WO2012147708A1 - Composition durcissable et adhésif pour l'optique - Google Patents

Composition durcissable et adhésif pour l'optique Download PDF

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Publication number
WO2012147708A1
WO2012147708A1 PCT/JP2012/060899 JP2012060899W WO2012147708A1 WO 2012147708 A1 WO2012147708 A1 WO 2012147708A1 JP 2012060899 W JP2012060899 W JP 2012060899W WO 2012147708 A1 WO2012147708 A1 WO 2012147708A1
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Prior art keywords
curable composition
polythiol
group
component
sulfur
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PCT/JP2012/060899
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English (en)
Japanese (ja)
Inventor
淳也 早川
岡崎　仁
竹内　基晴
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Mitsubishi Gas Chemical Co Inc
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Mitsubishi Gas Chemical Co Inc
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Priority claimed from JP2011101440A external-priority patent/JP5834474B2/ja
Priority claimed from JP2011103643A external-priority patent/JP5742443B2/ja
Application filed by Mitsubishi Gas Chemical Co Inc filed Critical Mitsubishi Gas Chemical Co Inc
Priority to CN201280020326.XA priority Critical patent/CN103562273B9/zh
Publication of WO2012147708A1 publication Critical patent/WO2012147708A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/06—Polythioethers from cyclic thioethers
    • C08G75/08—Polythioethers from cyclic thioethers from thiiranes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • 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
    • C09J181/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Adhesives based on polysulfones; Adhesives based on derivatives of such polymers
    • C09J181/02—Polythioethers; Polythioether-ethers

Definitions

  • the present invention relates to a curable composition suitable as an optical adhesive used for producing a composite optical element.
  • a photocurable composition mainly composed of an acrylate compound or the like is widely used as an adhesive for producing an optical element.
  • 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.
  • Application examples in which an adhesive having a high refractive index is used for example, as an example of a composite optical element, an achromatic lens (achromat lens) formed by bonding two lenses, and a composite of glass and resin Examples include a prism having a complicated shape such as a hybrid aspherical lens and a dichroic prism.
  • Adhesives used for these applications are required not only to have a high refractive index, but also to have performance such as adhesion, photocurability, colorless transparency, heat resistance, 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.
  • a polyfunctional (meth) acrylate compound having a high refractive index 9,9-bis (4- (2-acryloxyethoxy) phenyl) fluorene (hereinafter referred to as A-BPEF) (refractive index of cured product 1 .62), 4,4′-bis (methacryloylthio) diphenyl sulfide (hereinafter referred to as MPSMA) (refractive index of cured product 1.69) and the like.
  • A-BPEF 9,9-bis (4- (2-acryloxyethoxy) phenyl) fluorene
  • MPSMA 4,4′-bis (methacryloylthio) diphenyl sulfide
  • a polyfunctional (meth) acrylate compound has a large shrinkage due to curing, and causes a decrease in adhesion when used as an adhesive.
  • an ene / thiol composition combining an ethylenically unsaturated compound such as a (meth) acrylate compound and a thiol compound has a high refractive index cured product because the thiol compound contains a sulfur atom having a high atomic refraction.
  • a thiol compound contains a sulfur atom having a high atomic refraction.
  • Patent Document 5 describes an ene-thiol composition composed of a bifunctional thiol compound containing a 1,4-dithiane ring and triallyl isocyanurate or triallyl cyanurate.
  • the refractive index of the cured product is not particularly described.
  • the bifunctional thiol compound is used, the cured product is easily softened at a high temperature (see Comparative Example).
  • Patent Document 6 describes an ene-thiol composition composed of A-BPEF, an ethylenically unsaturated compound, and a thiol compound. According to the examples, the refractive index of the cured product is at most in the range of 1.58 to 1.61.
  • Patent Document 7 describes an ene / thiol composition composed of MPSMA, a vinyl monomer, and polythiol. According to the example, the refractive index of the cured product is 1.649 at the maximum. However, MPSMA is easily yellow-colored and has a limit in the amount of dissolution in the composition because it is solid.
  • Patent Document 8 describes a resin composition composed of a resin component having a fluorene ring and a sulfur-containing compound having a diphenyl sulfide skeleton such as MPSMA, and a resin having a refractive index of 1.724. Illustrated.
  • the resin composition in the present invention is substantially a thermoplastic resin obtained by kneading a polyester having a fluorene ring and a sulfur-containing compound and is not a curable composition, and of course, photocurability cannot be imparted.
  • 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 JP 2000-154251 A JP 2010-254732 A Japanese Patent Laid-Open No. 03-021638 JP 2005-187661 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.
  • component A a polythiol oligomer obtained by reacting polythiol and sulfur
  • component B a polyene compound obtained by reacting polythiol and sulfur
  • component C an episulfide compound obtained by reacting polythiol and sulfur
  • component D a photobase generator
  • 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 first curable composition of the present invention comprises a polythiol oligomer (A component) obtained by reacting polythiol and sulfur and a polyene compound (B component). First, the manufacturing method of a polythiol oligomer (A component) is demonstrated.
  • the polythiol used as the raw material of the polythiol 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.
  • Examples of the polythiol compound other than the compounds represented by the general formulas (1) to (3) include ethylene glycol bis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3 -Mercaptopropionate), benzenedithiol, tolylenedithiol and the like.
  • sulfur forms many allotropes, and generally well-known cyclic S8 sulfur is preferable.
  • Sulfur may be in any form, for example, crystalline, colloidal, powder, or sulfur.
  • reaction of polythiol is mainly represented by the following reaction formulas (6) and (7): (In the formula, R represents an organic group, and n represents an integer of 1 or more.) Proceed according to.
  • the amount of sulfur used is preferably in the range of 0.2 to 0.95 moles of sulfur atoms, more preferably in the range of 0.2 to 0.5 moles per mole of thiol group.
  • the reaction between polythiol and sulfur proceeds by heating in the presence or absence of a basic catalyst, but a method using a basic catalyst is preferred.
  • the basic catalyst include amines, ammonium salts, phosphines, and phosphonium salts.
  • the amount of the basic catalyst used is preferably in the range of 0.005 to 5 mol, more preferably in the range of 0.05 to 0.5 mol, with respect to 100 mol of the thiol group contained in the raw polythiol.
  • Each raw material can be added by adding a catalyst to the polythiol and sulfur mixed solution, adding sulfur to the polythiol and catalyst mixed solution, or adding the polythiol and sulfur mixed solution to the polythiol and sulfur mixed solution. May be. In order to allow the reaction to proceed gently, the catalyst and sulfur may be added in several portions.
  • the reaction between polythiol and sulfur may be performed in the presence of a polyene compound (component B). Since the reaction between polythiol and sulfur is accompanied by the generation of hydrogen sulfide, the reaction is preferably performed under exhaust or reduced pressure. You may use a solvent as needed. 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 ratio of polythiol and sulfur, and the reaction temperature, and thus cannot be defined unconditionally, but the reaction is continued until no unreacted sulfur remains.
  • the 1st curable composition of this invention is comprised including the polythiol oligomer (A component) and polyene compound (B component) which were mentioned above.
  • the polyene compound (component B) is a compound having two or more ethylenically unsaturated bond groups in one molecule, and examples of the ethylenically unsaturated bond group include acryloyl group, methacryloyl group, vinyl group, and allyl group. Can be mentioned.
  • a compound having an aromatic ring or a heterocyclic ring in the molecule is preferable. Examples of such a compound include triallyl isocyanurate, triallyl cyanurate, diallyl phthalate.
  • X represents a sulfur atom or a sulfonyl group
  • Z represents a (meth) acryloyl group, a vinyl group, or an allyl group.
  • m and n represent an integer in which the sum of m and n satisfies 0 to 4, R 3 represents an alkylene group having 1 to 5 carbon atoms, R 4 represents a hydrogen atom or a methyl group, R 5 represents a hydrogen atom or a methyl group.
  • Examples of the compound represented by the general formula (4) include 4,4′-bis (methacryloylthio) diphenyl sulfide, 4,4′-bis (methacryloylthio) diphenyl sulfone, and the like. Examples of the compound represented include 9,9-bis (4- (2-acryloxyethoxy) phenyl) fluorene.
  • the content of the polythiol oligomer in the first curable composition is preferably in the range of 10 to 80 parts by weight, more preferably in the range of 20 to 70 parts by weight with respect to 100 parts by weight of the curable composition.
  • the content of the polythiol oligomer is less than 10 parts by weight, the effect of increasing the viscosity or reducing the shrinkage is reduced, and when it exceeds 80 parts by weight, the toughness of the cured product is lowered, which is not preferable.
  • a polymerization inhibitor an antioxidant, a light stabilizer (HALS), an ultraviolet absorber, a silane coupling agent, a release agent, a pigment, a dye, and the like may be added to the curable composition of the present invention. Is possible.
  • the curable composition of the present invention is cured by irradiation with an actinic ray such as ultraviolet light or visible light in the presence of a radical photopolymerization initiator.
  • an actinic ray such as ultraviolet light or visible light
  • the radical photopolymerization initiator is not particularly limited as long as it generates an active free radical by photolysis.
  • Such compounds include 2,2-methoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1- ON, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, Examples thereof include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and the like.
  • the radical photopolymerization initiators may be used alone or in combination of two or more.
  • the content is not particularly limited, but is preferably in the range of 0.1 to 10 parts by weight, more preferably in the range of 0.5 to 5 parts by weight with respect to 100 parts by weight of the curable composition.
  • 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 adherend may be displaced during bonding, which is not preferable.
  • the viscosity is too high, it is not preferable because it becomes difficult to discharge or apply the adhesive, or the air bubbles are bitten at the time of bonding.
  • the viscosity suitable for workability in the first curable composition cannot be defined unconditionally because it depends on the use form of the adhesive such as the coating method and the laminating method, but is preferably 500 to 20,000 mPa ⁇ s. The range is more preferably 1,000 to 10,000 mPa ⁇ s.
  • the second curable composition of the present invention comprises a polythiol oligomer (A component) obtained by reacting polythiol and sulfur, an episulfide compound (C component), and a photobase generator (D component). .
  • the method for producing the polythiol oligomer (component A) in the second curable composition is generally as described for the first curable composition.
  • the manufacturing method of the polythiol oligomer (A component) in the second curable composition will be described focusing on the difference from the manufacturing method of the polythiol oligomer (A component) in the first curable composition.
  • the reaction between polythiol and sulfur proceeds by heating in the presence or absence of a basic catalyst, but a method using a basic catalyst is preferred.
  • a hindered amine is preferable as the base catalyst.
  • the hindered amine refers to an amine having a substituent on both sides of the amino group. Hindered amines are weak in activity as polymerization catalysts for episulfide compounds due to steric hindrance of substituents.
  • the curable composition combining the polythiol oligomer and the episulfide compound is sufficiently stable (the polymerization of the episulfide compound is sufficiently slow), and can be stored for a long period of time.
  • a compound having a 2,2,6,6-tetramethylpiperidine skeleton is preferable.
  • the amount of the basic catalyst used is preferably in the range of 0.005 to 5 mol, more preferably in
  • the reaction between polythiol and sulfur may be performed in the presence of an episulfide compound (component C).
  • component C an episulfide compound
  • the episulfide compound may be polymerized to cause gelation. Therefore, when a basic catalyst is used, hindered amine is preferable for the reason described above.
  • the 2nd curable composition of this invention is comprised including the polythiol oligomer (A component) mentioned above, an episulfide compound (C component), and a photobase generator (D component).
  • An episulfide compound (component C) is a compound having one or more episulfide groups in one molecule.
  • the following general formula (8) wherein m is an integer from 0 to 6, n is an integer from 0 to 4, R 3 and R 4 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 5 , R 4 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 (8) include bis (2,3-epithiopropyl) sulfide.
  • the episulfide compound represented by the general formula (8) has a large shrinkage due to curing, the shrinkage accompanying the curing can be suppressed by copolymerizing with the polythiol oligomer.
  • the episulfide compound represented by the general formula (8) generally has a low viscosity, but is adjusted to a viscosity excellent in workability by mixing with the polythiol oligomer.
  • the viscosity of the curable composition assuming that it is used as an adhesive, if the viscosity is too low, the adhesive may sag or flow, or the substrate may be displaced during pasting. It is not preferable. 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 in the second curable composition cannot be unconditionally defined because it depends on the use form of the adhesive such as the coating method and the laminating method, but is preferably in the range of 100 to 50,000 mPa ⁇ s. More preferably, it is in the range of 500 to 10,000 mPa ⁇ s.
  • the content of the polythiol oligomer in the second curable composition is preferably in the range of 10 to 70 parts by weight, more preferably in the range of 20 to 50 parts by weight with respect to 100 parts by weight of the curable composition. If the content of the polythiol 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 D) 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 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.
  • 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 from 0.01 to 10 parts by weight, more preferably from 0.1 to 5 parts by weight, based on 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 indexes of the curable composition and the cured product (cured film) were measured using an Abbe refractometer NAR-3T (manufactured by Atago Co., Ltd.).
  • the transmittance of the cured product 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, 65 g of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane and 0.05 g of dicyclohexylmethylamine were taken and stirred well. 4.7 g of sulfur powder was slowly added dropwise in several portions at room temperature. When sulfur powder was added, the solution turned yellow and gas was generated. After the generation of gas became slow, the temperature was raised to 60 ° C. while flowing nitrogen gas through the liquid surface, and stirring was continued for 3 hours. As the reaction progressed, gas generation almost disappeared and the solution became colorless and transparent. The polythiol oligomer was produced by the above procedure. After cooling the polythiol oligomer to room temperature, 35 g of triallyl isocyanurate was added and stirred until uniform. The 1st curable composition was produced in the above procedure.
  • Examples 2-5 A first curable composition and a cured product were prepared in the same manner as in Example 1 except that the types and amounts of polythiol, sulfur, and polyene compound were changed to the contents shown in Table 1. The physical properties of the first curable composition and the cured product were as shown in Table 1.
  • Comparative Example 1 In a 300 ml flask, 55 g of 2,5-dimercaptomethyl-1,4-dithiane and 45 g of triallyl isocyanurate were taken 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 product were as shown in Table 2. In addition, the value which performance is inferior compared with an Example was underlined.
  • Comparative Examples 2-4 A curable composition and a cured product were prepared in the same manner as in Comparative Example 1 except that the types and amounts of the thiol compound and ethylenically unsaturated compound were changed to those shown in Table 2. The physical properties of the curable composition and the cured product were as shown in Table 2. In addition, the value which performance is inferior compared with an Example was underlined.
  • Example 6 In a 300 ml flask, 40 g of 2,5-dimercaptomethyl-1,4-dithiane and 0.05 g of tributylamine were taken and stirred well. 6.0 g of sulfur powder was slowly added dropwise in several portions at room temperature. When sulfur powder was added, the solution turned yellow and gas was generated. After the generation of gas became slow, the temperature was raised to 60 ° C. while flowing nitrogen gas through the liquid surface, and stirring was continued for 3 hours. As the reaction progressed, gas generation almost disappeared and the solution became colorless and transparent. The polythiol oligomer was produced by the above procedure.
  • 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 second curable composition and the cured film were as shown in Table 3.
  • Example 7 In a 300 ml flask, 40 g of 2,5-dimercaptomethyl-1,4-dithiane, 60 g of bis (2,3-epithiopropyl) sulfide, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate .1 g was taken and stirred well. 6.0 g of sulfur powder was slowly added dropwise in several portions at room temperature. When sulfur powder was added, the solution turned yellow and gas was generated. After the generation of gas became slow, the temperature was raised to 60 ° C. while flowing nitrogen gas through the liquid surface, and stirring was continued for 3 hours. As the reaction progressed, gas generation almost disappeared and the solution became colorless and transparent.
  • a cured product was prepared in the same manner as in Example 6.
  • the physical properties of the second curable composition and the cured film were as shown in Table 3.
  • Examples 8-14 The 2nd curable composition and hardened
  • Comparative Example 5 100 g of bis (2,3-epithiopropyl) sulfide, 0.2 g of photobase generator (component D) represented by the structural formula (9), 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 product was produced in the same manner as in Example 6.
  • the physical properties of the curable composition and the cured product were as shown in Table 5. In addition, physical properties that are inferior to those of the examples are underlined.

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

Abstract

L'invention porte sur une composition durcissable et similaire qui présente un indice de réfraction élevé et qui possède les propriétés requises d'un adhésif pour l'optique dans la mesure où elle est photodurcissable, elle présente un faible retrait, elle est incolore et transparente et elle présente une viscosité permettant de la travailler. La composition durcissable selon l'invention comprend un oligomère de polythiol obtenu par réaction d'un polythiol et de soufre (composant A) et un composé polyène (composant B) et une autre composition durcissable selon l'invention comprend un oligomère de polythiol obtenu par réaction d'un polythiol et de soufre (composant A), d'un composé épisulfure (composant C) et d'un générateur de photobase (composant D).
PCT/JP2012/060899 2011-04-28 2012-04-24 Composition durcissable et adhésif pour l'optique Ceased WO2012147708A1 (fr)

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JP2014047334A (ja) * 2012-09-04 2014-03-17 Mitsubishi Gas Chemical Co Inc 光学材料用重合性組成物の製造方法
JP2014047333A (ja) * 2012-09-04 2014-03-17 Mitsubishi Gas Chemical Co Inc 光学材料の製造方法
US9458293B2 (en) 2012-02-02 2016-10-04 Mitsubishi Gas Chemical Company, Inc. Method for producing composition for optical material
WO2020080391A1 (fr) * 2018-10-17 2020-04-23 ナミックス株式会社 Composition de résine
US11214650B2 (en) 2016-04-11 2022-01-04 Mitsubishi Gas Chemical Company, Inc. Composition for high refractive index low dispersion resins for composite diffractive optical elements, and composite diffractive optical element using the same
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