90 ° C. for 2 hours while reducing the pressure to 70 kPa. Next, 10 parts by mass of titanium tetraisopropoxide (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the transesterification reaction was carried out by stirring at 100 ° C. for 5 hours with the bubbling and depressurization unchanged. As a result, an ester compound A having a hydroxy group and a disulfide bond (hydroxyl value: 108 mgKOH / g) was obtained.
（実施例２）
　ポリエチレングリコール（三洋化成株式会社製、商品名「ＰＥＧ－２０００」、分子量２０００）２０００質量部、及び３，３’－ジチオジプロピオン酸ジメチル１１９質量部を実施例１と同様のフラスコに仕込み、液相へ窒素流入にてバブリング、７０ｋＰａまで減圧しつつ９０℃で２時間撹拌した。次いで、チタンテトライソプロポキシド（富士フイルム和光純薬株式会社製）２２質量部を加え、バブリングと減圧はそのままで、１００℃で１２時間撹拌してエステル交換反応を行った。これにより、ヒドロキシ基及びジスルフィド結合を有するエステル化合物Ｂ（水酸基価：２７ｍｇＫＯＨ／ｇ）を得た。 (Example 2)
2000 parts by mass of polyethylene glycol (manufactured by Sanyo Chemical Industries, Ltd., trade name "PEG-2000", molecular weight 2000) and 119 parts by mass of dimethyl 3,3'-dithiodipropionate are placed in the same flask as in Example 1 and liquid. The phase was bubbled by influx of nitrogen, and the mixture was stirred at 90 ° C. for 2 hours while reducing the pressure to 70 kPa. Next, 22 parts by mass of titanium tetraisopropoxide (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the transesterification reaction was carried out by stirring at 100 ° C. for 12 hours with the bubbling and depressurization unchanged. As a result, an ester compound B having a hydroxy group and a disulfide bond (hydroxyl value: 27 mgKOH / g) was obtained.
［樹脂組成物］
（実施例３）
　１００質量部のエステル化合物Ａと、１０質量部の光ラジカル発生剤（２，４，６－トリメチルベンゾイル－ジフェニルホスフィンオキサイド、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社製、商品名「Ｏｍｎｉｒａｄ　ＴＰＯ」）とを混合して、樹脂組成物を作製した。 [Resin composition]
(Example 3)
A mixture of 100 parts by mass of ester compound A and 10 parts by mass of a photoradical generator (2,4,6-trimethylbenzoyl-diphenylphosphine oxide, manufactured by IGM Resins B.V., trade name "Omnirad TPO"). To prepare a resin composition.
（実施例４）
　１００質量部のエステル化合物Ｂと、１０質量部のＯｍｎｉｒａｄ　ＴＰＯとを混合して、樹脂組成物を作製した。 (Example 4)
A resin composition was prepared by mixing 100 parts by mass of ester compound B and 10 parts by mass of Omnirad TPO.
（実施例５）
　１００質量部のエステル化合物Ａと、２５質量部のジフェニルメタンジイソシアネート（東ソー株式会社製、商品名「ミリオネートＭＴ」）、１３質量部のＯｍｎｉｒａｄ　ＴＰＯと混合した後、８０℃で２４時間養生して樹脂組成物を作製した。 (Example 5)
After mixing 100 parts by mass of ester compound A, 25 parts by mass of diphenylmethane diisocyanate (manufactured by Tosoh Corporation, trade name "Millionate MT"), and 13 parts by mass of Omnirad TPO, it is cured at 80 ° C. for 24 hours to form a resin composition. I made a thing.
（比較例１）
　エステル化合物Ｂを他の成分と混合しないで、樹脂組成物として用いた。 (Comparative Example 1)
Ester compound B was used as a resin composition without being mixed with other components.
（比較例２）
　１００質量部のポリエチレングリコール（三洋化成株式会社製、商品名「ＰＥＧ－２０００」、分子量２０００）と、１０質量部のＯｍｎｉｒａｄ　ＴＰＯとを混合して、樹脂組成物を作製した。 (Comparative Example 2)
A resin composition was prepared by mixing 100 parts by mass of polyethylene glycol (manufactured by Sanyo Chemical Industries, Ltd., trade name "PEG-2000", molecular weight 2000) with 10 parts by mass of Omnirad TPO.
　樹脂組成物に、高圧水銀灯を用いて、照度１００ｍＷにて２０００ｍＪ／ｃｍ２の積算光量で光照射した。樹脂組成物の光照射前後の粘度を、Ｅ型粘度計（東機産業株式会社製、ＴＶ－２２）を用いて、２５℃又は６０℃で測定した。結果を表１に示す。 The resin composition was irradiated with light using a high-pressure mercury lamp at an illuminance of 100 mW and an integrated light amount of 2000 mJ / cm 2 . The viscosity of the resin composition before and after light irradiation was measured at 25 ° C. or 60 ° C. using an E-type viscometer (TV-22, manufactured by Toki Sangyo Co., Ltd.). The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001

Claims (10)

  1. 　ジスルフィド結合を有するジカルボン酸エステルと、ポリオールとのエステル交換反応物であり、分子鎖中にジスルフィド結合を有し、末端にヒドロキシ基を有する、エステル化合物。 An ester compound that is a transesterification product of a dicarboxylic acid ester having a disulfide bond and a polyol, having a disulfide bond in the molecular chain, and having a hydroxy group at the end.
  2. 　水酸基価が、２０～１５０ｍｇＫＯＨ／ｇである、請求項１に記載のエステル化合物。 The ester compound according to claim 1, wherein the hydroxyl value is 20 to 150 mgKOH / g.
  3. 　前記ジカルボン酸エステルが、３，３’－ジチオプロピオン酸ジメチル、ジチオ二酢酸ジメチル、及び４，４’－ジチオ二酪酸ジメチルからなる群より選ばれる少なくとも１種を含む、請求項１又は２に記載のエステル化合物。 Claim 1 or 2, wherein the dicarboxylic acid ester comprises at least one selected from the group consisting of dimethyl 3,3'-dithiopropionic acid, dimethyl dithiodiacetate, and dimethyl 4,4'-dithiodibutyrate. Ester compound.
  4. 　前記ポリオールが、ポリエーテルポリオール、ポリエステルポリオール、ポリカプロラクトンポリオール、ポリカーボネートポリオール、ポリブタジエンポリオール、及びビスフェノールＡ・エチレンオキサイド付加ジオールからなる群より選ばれる少なくとも１種を含む、請求項１～３のいずれか一項に記載のエステル化合物。 Any one of claims 1 to 3, wherein the polyol comprises at least one selected from the group consisting of a polyether polyol, a polyester polyol, a polycaprolactone polyol, a polycarbonate polyol, a polybutadiene polyol, and a bisphenol A / ethylene oxide-added diol. The ester compound according to the section.
  5. 　ジスルフィド結合を有するジカルボン酸エステルと、ポリオールとのエステル交換反応により、分子鎖中にジスルフィド結合を有し、末端にヒドロキシ基を有するエステル化合物を得る、エステル化合物の合成方法。 A method for synthesizing an ester compound, which obtains an ester compound having a disulfide bond in the molecular chain and a hydroxy group at the terminal by an ester exchange reaction between a dicarboxylic acid ester having a disulfide bond and a polyol.
  6. 　前記ジカルボン酸エステルが有するアルキルエステル基のモル比が、前記ポリオールが有するヒドロキシ基が１モルに対して０．５～０．９モルである、請求項５に記載のエステル化合物の合成方法。 The method for synthesizing an ester compound according to claim 5, wherein the molar ratio of the alkyl ester group of the dicarboxylic acid ester is 0.5 to 0.9 mol with respect to 1 mol of the hydroxy group of the polyol.
  7. 　前記ジカルボン酸エステルが、３，３’－ジチオプロピオン酸ジメチル、ジチオ二酢酸ジメチル、及び４，４’－ジチオ二酪酸ジメチルからなる群より選ばれる少なくとも１種を含む、請求項５又は６に記載のエステル化合物の合成方法。 5. The claim 5 or 6, wherein the dicarboxylic acid ester comprises at least one selected from the group consisting of dimethyl 3,3'-dithiopropionic acid, dimethyl dithiodiacetate, and dimethyl 4,4'-dithiodibutyrate. Method for synthesizing the ester compound of.
  8. 　前記ポリオールが、ポリエーテルポリオール、ポリエステルポリオール、ポリカプロラクトンポリオール、ポリカーボネートポリオール、ポリブタジエンポリオール、及びビスフェノールＡ・エチレンオキサイド付加ジオールからなる群より選ばれる少なくとも１種を含む、請求項５～７のいずれか一項に記載のエステル化合物の合成方法。 Any one of claims 5 to 7, wherein the polyol comprises at least one selected from the group consisting of a polyether polyol, a polyester polyol, a polycaprolactone polyol, a polycarbonate polyol, a polybutadiene polyol, and a bisphenol A / ethylene oxide-added diol. The method for synthesizing the ester compound according to the section.
  9. 　請求項１～４のいずれか一項に記載のエステル化合物と、光ラジカル発生剤とを含有する、樹脂組成物。 A resin composition containing the ester compound according to any one of claims 1 to 4 and a photoradical generator.
  10. 　ポリイソシアネートを更に含有する、請求項９に記載の樹脂組成物。 The resin composition according to claim 9, further containing polyisocyanate.
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