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WO2012147709A1 - Curable composition and adhesive for optical applications - Google Patents

Curable composition and adhesive for optical applications Download PDF

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Publication number
WO2012147709A1
WO2012147709A1 PCT/JP2012/060900 JP2012060900W WO2012147709A1 WO 2012147709 A1 WO2012147709 A1 WO 2012147709A1 JP 2012060900 W JP2012060900 W JP 2012060900W WO 2012147709 A1 WO2012147709 A1 WO 2012147709A1
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Prior art keywords
curable composition
component
alkyl
general formula
group
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PCT/JP2012/060900
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French (fr)
Japanese (ja)
Inventor
岡崎　仁
竹内　基晴
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三菱瓦斯化学株式会社
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Priority to JP2013512361A priority Critical patent/JP6230419B2/en
Priority to CN201280019915.6A priority patent/CN103562272B/en
Publication of WO2012147709A1 publication Critical patent/WO2012147709A1/en

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Classifications

    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
    • C08G18/3876—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing mercapto groups
    • 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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
    • C08G18/7642—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group containing at least two isocyanate or isothiocyanate groups linked to the aromatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate groups, e.g. xylylene diisocyanate or homologues substituted on the aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes

Definitions

  • the present invention relates to a curable composition suitable as an optical adhesive used for producing a composite optical element.
  • Photocurable compositions such as acrylate compounds are widely used as adhesives when producing optical elements.
  • Adhesives, photocurability, mechanical strength, durability, and optical properties are basic performances for adhesives, but in recent years, the refractive index has become an important performance as optical elements become more sophisticated. . In particular, increasing the refractive index of the adhesive is highly desired because the degree of freedom in optical design is expanded.
  • Examples of applications in which an adhesive having a high refractive index is used include an achromatic lens (achromatic lens) composed of two lenses bonded together, a hybrid aspherical lens composed of a composite of glass and resin, and dichroic Examples include prisms having complicated shapes such as prisms.
  • Adhesives used for these applications naturally require not only a high refractive index but also performance such as adhesion, photocurability, colorless transparency, and viscosity suitable for work.
  • the refractive index of a cured product of bis (2,3-epithiopropyl) sulfide is 1.70. Since the episulfide compound has a low viscosity and can be easily injected into a mold, it is suitable for producing a molded article such as a spectacle lens. However, assuming use as an adhesive, if the viscosity is too low, the adhesive may sag or flow, and the adherend may be displaced during pasting, which causes problems in workability. Moreover, since the episulfide compound generally has a large shrinkage due to curing, when used as an adhesive, it causes a decrease in adhesion.
  • Japanese Patent Laid-Open No. 9-71580 Japanese Patent Laid-Open No. 9-110979 Japanese Patent Laid-Open No. 9-255781 JP 2001-163874 A
  • an object of the present invention is to provide a curable composition having a high refractive index and also having performances required as an optical adhesive such as photocurability, low shrinkage, colorless transparency, and viscosity suitable for work. Is to provide.
  • the present inventors have found that a polythiourethane oligomer (component A), an episulfide compound (component B) and a photobase generator (C) obtained by reacting polythiol and polyisocyanate. It has been found that the curable composition containing the component) is suitable as an optical adhesive because it has a viscosity suitable for workability as an adhesive and has little shrinkage due to curing. Based on the above findings, the present invention has been achieved.
  • a curable composition having a high refractive index and also having performance as an optical adhesive such as photocurability, low shrinkage, colorless transparency and viscosity suitable for work. be able to.
  • the curable composition of the present invention comprises a polythiourethane oligomer (A component) obtained by reacting polythiol and polyisocyanate, an episulfide compound (B component), and a photobase generator (C component). .
  • a component polythiourethane oligomer obtained by reacting polythiol and polyisocyanate, an episulfide compound (B component), and a photobase generator (C component).
  • the polythiol used as a raw material for the polythiourethane oligomer is a compound having two or more thiol groups in one molecule, and may be any of linear, branched, and cyclic.
  • compounds represented by the following general formulas (1) to (3) are preferable.
  • p1 and p2 each independently represents an integer of 0 to 1
  • X 1 to X 8 each independently represents a hydrogen atom or a methylthiol group.
  • q represents an integer of 0 to 3
  • R 1 represents a simple bond or an alkylene group having 1 to 3 carbon atoms.
  • r represents an integer of 0 to 3
  • R 2 represents an alkylene group having 1 to 3 carbon atoms.
  • Examples of the compound represented by the general formula (1) include 1,5-dimercapto-3-thiapentane, 2-mercaptomethyl-1,5-dimercapto-3-thiapentane, 2,4-bis (mercaptomethyl) -1 , 5-dimercapto-3-thiapentane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-bis (mercaptomethyl) -1,11-dimercapto-3,6,9-trithia Undecane, 4,7-bis (mercaptomethyl) -1,11-dimercapto-3,6,9-trithiaundecane, 5,7-bis (mercaptomethyl) -1,11-dimercapto-3,6,9- Examples of the compound represented by the general formula (2) include 2,5-dimercapto-1,4-dithiane and 2,5-dithiane.
  • polythiol compounds other than the compounds represented by the general formulas (1) to (3) include ethylene glycol bis (3-mercaptopropionate), trimethiolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3 -Mercaptopropionate), benzenedithiol, tolylenedithiol and the like.
  • the polyisocyanate used as a raw material for the polythiourethane oligomer is a compound having two or more isocyanate groups in one molecule, and may be any of linear, branched, and cyclic.
  • polyisocyanates include m-xylylene diisocyanate, 1,3-bis (2-isocyanato-2-propyl) benzene, tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, 1,3-bis (2-isocyanato-2-propyl) cyclohexane, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tris (6-isocyanatohexyl) isocyanurate and the like.
  • preferred polyisocyanates are m-xylylene diisocyanate, 1,3-bis (2-isocyanato-2-propyl) benzene, 1,3 -Bis (2-isocyanato-2-propyl) cyclohexane, isophorone diisocyanate.
  • the reaction of polythiol and polyisocyanate is, for example, when the product is a dimer, the following reaction formula (In the formula, R and R ′ represent an organic group, and a and b represent an integer of 1 or more.) Proceed according to. Since the thiol group and the isocyanate group react with each other at a ratio of 1: 1, a polythiourethane oligomer having a larger molecular weight is generated as the molar ratio of the thiol group to the isocyanate group is closer to 1.
  • the mixing ratio of polythiol and polyisocyanate is preferably in the range of 0.2 to 0.95 mol of isocyanate group, more preferably in the range of 0.4 to 0.95 mol with respect to 1 mol of thiol group. If it is less than 0.2 mol, the conversion rate of the thiol group is too low to be practical, and if it exceeds 0.95 mol, an unreacted isocyanate group remains, which is not preferable.
  • the reaction between polythiol and polyisocyanate proceeds by heating in the presence or absence of a catalyst, but a method using a catalyst is preferred.
  • a catalyst include tin compounds such as dibutyltin dilaurate and dibutyldichlorotin, and basic compounds such as amine and phosphine.
  • the amount of the catalyst used is preferably in the range of 0.01 to 10 parts by weight and more preferably in the range of 0.1 to 1.0 parts by weight with respect to 100 parts by weight of the raw polythiol.
  • the reaction between polythiol and polyisocyanate may be performed in the presence of an episulfide compound (component B).
  • a solvent may be used as necessary.
  • a post-process for distilling off the solvent is required.
  • the reaction temperature is not particularly limited, but it is preferably in the range of 0 to 100 ° C. The temperature may be gradually raised while checking the progress of the reaction.
  • the reaction time depends on various conditions such as the type of raw material, the mixing ratio of polythiol and polyisocyanate, and the reaction temperature, but cannot be defined unconditionally, but the reaction is continued until no unreacted polyisocyanate remains.
  • the curable composition of the present invention includes the polythiourethane oligomer (A component), the episulfide compound (B component), and the photobase generator (C component) described above.
  • An episulfide compound (component B) is a compound having one or more episulfide groups in one molecule.
  • the following general formula (4) (Wherein, m is an integer from 0 to 6, n is an integer from 0 to 4, each R 3 and R 4 are independently hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R 5 and R 6 is each independently an alkylene group having 1 to 10 carbon atoms.)
  • the compound represented by these is preferable.
  • Examples of the episulfide compound represented by the general formula (4) include bis (2,3-epithiopropyl) sulfide.
  • the episulfide compound represented by the general formula (4) has a large shrinkage due to curing, the shrinkage due to the curing can be suppressed by copolymerizing with the polythiourethane oligomer.
  • the episulfide compound represented by the general formula (4) generally has a low viscosity, but is adjusted to a viscosity excellent in workability by mixing with the polythiourethane oligomer.
  • the curable composition is used as an adhesive with respect to the viscosity of the curable composition
  • the adhesive may sag or flow, or the substrate may be displaced during bonding.
  • the viscosity is too high, it is not preferable because it becomes difficult to discharge or apply the adhesive, or bubbles are bitten during the bonding.
  • the viscosity suitable for workability as referred to in the present invention depends on the use form of the adhesive such as the coating method and the laminating method, and cannot be defined unconditionally, but is preferably in the range of 500 to 20,000 mPa ⁇ s, more The range is preferably 500 to 10,000 mPa ⁇ s.
  • the content of the polythiourethane oligomer is preferably in the range of 10 to 70 parts by weight, more preferably in the range of 20 to 60 parts by weight with respect to 100 parts by weight of the curable composition. If the content of the polythiourethane oligomer is less than 10 parts by weight, the effect of increasing the viscosity or reducing the shrinkage is reduced, and if it exceeds 70 parts by weight, the toughness of the cured product is lowered, which is not preferable.
  • the photobase generator (component C) is a compound that generates a base by photolysis with actinic rays.
  • amidine such as DBN (diazabicyclononene) and DBU (diazabicycloundecene)
  • photobase generators that generate these bases are preferred.
  • the amidinium ketone (the left side of the following formula (5)) forming the tetraarylborate salt described in JP-T-2001-513765 and the aryl described in JP-T-2005-511536 1,3-diamine substituted with an alkyl group left side of the following formula (6)
  • the addition amount of the photobase generator is preferably in the range of 0.01 to 10 parts by weight, more preferably in the range of 0.1 to 5 parts by weight with respect to 100 parts by weight of the curable composition.
  • Ar 1 is phenyl, biphenyl, naphthyl, phenanthryl, anthracyl, pyrenyl, 5,6,7,8-tetrahydro-2-naphthyl, 5,6,7,8-tetrahydro-1-naphthyl, thienyl, Benzo [b] thienyl, naphtho [2,3-b] thienyl, thiatrenyl, dibenzofuryl, chromenyl, xanthenyl, thioxanthyl, phenoxathiinyl, terphenyl, stilbenyl or fluorenyl, these groups being unsubstituted Or C1-C18
  • a photosensitizer may be included. By adding the photosensitizer, the photodecomposition of the photobase generator is accelerated, and the curing time of the photocurable composition can be shortened.
  • Specific examples of the photosensitizer include benzophenones, thioxanthones, anthraquinones, camphorquinones, benzyls, Michler ketones, and anthracenes. These may be used alone or in combination of two or more.
  • the addition amount of the photosensitizer is preferably in the range of 0.01 to 10 parts by weight and more preferably in the range of 0.1 to 5 parts by weight with respect to 100 parts by weight of the curable composition.
  • a polymerization inhibitor a polymerization inhibitor, an antioxidant, an ultraviolet absorber, a silane coupling agent, a release agent, a pigment, a dye, and the like can be added to the curable composition. . Moreover, you may perform filtration, defoaming, etc. as needed.
  • the cure shrinkage rate in an Example was computed from the refractive index before and behind hardening according to the following formula.
  • X (1 ⁇ d1 / d2) ⁇ 100 [%]
  • the refractive index of M and M represents the molecular weight.
  • the viscosity of the curable composition was measured at a temperature of 25 ° C. using a cone / plate viscometer DV-II + (manufactured by Brookfield).
  • the refractive indexes of the curable composition and the cured film were measured using an Abbe refractometer NAR-3T (manufactured by Atago Co., Ltd.).
  • the transmittance of the cured film was measured using a spectrophotometer U-3500 (manufactured by Hitachi High-Tech) at a thickness of 0.25 mm and a wavelength of 400 nm.
  • Example 1 In a 300 ml flask, 25 g of 2,5-dimercaptomethyl-1,4-dithiane, 15 g of m-xylylene diisocyanate and 0.1 g of dibutyltin dilaurate were placed, and stirring was continued at 60 ° C. for 24 hours.
  • the curable composition was sandwiched between two release-treated glass plates, irradiated with light from a metal halide lamp (120 W / cm) for 3 minutes from a distance of 30 cm, and then the cured film was peeled from the glass plate.
  • a cured film having a thickness of 0.25 mm was produced by the above procedure.
  • the physical properties of the curable composition and the cured film were as shown in Table 1.
  • Examples 2-5 A curable composition and a cured film were prepared in the same manner as in Example 1 except that the types and amounts of polythiol, polyisocyanate, and episulfide compound were changed to those shown in Table 1.
  • the physical properties of the curable composition and the cured film were as shown in Table 1.
  • Comparative Example 1 100 g of bis (2,3-epithiopropyl) sulfide, 0.5 g of photobase generator represented by the structural formula (7) (C component), and 4-benzoyl-4′-methyldiphenyl sulfide as a sensitizer 1 g was added and stirred until uniform.
  • the curable composition was produced in the above procedure.
  • a cured film was produced in the same manner as in Example 1.
  • the physical properties of the curable composition and the cured film were as shown in Table 2. In addition, physical properties that are inferior to those of the examples are underlined.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Abstract

Provided is a curable composition which has a high refractive index and also has simultaneously the capabilities required of adhesives for optical applications: light-curability, low shrinkage, colorless transparency, and viscosity suitable for operations. This invention provides a curable composition containing polythiourethane oligomers (component A) obtained by reacting polyols and polyisocyanates, an episulfide compound (component B) and a photobase generator (component C).

Description

硬化性組成物および光学用接着剤Curable composition and optical adhesive
　本発明は、複合光学素子を作製する際に使用される光学用接着剤として好適な硬化性組成物に関するものである。 The present invention relates to a curable composition suitable as an optical adhesive used for producing a composite optical element.
　アクリレート化合物等の光硬化性組成物は、光学素子を作製する際の接着剤として幅広く使用されている。接着剤にとって、密着性、光硬化性、機械的強度、耐久性、および光学特性は基本性能であるが、近年では光学素子の高機能化に伴って、屈折率が重要な性能になっている。特に接着剤の高屈折率化は光学設計の自由度が広がるので要望が高い。高い屈折率を有する接着剤が使用される用途例としては、２枚のレンズの張り合わせで構成される色消しレンズ（アクロマートレンズ）、ガラスと樹脂の複合で構成されるハイブリッド型非球面レンズ、ダイクロイックプリズムなどの複雑形状をしたプリズム等が挙げられる。これらの用途に使用される接着剤には、高い屈折率だけでなく、密着性、光硬化性、無色透明性、作業に適した粘度といった性能も当然要求される。 Photocurable compositions such as acrylate compounds are widely used as adhesives when producing optical elements. Adhesives, photocurability, mechanical strength, durability, and optical properties are basic performances for adhesives, but in recent years, the refractive index has become an important performance as optical elements become more sophisticated. . In particular, increasing the refractive index of the adhesive is highly desired because the degree of freedom in optical design is expanded. Examples of applications in which an adhesive having a high refractive index is used include an achromatic lens (achromatic lens) composed of two lenses bonded together, a hybrid aspherical lens composed of a composite of glass and resin, and dichroic Examples include prisms having complicated shapes such as prisms. Adhesives used for these applications naturally require not only a high refractive index but also performance such as adhesion, photocurability, colorless transparency, and viscosity suitable for work.
　高い屈折率を有する化合物として、分子構造中に硫黄原子を高濃度で含有するエピスルフィド化合物が多数見出されている（特許文献１～４）。例えば、ビス（２，３－エピチオプロピル）スルフィドの硬化物の屈折率は１．７０である。該エピスルフィド化合物は粘度が低く、容易にモールド注入できるため、眼鏡レンズなどの成形体の作製には好適である。しかしながら、接着剤としての使用を想定した場合、粘度が低すぎると接着剤が垂れたり流れたり、張り合わせの際に被着体がずれたりして作業性に課題がある。また、一般的にエピスルフィド化合物は硬化に伴う収縮が大きいため、接着剤として使用した場合には密着性が低下する原因となる。 As compounds having a high refractive index, many episulfide compounds containing a high concentration of sulfur atoms in the molecular structure have been found (Patent Documents 1 to 4). For example, the refractive index of a cured product of bis (2,3-epithiopropyl) sulfide is 1.70. Since the episulfide compound has a low viscosity and can be easily injected into a mold, it is suitable for producing a molded article such as a spectacle lens. However, assuming use as an adhesive, if the viscosity is too low, the adhesive may sag or flow, and the adherend may be displaced during pasting, which causes problems in workability. Moreover, since the episulfide compound generally has a large shrinkage due to curing, when used as an adhesive, it causes a decrease in adhesion.
特開平９－７１５８０号公報Japanese Patent Laid-Open No. 9-71580 特開平９－１１０９７９号公報Japanese Patent Laid-Open No. 9-110979 特開平９－２５５７８１号公報Japanese Patent Laid-Open No. 9-255781 特開２００１－１６３８７４号公報JP 2001-163874 A
　従って、本発明の目的は、高い屈折率を有し、且つ、光硬化性、低収縮性、無色透明性、作業に適した粘度といった光学用接着剤として求められる性能も兼ね備えた硬化性組成物を提供することにある。 Accordingly, an object of the present invention is to provide a curable composition having a high refractive index and also having performances required as an optical adhesive such as photocurability, low shrinkage, colorless transparency, and viscosity suitable for work. Is to provide.
　本発明者らは、上記課題を解決するために鋭意検討した結果、ポリチオールとポリイソシアネートを反応させて得られるポリチオウレタンオリゴマー（Ａ成分）、エピスルフィド化合物（Ｂ成分）および光塩基発生剤（Ｃ成分）を含有した硬化性組成物が、接着剤として作業性に適した粘度を有し、且つ硬化に伴う収縮が小さいことから、光学用接着剤として好適であることを見出した。以上の知見に基づき、本発明に至った。 As a result of intensive studies to solve the above problems, the present inventors have found that a polythiourethane oligomer (component A), an episulfide compound (component B) and a photobase generator (C) obtained by reacting polythiol and polyisocyanate. It has been found that the curable composition containing the component) is suitable as an optical adhesive because it has a viscosity suitable for workability as an adhesive and has little shrinkage due to curing. Based on the above findings, the present invention has been achieved.
　本発明によれば、高い屈折率を有し、且つ、光硬化性、低収縮性、無色透明性、作業に適した粘度といった光学用接着剤としての性能も兼ね備えた硬化性組成物を提供することができる。 According to the present invention, there is provided a curable composition having a high refractive index and also having performance as an optical adhesive such as photocurability, low shrinkage, colorless transparency and viscosity suitable for work. be able to.
　本発明の硬化性組成物は、ポリチオールとポリイソシアネートを反応させて得られるポリチオウレタンオリゴマー（Ａ成分）、エピスルフィド化合物（Ｂ成分）および光塩基発生剤（Ｃ成分）を含有して構成される。 The curable composition of the present invention comprises a polythiourethane oligomer (A component) obtained by reacting polythiol and polyisocyanate, an episulfide compound (B component), and a photobase generator (C component). .
　まず、ポリチオウレタンオリゴマー（Ａ成分）の製造方法について説明する。
　ポリチオウレタンオリゴマーの原料となるポリチオールとは、１分子中に２個以上のチオール基を有する化合物であり、直鎖状、分岐鎖状、環状のいずれであってもよい。特に、硬化性組成物の高屈折率化と作業性に適した粘度を追求した場合、下記一般式（１）から（３）で表わされる化合物が好ましい。
Figure JPOXMLDOC01-appb-C000007
 （式中、ｐ１およびｐ２はそれぞれ独立に０～１の整数を表し、Ｘ１～Ｘ８はそれぞれ独立に水素原子またはメチルチオール基を表す。）
Figure JPOXMLDOC01-appb-C000008
 （式中、ｑは０～３の整数を表し、Ｒ１は単なる結合または炭素数１～３のアルキレン基を表す。）
Figure JPOXMLDOC01-appb-C000009
 （式中、ｒは０～３の整数を表し、Ｒ２は炭素数１～３のアルキレン基を表す。） First, the manufacturing method of a polythiourethane oligomer (component A) will be described.
The polythiol used as a raw material for the polythiourethane oligomer is a compound having two or more thiol groups in one molecule, and may be any of linear, branched, and cyclic. In particular, when pursuing a viscosity suitable for increasing the refractive index and workability of the curable composition, compounds represented by the following general formulas (1) to (3) are preferable.
Figure JPOXMLDOC01-appb-C000007
 (Wherein p1 and p2 each independently represents an integer of 0 to 1, and X 1 to X 8 each independently represents a hydrogen atom or a methylthiol group.)
Figure JPOXMLDOC01-appb-C000008
 (In the formula, q represents an integer of 0 to 3, and R 1 represents a simple bond or an alkylene group having 1 to 3 carbon atoms.)
Figure JPOXMLDOC01-appb-C000009
 (In the formula, r represents an integer of 0 to 3, and R 2 represents an alkylene group having 1 to 3 carbon atoms.)
　一般式（１）で表わされる化合物の例としては、１，５－ジメルカプト－３－チアペンタン、２－メルカプトメチル－１，５－ジメルカプト－３－チアペンタン、２，４－ビス（メルカプトメチル）－１，５－ジメルカプト－３－チアペンタン、４－メルカプトメチル－１，８－ジメルカプト－３，６－ジチアオクタン、４，８－ビス（メルカプトメチル）－１，１１－ジメルカプト－３，６，９－トリチアウンデカン、４，７－ビス（メルカプトメチル）－１，１１－ジメルカプト－３，６，９－トリチアウンデカン、５，７－ビス（メルカプトメチル）－１，１１－ジメルカプト－３，６，９－トリチアウンデカン等が挙げられ、一般式（２）で表わされる化合物の例としては、２，５－ジメルカプト－１，４－ジチアン、２，５－ジメルカプトメチル－１，４－ジチアン、２，５－ジメルカプトエチル－１，４－ジチアン等が挙げられ、一般式（３）で表わされる化合物の例としては、キシリレンジチオール等が挙げられる。一般式（１）から（３）で表わされる化合物以外のポリチオール化合物としては、エチレングリコールビス（３－メルカプトプロピオネート）、トリメチオールプロパントリス（３－メルカプトプロピオネート）、ペンタエリスリトールテトラキス（３－メルカプトプロピオネート）、ベンゼンジチオール、トリレンジチオール等が挙げられる。 Examples of the compound represented by the general formula (1) include 1,5-dimercapto-3-thiapentane, 2-mercaptomethyl-1,5-dimercapto-3-thiapentane, 2,4-bis (mercaptomethyl) -1 , 5-dimercapto-3-thiapentane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-bis (mercaptomethyl) -1,11-dimercapto-3,6,9-trithia Undecane, 4,7-bis (mercaptomethyl) -1,11-dimercapto-3,6,9-trithiaundecane, 5,7-bis (mercaptomethyl) -1,11-dimercapto-3,6,9- Examples of the compound represented by the general formula (2) include 2,5-dimercapto-1,4-dithiane and 2,5-dithiane. Rukaputomechiru dithiane, 2,5-mercaptoethyl-1,4-dithiane, and examples of the compound represented by formula (3), xylylenedithiol and the like. Examples of polythiol compounds other than the compounds represented by the general formulas (1) to (3) include ethylene glycol bis (3-mercaptopropionate), trimethiolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3 -Mercaptopropionate), benzenedithiol, tolylenedithiol and the like.
　ポリチオウレタンオリゴマーの原料となるポリイソシアネートとは、１分子中に２個以上のイソシアネート基を有する化合物であり、直鎖状、分岐鎖状、環状のいずれであってもよい。このようなポリイソシアネートの例としては、ｍ－キシリレンジイソシアネート、１，３－ビス（２－イソシアナト－２－プロピル）ベンゼン、トリレンジイソシアネート、ジフェニルメタン－４，４’－ジイソシアネート、１，３－ビス（２－イソシアナト－２－プロピル）シクロヘキサン、イソホロンジイソシアネート、ジシクロヘキシルメタン－４，４’－ジイソシアネート、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、トリス（６－イソシアナトヘキシル）イソシアヌレート等が挙げられる。これらは単独で用いてもよいし、２種類以上を組み合わせて用いてもよい。特に、硬化性組成物の高屈折率化と低黄色性を追求した場合、好ましいポリイソシアネートは、ｍ－キシリレンジイソシアネート、１，３－ビス（２－イソシアナト－２－プロピル）ベンゼン、１，３－ビス（２－イソシアナト－２－プロピル）シクロヘキサン、イソホロンジイソシアネートである。 The polyisocyanate used as a raw material for the polythiourethane oligomer is a compound having two or more isocyanate groups in one molecule, and may be any of linear, branched, and cyclic. Examples of such polyisocyanates include m-xylylene diisocyanate, 1,3-bis (2-isocyanato-2-propyl) benzene, tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, 1,3-bis (2-isocyanato-2-propyl) cyclohexane, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tris (6-isocyanatohexyl) isocyanurate and the like. These may be used alone or in combination of two or more. In particular, when pursuing high refractive index and low yellowness of the curable composition, preferred polyisocyanates are m-xylylene diisocyanate, 1,3-bis (2-isocyanato-2-propyl) benzene, 1,3 -Bis (2-isocyanato-2-propyl) cyclohexane, isophorone diisocyanate.
　ポリチオールとポリイソシアネートの反応は、例えば生成物が２量体の場合、下記の反応式
Figure JPOXMLDOC01-appb-C000010
 （式中、ＲおよびＲ’は有機基を表し、ａおよびｂは１以上の整数を表す。）
に従って進行する。チオール基とイソシアネート基が１対１モルで反応するため、チオール基とイソシアネート基のモル比が１に近いほど分子量が大きなポリチオウレタンオリゴマーが生成する。ポリチオールとポリイソシアネートの混合比は、チオール基１モルに対してイソシアネート基が０．２～０．９５モルの範囲が好ましく、０．４～０．９５モルの範囲がより好ましい。０．２モル未満ではチオール基の転化率が低すぎて実用的でないし、０．９５モルを超えると未反応のイソシアネート基が残存して好ましくない。 The reaction of polythiol and polyisocyanate is, for example, when the product is a dimer, the following reaction formula
Figure JPOXMLDOC01-appb-C000010
 (In the formula, R and R ′ represent an organic group, and a and b represent an integer of 1 or more.)
Proceed according to. Since the thiol group and the isocyanate group react with each other at a ratio of 1: 1, a polythiourethane oligomer having a larger molecular weight is generated as the molar ratio of the thiol group to the isocyanate group is closer to 1. The mixing ratio of polythiol and polyisocyanate is preferably in the range of 0.2 to 0.95 mol of isocyanate group, more preferably in the range of 0.4 to 0.95 mol with respect to 1 mol of thiol group. If it is less than 0.2 mol, the conversion rate of the thiol group is too low to be practical, and if it exceeds 0.95 mol, an unreacted isocyanate group remains, which is not preferable.
　ポリチオールとポリイソシアネートの反応は、触媒の存在下あるいは非存在下で加熱することで進行するが、触媒を使用する方法が好ましい。触媒としては、ジラウリン酸ジブチルスズやジブチルジクロロスズなどのスズ化合物や、アミンやホスフィンなどの塩基性化合物が挙げられる。触媒の使用量は、原料のポリチオール１００重量部に対して、０．０１～１０重量部の範囲が好ましく、０．１～１．０重量部の範囲がより好ましい。 The reaction between polythiol and polyisocyanate proceeds by heating in the presence or absence of a catalyst, but a method using a catalyst is preferred. Examples of the catalyst include tin compounds such as dibutyltin dilaurate and dibutyldichlorotin, and basic compounds such as amine and phosphine. The amount of the catalyst used is preferably in the range of 0.01 to 10 parts by weight and more preferably in the range of 0.1 to 1.0 parts by weight with respect to 100 parts by weight of the raw polythiol.
　ポリチオールとポリイソシアネートの反応は、エピスルフィド化合物（Ｂ成分）の存在下で行ってもよい。ポリチオールとポリイソシアネートの反応は、必要に応じて溶媒を使用してもよい。溶媒を使用する場合には溶媒を留去する後工程が必要となる。反応温度は特に限定されないが、０～１００℃の範囲が好ましく、反応の進行具合を見ながら徐々に温度を上げていってもよい。反応時間は、原料の種類、ポリチオールとポリイソシアネートの混合比、反応温度などの様々な条件に依るので一概には規定できないが、未反応のポリイソシアネートが残存しなくなるまで反応させる。 The reaction between polythiol and polyisocyanate may be performed in the presence of an episulfide compound (component B). In the reaction of polythiol and polyisocyanate, a solvent may be used as necessary. When using a solvent, a post-process for distilling off the solvent is required. The reaction temperature is not particularly limited, but it is preferably in the range of 0 to 100 ° C. The temperature may be gradually raised while checking the progress of the reaction. The reaction time depends on various conditions such as the type of raw material, the mixing ratio of polythiol and polyisocyanate, and the reaction temperature, but cannot be defined unconditionally, but the reaction is continued until no unreacted polyisocyanate remains.
　次に、本発明の硬化性組成物について説明する。
　本発明の硬化性組成物とは、前述したポリチオウレタンオリゴマー（Ａ成分）、エピスルフィド化合物（Ｂ成分）、および光塩基発生剤（Ｃ成分）を含有して構成される。
　エピスルフィド化合物（Ｂ成分）とは、１分子中に１個以上のエピスルフィド基を有する化合物である。特に、硬化性組成物の高屈折率化を追求した場合、下記の一般式（４）
Figure JPOXMLDOC01-appb-C000011
 （式中、ｍは０から６の整数、ｎは０から４の整数であり、Ｒ３およびＲ４はそれぞれ独立に、水素原子または炭素数１～１０のアルキル基であり、Ｒ５およびＲ６はそれぞれ独立に炭素数１～１０のアルキレン基である。）
で表わされる化合物が好ましい。一般式（４）で表わされるエピスルフィド化合物の例としては、ビス（２，３－エピチオプロピル）スルフィド等が挙げられる。 Next, the curable composition of this invention is demonstrated.
The curable composition of the present invention includes the polythiourethane oligomer (A component), the episulfide compound (B component), and the photobase generator (C component) described above.
An episulfide compound (component B) is a compound having one or more episulfide groups in one molecule. In particular, when pursuing higher refractive index of the curable composition, the following general formula (4)
Figure JPOXMLDOC01-appb-C000011
 (Wherein, m is an integer from 0 to 6, n is an integer from 0 to 4, each R 3 and R 4 are independently hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R 5 and R 6 is each independently an alkylene group having 1 to 10 carbon atoms.)
The compound represented by these is preferable. Examples of the episulfide compound represented by the general formula (4) include bis (2,3-epithiopropyl) sulfide.
　一般式（４）で表わされるエピスルフィド化合物は硬化に伴う収縮が大きいが、ポリチオウレタンオリゴマーと共重合することによって硬化に伴う収縮を抑えることができる。また、一般式（４）で表わされるエピスルフィド化合物は概して粘度が低いが、ポリチオウレタンオリゴマーと混合することで、作業性に優れた粘度に調整される。 Although the episulfide compound represented by the general formula (4) has a large shrinkage due to curing, the shrinkage due to the curing can be suppressed by copolymerizing with the polythiourethane oligomer. In addition, the episulfide compound represented by the general formula (4) generally has a low viscosity, but is adjusted to a viscosity excellent in workability by mixing with the polythiourethane oligomer.
　硬化性組成物の粘度に関して、接着剤としての使用を想定した場合、粘度が低すぎると、接着剤が垂れたり流れたり、張り合わせの際に基板がずれたりして好ましくない。また、粘度が高すぎると、接着剤の吐出や塗布が困難になったり、張り合わせの際に気泡が噛んだりして好ましくない。本発明で言う作業性に適した粘度とは、塗布方法や張り合わせ方法といった接着剤の使用形態にも依るので一概には規定できないが、好ましくは５００～２０，０００ｍＰａ・ｓの範囲であり、より好ましくは５００～１０，０００ｍＰａ・ｓの範囲である。 Assuming that the curable composition is used as an adhesive with respect to the viscosity of the curable composition, if the viscosity is too low, the adhesive may sag or flow, or the substrate may be displaced during bonding. On the other hand, if the viscosity is too high, it is not preferable because it becomes difficult to discharge or apply the adhesive, or bubbles are bitten during the bonding. The viscosity suitable for workability as referred to in the present invention depends on the use form of the adhesive such as the coating method and the laminating method, and cannot be defined unconditionally, but is preferably in the range of 500 to 20,000 mPa · s, more The range is preferably 500 to 10,000 mPa · s.
　ポリチオウレタンオリゴマーの含有量について、硬化性組成物１００重量部に対して、１０～７０重量部の範囲が好ましく、２０～６０重量部の範囲がさらに好ましい。ポリチオウレタンオリゴマーの含有量が１０重量部未満では高粘度化や低収縮化の効果が小さくなり、７０重量部を超えると硬化物の靭性が低下して、好ましくない。 The content of the polythiourethane oligomer is preferably in the range of 10 to 70 parts by weight, more preferably in the range of 20 to 60 parts by weight with respect to 100 parts by weight of the curable composition. If the content of the polythiourethane oligomer is less than 10 parts by weight, the effect of increasing the viscosity or reducing the shrinkage is reduced, and if it exceeds 70 parts by weight, the toughness of the cured product is lowered, which is not preferable.
　光塩基発生剤（Ｃ成分）とは、活性光線によって光分解して塩基を発生する化合物である。特に、エピスルフィド化合物の重合はＤＢＮ（ジアザビシクロノネン）やＤＢＵ（ジアザビシクロウンデセン）等のアミジンによって促進されるので、これらの塩基を発生させる光塩基発生剤が好ましい。具体的には、特表２００１－５１３７６５に記載されているテトラアリールボラート塩を形成しているアミジニウムケトン（下記式（５）の左辺）や特表２００５－５１１５３６に記載されているアリールアルキル基によって置換された１，３－ジアミン（下記式（６）の左辺）等が挙げられる。これらは単独でも２種類以上を混合して使用しても構わない。光塩基発生剤の添加量は、硬化性組成物１００重量部に対して、０.０１～１０重量部の範囲が好ましく、０．１～５重量部の範囲がより好ましい。
Figure JPOXMLDOC01-appb-C000012
 （式中、Ａｒ１は、フェニル、ビフェニル、ナフチル、フェナントリル、アントラシル、ピレニル、５，６，７，８－テトラヒドロ－２－ナフチル、５，６，７，８－テトラヒドロ-１-ナフチル、チエニル、ベンゾ［ｂ］チエニル、ナフト［２，３－ｂ］チエニル、チアトレニル、ジベンゾフリル、クロメニル、キサンテニル、チオキサンチル、フェノキサチイニル、ターフェニル、スチルベニルまたはフルオレニルであって、これらの基は非置換であるか、またはＣ１～Ｃ１８アルキル、Ｃ３～Ｃ１８アルケニル、Ｃ３～Ｃ１８アルキニル、Ｃ１～Ｃ１８ハロアルキル、ＮＯ２、ＯＨ、ＣＮ、ＯＲ７、ＳＲ８、Ｃ（Ｏ）Ｒ９、Ｃ（Ｏ）ＯＲ１０もしくはハロゲンによって１回以上置換されており、Ｒ７～Ｒ１０はそれぞれ独立に水素またはＣ１～Ｃ１８アルキルである。）
Figure JPOXMLDOC01-appb-C000013
 （式中、Ａｒ２は、フェニル、ナフチル、アントリルまたはアントラキノニルであって、これらの基は非置換であるか、またはＣ１～Ｃ４アルキル、Ｃ２～Ｃ４アルケニル、ＮＯ２、ＣＮ、ＯＲ１１、ＳＲ１２、Ｃ（Ｏ）Ｒ１３、Ｃ（Ｏ）ＯＲ１４、もしくはハロゲンによって１回以上置換されており、Ｒ１１～Ｒ１４はそれぞれ独立に水素またはＣ１～Ｃ４アルキルであり、Ｒ１５は水素またはＣ１～Ｃ６アルキルである。） The photobase generator (component C) is a compound that generates a base by photolysis with actinic rays. In particular, since the polymerization of episulfide compounds is promoted by amidine such as DBN (diazabicyclononene) and DBU (diazabicycloundecene), photobase generators that generate these bases are preferred. Specifically, the amidinium ketone (the left side of the following formula (5)) forming the tetraarylborate salt described in JP-T-2001-513765 and the aryl described in JP-T-2005-511536 1,3-diamine substituted with an alkyl group (left side of the following formula (6)) and the like. These may be used alone or in combination of two or more. The addition amount of the photobase generator is preferably in the range of 0.01 to 10 parts by weight, more preferably in the range of 0.1 to 5 parts by weight with respect to 100 parts by weight of the curable composition.
Figure JPOXMLDOC01-appb-C000012
 Wherein Ar 1 is phenyl, biphenyl, naphthyl, phenanthryl, anthracyl, pyrenyl, 5,6,7,8-tetrahydro-2-naphthyl, 5,6,7,8-tetrahydro-1-naphthyl, thienyl, Benzo [b] thienyl, naphtho [2,3-b] thienyl, thiatrenyl, dibenzofuryl, chromenyl, xanthenyl, thioxanthyl, phenoxathiinyl, terphenyl, stilbenyl or fluorenyl, these groups being unsubstituted Or C1-C18 alkyl, C3-C18 alkenyl, C3-C18 alkynyl, C1-C18 haloalkyl, NO 2 , OH, CN, OR 7 , SR 8 , C (O) R 9 , C (O) OR 10 or is substituted one or more times by halogen, water each R 7 ~ R 10 is independently Or C1 ~ C18 alkyl.)
Figure JPOXMLDOC01-appb-C000013
 Wherein Ar 2 is phenyl, naphthyl, anthryl or anthraquinonyl, and these groups are unsubstituted or C1-C4 alkyl, C2-C4 alkenyl, NO 2 , CN, OR 11 , SR 12 , C (O) R 13 , C (O) OR 14 , or halogen one or more times, R 11 to R 14 are each independently hydrogen or C1-C4 alkyl, and R 15 is hydrogen or C1 ~ C6 alkyl.)
　また、光塩基発生剤に加えて光増感剤を含んでもよい。光増感剤を添加することにより、光塩基発生剤の光分解が速まり、光硬化性組成物の硬化時間を短縮することができる。光増感剤の具体例としては、ベンゾフェノン類、チオキサントン類、アンスラキノン類、カンファーキノン類、ベンジル類、ミヒラーケトン類、アントラセン類が挙げられる。これらは単独でも２種類以上を混合して使用しても構わない。光増感剤の添加量は、硬化性組成物１００重量部に対して、０.０１～１０重量部の範囲が好ましく、０．１～５重量部の範囲がより好ましい。 In addition to the photobase generator, a photosensitizer may be included. By adding the photosensitizer, the photodecomposition of the photobase generator is accelerated, and the curing time of the photocurable composition can be shortened. Specific examples of the photosensitizer include benzophenones, thioxanthones, anthraquinones, camphorquinones, benzyls, Michler ketones, and anthracenes. These may be used alone or in combination of two or more. The addition amount of the photosensitizer is preferably in the range of 0.01 to 10 parts by weight and more preferably in the range of 0.1 to 5 parts by weight with respect to 100 parts by weight of the curable composition.
　前記の硬化性組成物には必要に応じて、重合禁止剤、重合抑制剤、酸化防止剤、紫外線吸収剤、シランカップリング剤、離型剤、顔料、染料等を添加することが可能である。また、必要に応じて、ろ過や脱泡などを行っても構わない。 If necessary, a polymerization inhibitor, a polymerization inhibitor, an antioxidant, an ultraviolet absorber, a silane coupling agent, a release agent, a pigment, a dye, and the like can be added to the curable composition. . Moreover, you may perform filtration, defoaming, etc. as needed.
　以下、実施例により本発明を具体的に説明するが、本発明はこれらに限定されるものではない。なお、実施例中における硬化収縮率は、下記の計算式に従い、硬化前後における屈折率から計算した。
Ｘ＝（１－ｄ１／ｄ２）×１００［％］
Ｒ＝（ｎ２－１）／（ｎ２＋２）×Ｍ／ｄ
硬化前後でＲ／Ｍは一定なので、上の２式より、
Ｘ＝［１－｛（ｎ１２－１）/（ｎ１２＋２）｝／｛（ｎ２２－１）/（ｎ２２＋２）｝］×１００［％］
（式中、Ｘは硬化収縮率、ｄは比重、ｄ１は硬化前の比重、ｄ２は硬化後の比重、Ｒは分子屈折、ｎは屈折率、ｎ１は硬化前の屈折率、ｎ２は硬化後の屈折率、Ｍは分子量を表す。）
また、硬化性組成物の粘度は、コーン／プレート型粘度計ＤＶ－II＋（ブルックフィールド社製）を用いて、温度２５℃にて測定した。硬化性組成物および硬化膜の屈折率は、アッベ屈折計ＮＡＲ－３Ｔ（アタゴ社製）を用いて測定した。硬化膜の透過率は、分光光度計Ｕ－３５００（日立ハイテク社製）を用いて、硬化膜の厚み０．２５ｍｍ、波長４００ｎｍにて測定した。 EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, the cure shrinkage rate in an Example was computed from the refractive index before and behind hardening according to the following formula.
X = (1−d1 / d2) × 100 [%]
R = (n 2 −1) / (n 2 +2) × M / d
Since R / M is constant before and after curing,
X = [1-{(n1 2 −1) / (n1 2 +2)} / {(n2 2 −1) / (n2 2 +2)}] × 100 [%]
(Where X is the curing shrinkage ratio, d is the specific gravity, d1 is the specific gravity before curing, d2 is the specific gravity after curing, R is the molecular refraction, n is the refractive index, n1 is the refractive index before curing, and n2 is the after curing. The refractive index of M and M represents the molecular weight.)
The viscosity of the curable composition was measured at a temperature of 25 ° C. using a cone / plate viscometer DV-II + (manufactured by Brookfield). The refractive indexes of the curable composition and the cured film were measured using an Abbe refractometer NAR-3T (manufactured by Atago Co., Ltd.). The transmittance of the cured film was measured using a spectrophotometer U-3500 (manufactured by Hitachi High-Tech) at a thickness of 0.25 mm and a wavelength of 400 nm.
実施例１
　３００ｍｌフラスコに、２，５－ジメルカプトメチル－１，４－ジチアン２５ｇ、ｍ－キシリレンジイソシアネート１５ｇ、およびジラウリン酸ジブチルスズ０．１ｇをとり、６０℃にて２４時間撹拌を続けた。赤外分光光度計にてイソシアネート基のＩＲ吸収（２２８０ｃｍ－１）が無くなったことを確認した後、ビス（２，３－エピチオプロピル）スルフィド６０ｇ、下記構造式（７）
Figure JPOXMLDOC01-appb-C000014
 で表わされる光塩基発生剤０．５ｇ（Ｃ成分）、および増感剤として４－ベンゾイル－４’－メチルジフェニルスルフィド１ｇを加えて、均一になるまで撹拌した。以上の手順で硬化性組成物を作製した。 Example 1
In a 300 ml flask, 25 g of 2,5-dimercaptomethyl-1,4-dithiane, 15 g of m-xylylene diisocyanate and 0.1 g of dibutyltin dilaurate were placed, and stirring was continued at 60 ° C. for 24 hours. After confirming that IR absorption (2280 cm −1 ) of the isocyanate group disappeared with an infrared spectrophotometer, 60 g of bis (2,3-epithiopropyl) sulfide, the following structural formula (7)
Figure JPOXMLDOC01-appb-C000014
 And 0.5 g (component C) of a photobase generator represented by the formula (1) and 1 g of 4-benzoyl-4′-methyldiphenyl sulfide as a sensitizer were added and stirred until uniform. The curable composition was produced in the above procedure.
　硬化性組成物を離型処理された２枚のガラス板で挟み、メタルハライドランプ（１２０Ｗ／ｃｍ）からの光を３０ｃｍの距離から３分間照射した後、硬化した膜をガラス板から剥がした。以上の手順で厚み０．２５ｍｍの硬化膜を作製した。
　硬化性組成物および硬化膜の物性は表１に示す通りであった。 The curable composition was sandwiched between two release-treated glass plates, irradiated with light from a metal halide lamp (120 W / cm) for 3 minutes from a distance of 30 cm, and then the cured film was peeled from the glass plate. A cured film having a thickness of 0.25 mm was produced by the above procedure.
The physical properties of the curable composition and the cured film were as shown in Table 1.
実施例２～５
　ポリチオール、ポリイソシアネート、およびエピスルフィド化合物の種類と仕込み量を表１に示す内容に変える以外は実施例１と同様にして硬化性組成物および硬化膜の作製を行った。硬化性組成物および硬化膜の物性は表１に示す通りであった。 Examples 2-5
A curable composition and a cured film were prepared in the same manner as in Example 1 except that the types and amounts of polythiol, polyisocyanate, and episulfide compound were changed to those shown in Table 1. The physical properties of the curable composition and the cured film were as shown in Table 1.
比較例１
　ビス（２，３－エピチオプロピル）スルフィド１００ｇ、前記の構造式（７）で表わされる光塩基発生剤０．５ｇ（Ｃ成分）、および増感剤として４－ベンゾイル－４’－メチルジフェニルスルフィド１ｇを加えて、均一になるまで撹拌した。以上の手順で硬化性組成物を作製した。
　実施例１と同様にして硬化膜を作製した。硬化性組成物および硬化膜の物性は表２に示す通りであった。なお、実施例と比較して劣る物性には下線を引いた。 Comparative Example 1
100 g of bis (2,3-epithiopropyl) sulfide, 0.5 g of photobase generator represented by the structural formula (7) (C component), and 4-benzoyl-4′-methyldiphenyl sulfide as a sensitizer 1 g was added and stirred until uniform. The curable composition was produced in the above procedure.
A cured film was produced in the same manner as in Example 1. The physical properties of the curable composition and the cured film were as shown in Table 2. In addition, physical properties that are inferior to those of the examples are underlined.
比較例２
　２，５－ジメルカプトメチル－１，４－ジチアン２０ｇ、ビス（２，３－エピチオプロピル）スルフィド８０ｇ、前記の構造式（７）で表わされる光塩基発生剤０．５ｇ（Ｃ成分）、および増感剤として４－ベンゾイル－４’－メチルジフェニルスルフィド１ｇを加えて、均一になるまで撹拌した。以上の手順で硬化性組成物を作製した。
　実施例１と同様にして硬化膜を作製した。硬化性組成物および硬化膜の物性は表２に示す通りであった。なお、実施例と比較して劣る物性には下線を引いた。 Comparative Example 2
2,5-dimercaptomethyl-1,4-dithiane 20 g, bis (2,3-epithiopropyl) sulfide 80 g, photobase generator 0.5 g (component C) represented by the structural formula (7), Then, 1 g of 4-benzoyl-4′-methyldiphenyl sulfide was added as a sensitizer and stirred until uniform. The curable composition was produced in the above procedure.
A cured film was produced in the same manner as in Example 1. The physical properties of the curable composition and the cured film were as shown in Table 2. In addition, physical properties that are inferior to those of the examples are underlined.
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000016
Figure JPOXMLDOC01-appb-T000016
表中略語の説明
（ａ－１）２，５－ジメルカプトメチル－１，４－ジチアン
（ａ－２）ペンタエリスリトールテトラキス（３－メルカプトプロピオネート）
（ａ－３）ｍ－キシリレンジチオール
（ａ－４）１，５－ジメルカプト－３－チアペンタン
（ｂ－１）ｍ－キシリレンジイソシアネート
（ｂ－２）１，３－ビス（２－イソシアナト－２－プロピル）シクロヘキサン
（ｂ－３）１，３－ビス（２－イソシアナト－２－プロピル）ベンゼン
（ｂ－４）イソホロンジイソシアネート
（ｃ－１）ビス（２，３－エピチオプロピル）スルフィド Explanation of Abbreviations in Table (a-1) 2,5-Dimercaptomethyl-1,4-dithiane (a-2) Pentaerythritol tetrakis (3-mercaptopropionate)
(A-3) m-xylylenedithiol (a-4) 1,5-dimercapto-3-thiapentane (b-1) m-xylylene diisocyanate (b-2) 1,3-bis (2-isocyanato-2 -Propyl) cyclohexane (b-3) 1,3-bis (2-isocyanato-2-propyl) benzene (b-4) isophorone diisocyanate (c-1) bis (2,3-epithiopropyl) sulfide

Claims (7)

  1. 　ポリチオールとポリイソシアネートを反応させて得られるポリチオウレタンオリゴマー（Ａ成分）、エピスルフィド化合物（Ｂ成分）および光塩基発生剤（Ｃ成分）を含有する硬化性組成物。 A curable composition containing a polythiourethane oligomer (component A) obtained by reacting polythiol and polyisocyanate, an episulfide compound (component B), and a photobase generator (component C).
  2. 　ポリチオールが、下記一般式（１）、下記一般式（２）および下記一般式（３）から成る群から選択される一種以上である請求項１に記載の硬化性組成物。
    Figure JPOXMLDOC01-appb-C000001
     （式中、ｐ１およびｐ２はそれぞれ独立に０～１の整数を表し、Ｘ１～Ｘ８はそれぞれ独立に水素原子またはメチルチオール基を表す。）
    Figure JPOXMLDOC01-appb-C000002
     （式中、ｑは０～３の整数を表し、Ｒ１は単なる結合または炭素数１～３のアルキレン基を表す。）
    Figure JPOXMLDOC01-appb-C000003
     （式中、ｒは０～３の整数を表し、Ｒ２は炭素数１～３のアルキレン基を表す。）     The curable composition according to claim 1, wherein the polythiol is at least one selected from the group consisting of the following general formula (1), the following general formula (2), and the following general formula (3).
    Figure JPOXMLDOC01-appb-C000001
     (Wherein p1 and p2 each independently represents an integer of 0 to 1, and X 1 to X 8 each independently represents a hydrogen atom or a methylthiol group.)
    Figure JPOXMLDOC01-appb-C000002
     (In the formula, q represents an integer of 0 to 3, and R 1 represents a simple bond or an alkylene group having 1 to 3 carbon atoms.)
    Figure JPOXMLDOC01-appb-C000003
     (In the formula, r represents an integer of 0 to 3, and R 2 represents an alkylene group having 1 to 3 carbon atoms.)
  3. 　ポリチオールとポリイソシアネートを反応させる際のポリチオールとポリイソシアネートの比率が、チオール基１モルに対して、イソシアネート基が０．２～０．９５モルの範囲である、請求項１または２に記載の硬化性組成物。 The curing according to claim 1 or 2, wherein the ratio of polythiol to polyisocyanate in the reaction of polythiol and polyisocyanate is in the range of 0.2 to 0.95 mol of isocyanate group with respect to 1 mol of thiol group. Sex composition.
  4. 　エピスルフィド化合物（Ｂ成分）が、下記一般式（４）で表わされる化合物である請求項１から３のいずれかに記載の硬化性組成物。
    Figure JPOXMLDOC01-appb-C000004
     （式中、ｍは０から６の整数、ｎは０から４の整数であり、Ｒ３およびＲ４はそれぞれ独立に、水素原子または炭素数１～１０のアルキル基であり、Ｒ５およびＲ６はそれぞれ独立に炭素数１～１０のアルキレン基である。）     The curable composition according to any one of claims 1 to 3, wherein the episulfide compound (component B) is a compound represented by the following general formula (4).
    Figure JPOXMLDOC01-appb-C000004
     (Wherein, m is an integer from 0 to 6, n is an integer from 0 to 4, each R 3 and R 4 are independently hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R 5 and R 6 is each independently an alkylene group having 1 to 10 carbon atoms.)
  5. 　一般式（４）で表わされる化合物がビス（２，３－エピチオプロピル）スルフィドである請求項４に記載の硬化性組成物。 The curable composition according to claim 4, wherein the compound represented by the general formula (4) is bis (2,3-epithiopropyl) sulfide.
  6. 　光塩基発生剤（Ｃ成分）が、下記一般式（８）または（９）で表される化合物である請求項１から５のいずれかに記載の硬化性組成物。
    Figure JPOXMLDOC01-appb-C000005
     （式中、Ａｒ１は、フェニル、ビフェニル、ナフチル、フェナントリル、アントラシル、ピレニル、５，６，７，８－テトラヒドロ－２－ナフチル、５，６，７，８－テトラヒドロ-１-ナフチル、チエニル、ベンゾ［ｂ］チエニル、ナフト［２，３－ｂ］チエニル、チアトレニル、ジベンゾフリル、クロメニル、キサンテニル、チオキサンチル、フェノキサチイニル、ターフェニル、スチルベニルまたはフルオレニルであって、これらの基は非置換であるか、またはＣ１～Ｃ１８アルキル、Ｃ３～Ｃ１８アルケニル、Ｃ３～Ｃ１８アルキニル、Ｃ１～Ｃ１８ハロアルキル、ＮＯ２、ＯＨ、ＣＮ、ＯＲ７、ＳＲ８、Ｃ（Ｏ）Ｒ９、Ｃ（Ｏ）ＯＲ１０もしくはハロゲンによって１回以上置換されており、Ｒ７～Ｒ１０はそれぞれ独立に水素またはＣ１～Ｃ１８アルキルである。）
    Figure JPOXMLDOC01-appb-C000006
     （式中、Ａｒ２は、フェニル、ナフチル、アントリルまたはアントラキノニルであって、これらの基は非置換であるか、またはＣ１～Ｃ４アルキル、Ｃ２～Ｃ４アルケニル、ＮＯ２、ＣＮ、ＯＲ１１、ＳＲ１２、Ｃ（Ｏ）Ｒ１３、Ｃ（Ｏ）ＯＲ１４、もしくはハロゲンによって１回以上置換されており、Ｒ１１～Ｒ１４はそれぞれ独立に水素またはＣ１～Ｃ４アルキルであり、Ｒ１５は水素またはＣ１～Ｃ６アルキルである。）     The curable composition according to any one of claims 1 to 5, wherein the photobase generator (component C) is a compound represented by the following general formula (8) or (9).
    Figure JPOXMLDOC01-appb-C000005
     Wherein Ar 1 is phenyl, biphenyl, naphthyl, phenanthryl, anthracyl, pyrenyl, 5,6,7,8-tetrahydro-2-naphthyl, 5,6,7,8-tetrahydro-1-naphthyl, thienyl, Benzo [b] thienyl, naphtho [2,3-b] thienyl, thiatrenyl, dibenzofuryl, chromenyl, xanthenyl, thioxanthyl, phenoxathiinyl, terphenyl, stilbenyl or fluorenyl, these groups being unsubstituted Or C1-C18 alkyl, C3-C18 alkenyl, C3-C18 alkynyl, C1-C18 haloalkyl, NO 2 , OH, CN, OR 7 , SR 8 , C (O) R 9 , C (O) OR 10 or is substituted one or more times by halogen, water each R 7 ~ R 10 is independently Or C1 ~ C18 alkyl.)
    Figure JPOXMLDOC01-appb-C000006
     Wherein Ar 2 is phenyl, naphthyl, anthryl or anthraquinonyl, and these groups are unsubstituted or C1-C4 alkyl, C2-C4 alkenyl, NO 2 , CN, OR 11 , SR 12 , C (O) R 13 , C (O) OR 14 , or halogen one or more times, R 11 to R 14 are each independently hydrogen or C1-C4 alkyl, and R 15 is hydrogen or C1 ~ C6 alkyl.)
  7. 　請求項１から６のいずれかに記載の硬化性組成物を含有する光学用接着剤。
          The optical adhesive agent containing the curable composition in any one of Claim 1 to 6.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013129460A1 (en) * 2012-03-01 2013-09-06 三菱瓦斯化学株式会社 Polymerizable composition for optical materials
JPWO2023063398A1 (en) * 2021-10-15 2023-04-20
WO2024260512A1 (en) * 2023-06-20 2024-12-26 Rodenstock Gmbh Method for producing a glass body, glass body and polymerisable mixture

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11349658A (en) * 1998-06-11 1999-12-21 Sumitomo Seika Chem Co Ltd Curable composition and optical material obtained by using the same
JP2004059901A (en) * 2002-06-04 2004-02-26 Hoya Corp Method for producing plastic lens, and plastic lens
WO2005014696A1 (en) * 2003-08-06 2005-02-17 Mitsubishi Gas Chemical Company, Inc. Photocurable composition and coating composition
JP2005264156A (en) * 2004-02-16 2005-09-29 Mitsubishi Gas Chem Co Inc Photobase generator
JP2005272785A (en) * 2004-03-26 2005-10-06 Mitsui Chemicals Inc Highly refractive/highly weather-resistant resin and its manufacturing method
JP2007197615A (en) * 2006-01-27 2007-08-09 Mitsubishi Gas Chem Co Inc Composition for resin
JP2011038050A (en) * 2009-08-18 2011-02-24 Mitsubishi Gas Chemical Co Inc Photo-curable composition, method for curing the same, and cured product thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1564255B1 (en) * 2004-02-16 2007-09-26 Mitsubishi Gas Chemical Company, Inc. Photobase generator and curable composition

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11349658A (en) * 1998-06-11 1999-12-21 Sumitomo Seika Chem Co Ltd Curable composition and optical material obtained by using the same
JP2004059901A (en) * 2002-06-04 2004-02-26 Hoya Corp Method for producing plastic lens, and plastic lens
WO2005014696A1 (en) * 2003-08-06 2005-02-17 Mitsubishi Gas Chemical Company, Inc. Photocurable composition and coating composition
JP2005264156A (en) * 2004-02-16 2005-09-29 Mitsubishi Gas Chem Co Inc Photobase generator
JP2005272785A (en) * 2004-03-26 2005-10-06 Mitsui Chemicals Inc Highly refractive/highly weather-resistant resin and its manufacturing method
JP2007197615A (en) * 2006-01-27 2007-08-09 Mitsubishi Gas Chem Co Inc Composition for resin
JP2011038050A (en) * 2009-08-18 2011-02-24 Mitsubishi Gas Chemical Co Inc Photo-curable composition, method for curing the same, and cured product thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013129460A1 (en) * 2012-03-01 2013-09-06 三菱瓦斯化学株式会社 Polymerizable composition for optical materials
US9518153B2 (en) 2012-03-01 2016-12-13 Mitsubishi Gas Chemical Company, Inc. Polymerizable composition for optical materials
JPWO2023063398A1 (en) * 2021-10-15 2023-04-20
WO2023063398A1 (en) * 2021-10-15 2023-04-20 三井化学株式会社 Photocurable composition, cured article, laminated body, method for producing cured article, and method for producing lens
WO2024260512A1 (en) * 2023-06-20 2024-12-26 Rodenstock Gmbh Method for producing a glass body, glass body and polymerisable mixture

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