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WO2011102287A1 - Composition durcissable, et produit durci - Google Patents

Composition durcissable, et produit durci Download PDF

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Publication number
WO2011102287A1
WO2011102287A1 PCT/JP2011/052829 JP2011052829W WO2011102287A1 WO 2011102287 A1 WO2011102287 A1 WO 2011102287A1 JP 2011052829 W JP2011052829 W JP 2011052829W WO 2011102287 A1 WO2011102287 A1 WO 2011102287A1
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Prior art keywords
meth
ring
molecule
group
alicyclic
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English (en)
Japanese (ja)
Inventor
久保隆司
竹中啓起
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Daicel Corp
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Daicel Chemical Industries Ltd
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Publication of WO2011102287A1 publication Critical patent/WO2011102287A1/fr
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • the present invention relates to a curable composition, a cured product thereof, and an optical member. More specifically, a curable composition that can form a cured product that is excellent in optical properties and physical properties and does not deteriorate even at high temperatures, a cured resin that is obtained by curing the curable composition, and The present invention relates to an optical member such as a lens made of the cured resin.
  • Curable compositions are used as plastic materials in machine part materials, electrical / electronic parts materials, automotive parts materials, civil engineering and building materials, molding materials, paints, adhesives, sealing materials, etc. It is also attracting attention as a material for these optical members.
  • a plastic lens material mainly composed of a (meth) acrylic acid ester having a fluorene skeleton is known (Patent Document 1).
  • the (meth) acrylic acid ester having a fluorene skeleton has a high viscosity, the viscosity is lowered by adding a vinyl compound having an alkylene oxide group to the main chain or a monofunctional radically polymerizable monomer.
  • a vinyl compound having an alkylene oxide group to the main chain or a monofunctional radically polymerizable monomer.
  • Such a composition has a problem that the refractive index fluctuates or decreases.
  • cure shrinkage was large and the moisture absorption rate was also high.
  • Patent Document 2 discloses a (meth) acrylic acid ester having an aromatic ring and a cationically polymerizable compound in order to solve the problems of the cured composition mainly composed of (meth) acrylic acid ester having an aromatic ring as described above.
  • a curable composition using a combination thereof is proposed. According to this composition, improvement in the curing rate, improvement in workability by lowering the viscosity, suppression of curing shrinkage of the cured product, and maintenance of a high refractive index are achieved to some extent.
  • the plastic lens obtained from this composition is used as a low Abbe number lens having an Abbe number of 40 or less.
  • the plastic lens obtained by curing this composition cannot be said to have sufficient heat resistance, and the shape changes at a high temperature and the light transmittance is significantly reduced. Therefore, for example, camera-equipped mobile phones and the like are manufactured through a reflow soldering process (mounting process), but cannot withstand the process temperature (about 260 ° C.), and thus are manufactured separately after the soldering process. A process of connecting the camera module with a connector is required. Further, although there are high Abbe number resin materials having an Abbe number of 45 or more, few plastic materials with excellent heat resistance that can withstand the reflow method are known.
  • An object of the present invention is to provide a high Abbe number cured resin having an Abbe number of 45 or more (hereinafter referred to as an Abbe number) having high light transmittance and refractive index, and having characteristics that optical characteristics and physical characteristics are hardly changed even under high temperature conditions.
  • the present invention provides a curable composition capable of obtaining “a high Abbe number curable resin having an Abbe number of 45 or more” (sometimes simply referred to as a “high Abbe number curable resin”).
  • Another object of the present invention is to provide a high Abbe number cured resin having characteristics that optical characteristics and physical characteristics are hardly changed even under high temperature conditions such as reflow soldering, and an optical member made of the cured resin. There is to do.
  • an epoxy compound having a specific structure As a result of intensive studies to achieve the above object, the present inventors have found that an epoxy compound having a specific structure, a (meth) acrylic acid ester having a specific structure, and a (meth) acrylic acid ester having an epoxy group in the molecule.
  • the present invention has been completed by finding out that it can be obtained.
  • the present invention relates to an epoxy compound (A) having an alicyclic ring in the molecule, a (meth) acrylic acid ester (B) having an alicyclic ring in the molecule, and a (meth) acrylic acid having an epoxy group in the molecule.
  • a curable composition comprising an ester (C).
  • (meth) acrylic acid ester (C) having an epoxy group in the molecule for example, at least one selected from (meth) acrylic acid ester having alicyclic epoxy group and (meth) acrylic acid ester having glycidyl group Certain compounds can be used.
  • Examples of the epoxy compound (A) having an alicyclic ring in the molecule include an epoxy compound having an alicyclic epoxy group, an epoxy compound in which an epoxy group is directly bonded to the alicyclic ring by a single bond, and an alicyclic ring and a glycidyl ether group. It is possible to use at least one epoxy compound selected from epoxy compounds having:
  • the (meth) acrylic acid ester (B) having an alicyclic ring in the molecule is preferably a polyfunctional (meth) acrylic acid ester having an alicyclic ring in the molecule.
  • the present invention also provides a curable resin obtained by curing the curable composition.
  • the present invention further provides an optical member made of the cured resin.
  • the curable composition of the present invention by curing, it has high light transmittance and refractive index, and optical properties (light transmittance, refractive index, Abbe number, etc.)
  • a cured resin having a high Abbe number having a characteristic that physical characteristics hardly change can be obtained.
  • Such a cured resin is not easily yellowed even when subjected to a soldering process by a reflow method, and is not easily changed in shape, so that it can be used for an optical member such as a lens.
  • the camera module can be mounted at the same time in the reflow soldering process (mounting process), which is performed after the soldering process.
  • the connecting step of the camera module with the existing connector can be omitted.
  • the curable composition of the present invention comprises an epoxy compound (A) having an alicyclic ring (aliphatic carbocyclic ring) in the molecule, and a (meth) acrylic acid ester (B) having an alicyclic ring (aliphatic carbocyclic ring) in the molecule. ) And (meth) acrylic acid ester (C) having an epoxy group in the molecule.
  • a polymerizable compound having an epoxy group as a cationic polymerizable group and a (meth) acryloyloxy group as a radical polymerizable group in the molecule is added.
  • This polymerizable compound acts as a cross-linking agent between a cationic curable resin and a radical curable resin, and the heat resistance of the cured resin is remarkably improved.
  • Optical properties light transmittance, refractive index, Abbe number, etc.
  • physical properties even at high temperatures It is possible to obtain a cured resin that hardly changes.
  • Epoxy compound having alicyclic ring in molecule (A) is not particularly limited as long as it is a compound having an alicyclic ring and an epoxy group in the molecule (however, (meth) acrylic acid ester having an epoxy group in the molecule is except).
  • the epoxy compound (A) having an alicyclic ring in the molecule preferably does not have an aromatic ring.
  • the epoxy compound (A) having an alicyclic ring in the molecule can be used alone or in combination of two or more.
  • the epoxy compound (A) having an alicyclic ring in the molecule is preferably a polyfunctional epoxy compound having two or more epoxy groups in the molecule.
  • epoxy compound (A) having an alicyclic ring in the molecule (i) an alicyclic group having an epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring.
  • examples thereof include an epoxy compound, (ii) an epoxy compound in which an epoxy group is directly bonded to the alicyclic ring with a single bond, and (iii) a glycidyl ether type epoxy compound having an alicyclic ring and a glycidyl ether group.
  • alicyclic ring examples include monocyclic alicyclic rings such as cyclopentane ring, cyclohexane ring, cyclooctane ring and cyclododecane ring (3 to 15-membered, preferably about 5 to 6-membered cycloalkane ring); Hydronaphthalene ring), perhydroindene ring (bicyclo [4.3.0] nonane ring), perhydroanthracene ring, perhydrofluorene ring, perhydrophenanthrene ring, perhydroacenaphthene ring, perhydrophenalene ring, norbornane Ring (bicyclo [2.2.1] heptane ring), isobornane ring, adamantane ring, bicyclo [3.3.0] octane ring, tricyclo [5.2.1.0 2,6 ] decane ring, tricyclo [6 .2.1.0 2,7
  • Examples of the alicyclic epoxy group include an epoxycyclopentyl group, a 3,4-epoxycyclohexyl group, and a 3,4-epoxytricyclo [5.2.1.0 2,6 ] decane 8- (or 9).
  • Yl group epoxidized dicyclopentadienyl group and the like.
  • alicyclic epoxy compound (i) having the alicyclic epoxy group a compound represented by the following formula (A-1) (two alicyclic epoxy groups are bonded by a single bond or via a linking group). Compound).
  • Y 1 represents a single bond or a linking group.
  • the linking group include a divalent hydrocarbon group, a carbonyl group (—CO—), an ether bond (—O—), an ester bond (—COO—), an amide bond (—CONH—), a carbonate bond (— OCOO-) and a group in which a plurality of these are bonded.
  • divalent hydrocarbon group examples include linear or branched alkylene groups such as methylene, ethylidene, isopropylidene, ethylene, propylene, trimethylene, and tetramethylene groups (for example, C 1-6 alkylene groups); Divalent groups such as 2-cyclopentylene, 1,3-cyclopentylene, cyclopentylidene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, and cyclohexylidene groups And alicyclic hydrocarbon groups (particularly divalent cycloalkylene groups); groups in which a plurality of these are bonded.
  • alkylene groups such as methylene, ethylidene, isopropylidene, ethylene, propylene, trimethylene, and tetramethylene groups (for example, C 1-6 alkylene groups)
  • Divalent groups such as 2-cyclopentylene, 1,3-cyclopentylene, cycl
  • n is an integer from 1 to 30.
  • alicyclic epoxy compound there are two adjacent carbon atoms and oxygen having an alicyclic ring and two or more epoxy groups in the molecule, and only one of the two or more epoxy groups forms the alicyclic ring.
  • the compound which is an epoxy group (alicyclic epoxy group) comprised with an atom is mentioned. This representative compound (limonene diepoxide) is shown below.
  • an alicyclic epoxy compound the alicyclic epoxy compound which has the following 3 or more alicyclic epoxy groups, and an alicyclic which has only one alicyclic epoxy group and does not have an epoxy group in others
  • a formula epoxy compound can also be used.
  • a, b, c, d, e, and f are integers from 0 to 30.
  • Examples of the epoxy compound (ii) in which an epoxy group is directly bonded to the alicyclic ring with a single bond include a compound represented by the following formula (A-2).
  • R 1 is a group obtained by dividing q OH from a q-valent alcohol [R 1- (OH) q ], p is an integer of 1 to 30, and q is an integer of 1 to 10. In the groups in q parentheses, p may be the same or different.
  • q-valent alcohol As the q-valent alcohol [R 1- (OH) q ], monovalent alcohols such as methanol, ethanol, 1-propanol, isopropyl alcohol, 1-butanol; ethylene glycol, 1,2-propanediol, 1,3 -Divalent alcohols such as propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polypropylene glycol; glycerin, diglycerin, Examples include trihydric or higher alcohols such as erythritol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, and sorbitol.
  • monovalent alcohols such as methanol, ethanol, 1-propanol, isopropyl alcohol, 1-butan
  • the alcohol may be polyether polyol, polyester polyol, polycarbonate polyol, polyolefin polyol, or the like.
  • the alcohol is preferably an aliphatic alcohol having 1 to 10 carbon atoms (particularly an aliphatic polyhydric alcohol such as trimethylolpropane).
  • Examples of the glycidyl ether type epoxy compound (iii) having an alicyclic ring and a glycidyl ether group include glycidyl ethers of alicyclic alcohols (particularly alicyclic polyhydric alcohols).
  • This compound is an epoxy compound having an aromatic ring and an epoxy group in its molecule (for example, an epibis type glycidyl ether type obtained by a condensation reaction of bisphenols such as bisphenol A, bisphenol F, bisphenol S, and fluorene bisphenol with an epihalohydrin.
  • a compound in which an aromatic ring of an epoxy resin or the like is nuclear hydrogenated may be used.
  • Examples of the glycidyl ether type epoxy compound (iii) having an alicyclic ring and a glycidyl ether group include the following compounds.
  • the proportion of the epoxy compound (A) having an alicyclic ring in the molecule in the curable composition of the present invention varies depending on the use of the curable resin, etc., but with respect to the entire curable composition (or the total amount of the curable compound). For example, it is about 10 to 70% by weight, preferably about 20 to 60% by weight, and more preferably about 30 to 50% by weight. If the amount of the epoxy compound (A) having an alicyclic ring in the molecule is too small, curing shrinkage, which is a problem in terms of moldability, is increased, and problems such as increased hygroscopicity and reduced moisture resistance are likely to occur. .
  • the (meth) acrylic acid ester (B) having an alicyclic ring in the molecule is not particularly limited as long as it is a compound having an alicyclic ring and a (meth) acryloyloxy group in the molecule (provided that an epoxy group is present in the molecule). (Excluding (meth) acrylic acid ester).
  • the (meth) acrylic acid ester (B) having an alicyclic ring in the molecule preferably has no aromatic ring.
  • the (meth) acrylic acid ester (B) having an alicyclic ring in the molecule can be used alone or in combination of two or more.
  • the (meth) acrylic acid ester (B) having an alicyclic ring in the molecule is preferably a polyfunctional (meth) acrylic acid ester having two or more (meth) acryloyloxy groups in the molecule.
  • the (meth) acrylic acid ester (B) having an alicyclic ring in the molecule is more preferably an acrylic acid ester having an alicyclic ring in the molecule.
  • the former is slower.
  • radical polymerization is generally faster. In a system in which radical polymerization and cationic polymerization proceed in parallel as in the present invention, it is preferable that radical polymerization and cationic polymerization proceed as evenly as possible from the viewpoint of physical properties of the cured resin.
  • alicyclic ring examples include monocyclic alicyclic rings such as cyclopentane ring, cyclohexane ring, cyclooctane ring, and cyclododecane ring (3 to 15-membered, preferably about 5 to 6-membered cycloalkane ring); decalin ring ( Perhydronaphthalene ring), perhydroindene ring (bicyclo [4.3.0] nonane ring), perhydroanthracene ring, perhydrofluorene ring, perhydrophenanthrene ring, perhydroacenaphthene ring, perhydrophenalene ring, Norbornane ring (bicyclo [2.2.1] heptane ring), isobornane ring, adamantane ring, bicyclo [3.3.0] octane ring, tricyclo [5.2.1.0 2,6 ] decane ring, tricyclo
  • the alicyclic ring and the (meth) acryloyloxy group may be directly bonded or may be bonded via a linking group.
  • the linking group include a divalent hydrocarbon group, a carbonyl group (—CO—), an ether bond (—O—), an ester bond (—COO—), an amide bond (—CONH—), a carbonate bond (— OCOO-) and a group in which a plurality of these are bonded.
  • divalent hydrocarbon group examples include linear or branched alkylene groups such as methylene, ethylidene, isopropylidene, ethylene, propylene, trimethylene and tetramethylene groups (for example, C 1-10 alkylene groups, preferably C 1-6 alkylene group); 1,2-cyclopentylene, 1,3-cyclopentylene, cyclopentylidene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene And a divalent alicyclic hydrocarbon group (particularly a divalent cycloalkylene group) such as a cyclohexylidene group; and a group in which a plurality of these are bonded.
  • alkylene groups such as methylene, ethylidene, isopropylidene, ethylene, propylene, trimethylene and tetramethylene groups (for example, C 1-10 alkylene groups, preferably C 1-6 alkylene group
  • Examples of the (meth) acrylic acid ester (B) having an alicyclic ring in the molecule include a compound represented by the following formula (B-1).
  • ring Z 1 represents an alicyclic ring
  • Y 2 and Y 3 are the same or different and represent a single bond or a linking group.
  • Examples of the alicyclic ring in ring Z 1 include the alicyclic rings exemplified above.
  • the ring Z 1 is preferably a polycyclic alicyclic ring (bridged carbocyclic ring) such as a tricyclo [5.2.1.0 2,6 ] decane ring.
  • linking group for Y 2 and Y 3 examples include those exemplified above.
  • a divalent hydrocarbon group (particularly an alkylene group), or one or two or more divalent hydrocarbon groups (particularly an alkylene group) and one or two or more A group to which an oxygen atom (—O—) is bonded is preferable.
  • Representative examples of the compound represented by the formula (B-1) include 1,4-cyclohexanediol di (meth) acrylate, 1,4-cyclohexanedimethanol di (meth) acrylate, bicyclo [2.2.1 ] Heptane dimethanol di (meth) acrylate, 1,3-adamantanediol di (meth) acrylate, 1,3-adamantane dimethanol di (meth) acrylate, tricyclo [5.2.1.0 2,6 ] decandi Examples include methanol di (meth) acrylate.
  • Functional (meth) acrylic acid esters can also be used.
  • the ratio of the (meth) acrylic acid ester (B) having an alicyclic ring in the molecule in the curable composition of the present invention varies depending on the use of the curable resin, but the entire curable composition (or of the curable compound).
  • the total amount is, for example, about 10 to 70% by weight, preferably about 20 to 60% by weight, and more preferably about 30 to 50% by weight. If the amount of the (meth) acrylic acid ester (B) having an alicyclic ring in the molecule is too small, the amount of change in optical properties at high temperatures such as reflow conditions described later increases, resulting in problems in terms of heat resistance. Cheap.
  • the (meth) acrylic acid ester (C) having an epoxy group in the molecule is not particularly limited as long as it is a compound having an epoxy group and a (meth) acryloyloxy group in the molecule.
  • the (meth) acrylic acid ester (C) having an epoxy group in the molecule can be used alone or in combination of two or more.
  • the (meth) acrylic acid ester (C) having an epoxy group in the molecule has the same reason (radical polymerization and cationic polymerization as in the case of the (meth) acrylic acid ester (B) having an alicyclic ring in the molecule.
  • An acrylic ester having an epoxy group in the molecule is more preferable for the reason that it proceeds as uniformly as possible.
  • Examples of (meth) acrylic acid ester (C) having an epoxy group in the molecule include (i) (meth) acrylic acid ester having alicyclic epoxy group, (ii) (meth) acrylic acid ester having glycidyl group, etc. Is mentioned.
  • the alicyclic epoxy group is not particularly limited as long as it is an epoxy group composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring.
  • alicyclic ring examples include monocyclic alicyclic rings such as cyclopentane ring, cyclohexane ring, cyclooctane ring and cyclododecane ring (3 to 15 member, preferably about 5 to 6 membered cycloalkane ring); decalin ring (Perhydronaphthalene ring), perhydroindene ring (bicyclo [4.3.0] nonane ring), perhydroanthracene ring, perhydrofluorene ring, perhydrophenanthrene ring, perhydroacenaphthene ring, perhydrophenalene ring , Norbornane ring (bicyclo [2.2.1] heptane ring), isobornane ring, adamantane ring, bicyclo [3.3.0] octane ring, tricyclo [5.2.1.0 2,6 ] decane ring, tricyclo [6.2
  • Examples of the alicyclic epoxy group include an epoxycyclopentyl group, a 3,4-epoxycyclohexyl group, and a 3,4-epoxytricyclo [5.2.1.0 2,6 ] decane represented by the following formula (a).
  • An 8- (or 9) yl group and the like can be mentioned.
  • the alicyclic epoxy group includes a bridged carbocyclic ring such as a 3,4-epoxytricyclo [5.2.1.0 2,6 ] decane 8- (or 9) yl group represented by the formula (a).
  • an alicyclic epoxy group composed of an epoxy group composed of two adjacent carbon atoms and an oxygen atom constituting the bridged carbon ring is a bridged carbocyclic ring.
  • Examples of the (meth) acrylic acid ester (i) having the alicyclic epoxy group include compounds represented by the following formula (C-1).
  • Examples of the (meth) acrylic acid ester (ii) having a glycidyl group include a compound represented by the following formula (C-2).
  • R 3 represents a hydrogen atom or a methyl group
  • Y 4 represents a single bond, an alkylene group having 1 to 10 carbon atoms, or an alkylene group having 1 or 2 or more carbon atoms and 1 or 2 or more.
  • an oxygen atom (—O—) bonded to each other and ring Z 2 represents an alicyclic epoxy group.
  • alkylene group having 1 to 10 carbon atoms in Y 4 include linear or branched alkylene groups such as methylene, ethylene, propylene, trimethylene, tetramethylene, and hexamethylene groups.
  • Y 4 in particular, a single bond, an alkylene group having 1 to 6 carbon atoms, an alkyleneoxy group having 1 to 6 carbon atoms (the oxygen atom is at the right end), and a plurality of alkyleneoxy groups having 1 to 6 carbon atoms (for example, It is preferably a bonded polyalkyleneoxy group (terminal oxygen atom is at the right end).
  • R 3 and Y 4 are the same as described above.
  • (meth) acrylic acid ester (ii) having a glycidyl group examples include glycidyl (meth) acrylate.
  • the ratio of the (meth) acrylic acid ester (C) having an epoxy group in the molecule in the curable composition of the present invention is, for example, 1 to 1 with respect to the entire curable composition (or the total amount of the curable compound). It is about 50% by weight, preferably about 5 to 40% by weight, and more preferably about 10 to 30% by weight.
  • the amount of the (meth) acrylic acid ester (C) having an epoxy group in the molecule is within the above range, the above (C) is maintained while maintaining the merits of the respective cured resins of the cationic cured resin and the radical cured resin.
  • the heat resistance of the cured resin can be further improved by the action of the component as a crosslinking agent.
  • the curable composition of the present invention is a curable compound (cationic polymerizable compound, radical) other than the components (A), (B), and (C) as long as the optical properties and physical properties of the cured resin are not impaired.
  • a polymerizable compound, etc. contains a cationic polymerization initiator, a curing agent, a curing accelerator, a radical polymerization initiator, a photosensitizer, and various additives depending on the type of the curable compound to be used. You may go out.
  • the ratio of the total amount of the components (A), (B) and (C) to the total amount of the curable compound in the curable composition of the present invention is, for example, 60% by weight or more, preferably 80% by weight or more, more preferably 90% by weight or more.
  • the ratio of the total amount of the components (A), (B) and (C) to the total amount of the curable composition of the present invention is, for example, 60% by weight or more, preferably 80% by weight or more, more preferably 90% by weight or more. It is.
  • the cationic polymerization initiator is an initiator (curing catalyst; acid generator) that releases a substance that initiates cationic polymerization by heating or light.
  • a thermal cationic polymerization initiator is preferable.
  • the amount of the cationic polymerization initiator is, for example, 0 to 15% by weight, preferably 0.01 to 10% by weight, based on the entire curable composition. By mix
  • cationic polymerization initiator examples include aryldiazonium salts [for example, PP-33, manufactured by Asahi Denka Kogyo Co., Ltd.], aryliodonium salts, arylsulfonium salts [for example, FC-509, manufactured by 3M Corporation], UVE1014 [G. E. CP-66, CP-77 [Asahi Denka Kogyo Co., Ltd.], SI-60L, SI-80L, SI-100L, SI-110L [Sanshin Chemical Industry Co., Ltd.], Allen -Ion complexes [for example, CG-24-61 manufactured by Ciba Geigy Co., Ltd.].
  • aryldiazonium salts for example, PP-33, manufactured by Asahi Denka Kogyo Co., Ltd.
  • aryliodonium salts for example, FC-509, manufactured by 3M Corporation
  • UVE1014 G. E. CP-66,
  • a system of a chelate compound of a metal such as aluminum or titanium and an acetoacetate ester or diketone and a silanol or phenol is also used.
  • the chelate compound include aluminum trisacetylacetonate and aluminum trisacetoacetate ethyl.
  • silanols or phenols include triphenylsilanol and bisphenol S.
  • An acid anhydride can be used as a curing agent.
  • the acid anhydride those generally used for curing epoxy compounds can be used, but those which are liquid at room temperature are preferred, and specifically, for example, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride , Dodecenyl succinic anhydride, methylendomethylenetetrahydrophthalic anhydride, and the like.
  • acid anhydrides that are solid at room temperature such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylcyclohexene dicarboxylic acid anhydride, as long as the impregnation property of the curable composition of the present invention is not adversely affected. Etc. can be used.
  • an acid anhydride that is solid at room temperature it is preferably dissolved in a liquid acid anhydride at room temperature and used as a liquid mixture at room temperature.
  • the blending amount of the curing agent varies depending on the kind and amount of the cationic curable compound in the curable composition, but is, for example, 0 to 60% by weight, preferably 5 to 40% by weight based on the entire curable composition. Degree.
  • the curing accelerator is a compound having a function of accelerating the curing reaction when an acid anhydride is used as the curing agent.
  • the curing accelerator is not particularly limited as long as it is generally used.
  • a diazabicycloundecene-based curing accelerator (1,8-diazabicyclo [5.4.0] undecene-7 (DBU) or Salt thereof)
  • tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, etc.
  • Examples thereof include organic phosphine compounds such as imidazoles and triphenylphosphine, tertiary amine salts, quaternary ammonium salts, phosphonium salts, metal salts such as tin octylate and zinc octylate.
  • diazabicycloundecene curing accelerators are preferable.
  • the blending amount of the curing accelerator is, for example, about 0 to 5% by weight, preferably about 0.05 to 3% by weight, based on the entire curable composition. If the blending amount is too small, the curing accelerating effect may be insufficient, and if it is too large, the hue in the cured product may be deteriorated.
  • radical polymerization initiator those known and commonly used as light or thermal radical polymerization initiators can be used.
  • Representative photoradical polymerization initiators include, for example, benzoin / benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2, 2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino- Acetophenones such as 1- (4-morpholinophenyl) -butan-1-one; 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, 1-chloroanth
  • thermal radical polymerization initiators include, for example, diacyl peroxides, peroxydicarbonates, alkyl peroxides, dialkyl peroxides, perketals, ketone peroxides, and organic peroxides in the form of alkyl hydroperoxides. Can be mentioned. Specific examples of these thermal polymerization initiators include dibenzoyl peroxide, t-butyl perbenzoate, azobisisobutyronitrile, and the like.
  • radical polymerization initiators include, for example, Irgacure (registered trademark) 184 (1-hydroxycyclohexyl phenyl ketone) and Irgacure (registered trademark) 500 (1-hydroxycyclohexyl) available from Ciba as photo radical polymerization initiators. Phenylketone, benzophenone), and other photopolymerization initiators of the Irgacure® type; Darocur® 1173, 1116, 1398, 1174, and 1020 (available from Merck).
  • the blending amount of the radical polymerization initiator varies depending on the kind and amount of the radical polymerizable compound in the curable composition, but is, for example, about 0.1 to 20% by weight with respect to the entire curable composition.
  • the photosensitizer is preferably used in combination with a photopolymerization initiator.
  • a photopolymerization initiator As the photosensitizer, those known and commonly used as photosensitizers can be used. For example, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylamino is used. Tertiary amines such as benzoate, triethylamine, triethanolamine and the like can be mentioned. These photosensitizers can be used alone or in combination of two or more. The content of the photosensitizer is not particularly limited, but is, for example, about 0.1 to 5% by weight with respect to the entire curable composition.
  • the compounding quantity of these various additives is 5 weight% or less with respect to the whole curable composition, for example.
  • the curable composition of the present invention may contain a solvent, but if it is too much, bubbles may be formed in the cured resin. Therefore, it is preferably 10% by weight or less, particularly 1% by weight based on the entire curable composition. It is as follows.
  • the curable composition of the present invention includes, for example, the above components (A), (B) and (C), a cationic polymerization initiator, a curing agent, a curing accelerator, a radical polymerization initiator, a photosensitizer, which are added as necessary. It is prepared by blending a sensitizer and various additives, and stirring and mixing while excluding bubbles as necessary under vacuum.
  • the temperature at the time of stirring and mixing is, for example, about 10 to 60 ° C.
  • a known apparatus such as a rotation / revolution mixer, a single-screw or multi-screw extruder, a planetary mixer, a kneader, or a dissolver can be used.
  • the curable composition of the present invention it is possible to obtain a cured resin excellent in both optical characteristics and physical characteristics.
  • the obtained cured resin has a light transmittance (400 nm) of, for example, 80% or more (preferably 85% or more), an internal transmittance (400 nm) of, for example, 85% or more (preferably 90% or more), and a refractive index (589 nm).
  • the water absorption is, for example, 2% by weight or less (preferably 1% by weight or less), the glass transition point is, for example, 100 ° C.
  • the linear expansion coefficient is, for example, 120 ppm / K or less (preferably , 100 ppm / K or less), and the curing shrinkage rate is, for example, 10% or less (preferably 8% or less), and can be a cured resin excellent in terms of moldability and moisture resistance. Further, even when the cured resin is subjected to high temperature conditions (for example, about 260 ° C.), the light transmittance, the refractive index, and the Abbe number hardly change and the shape does not change.
  • the cationic curable composition of the present invention provides a cured resin that hardly changes in optical properties and physical properties even at high temperatures due to curing. Therefore, in particular, optical applications (optical material applications), optical device applications, display device applications, electrical -It can be suitably used for electronic component material applications.
  • the refractive index of the lens varies depending on the wavelength of light, and a phenomenon (chromatic aberration) that causes deviation (bleeding or blurring) in the image occurs.
  • a normal lens has a structure that corrects chromatic aberration by combining a lens resin having a high Abbe number and a lens resin having a low Abbe number.
  • the glass of a lens used in a camera is classified into two types according to the Abbe number. Generally, those having an Abbe number of 50 or less are called flint glass, and those having 50 or more are called crown glass.
  • the cured resin obtained from the curable composition of the present invention can be suitably used as a lens resin having a high Abbe number.
  • the cured product of the present invention can be obtained by curing the curable composition.
  • a curing method an appropriate method can be selected from known curing methods according to the type of the curable compound in the curable composition.
  • the curable composition can be placed in a mold matched to the shape of the cured product, cured by irradiation with active energy rays (for example, ultraviolet rays), and further heated to obtain the desired cured product.
  • active energy rays for example, ultraviolet rays
  • cured material can also be obtained only by heating.
  • the irradiation amount is, for example, about 1000 to 4000 mJ / cm 2 .
  • the heating temperature varies depending on the type of the curable compound, but is, for example, about 80 to 200 ° C., preferably about 110 to 160 ° C.
  • the cured product of the present invention is preferably used as an optical member because its optical characteristics and physical characteristics are hardly changed even at a high temperature of about 260 ° C., for example.
  • the optical member include an imaging lens, a spectacle lens, a filter, a diffraction grating, a prism, a light guide, and a light beam collection for a camera (on-vehicle camera, digital camera, PC camera, mobile phone camera, surveillance camera, etc.).
  • Optical lens, light diffusion lens, cover glass for display device photo sensor, photo switch, LED, light emitting element, optical waveguide, optical splitter, optical fiber adhesive, display element substrate, color filter substrate, touch panel substrate, Examples include a display protective film, a display backlight, a light guide plate, and an antireflection film.
  • the cast optical material composition is irradiated with ultraviolet rays (irradiation amount: 2,600 mJ / cm 2 ) to produce a cured resin, and the produced cured product is heated at 160 ° C. for 1 hour in an air atmosphere.
  • a plate-shaped transparent and uniform cured resin having a thickness of 0.5 mm was obtained. This cured resin could be easily released from the glass mold. The obtained cured resin was subjected to the evaluation described later.
  • Example 2 A cured resin was obtained in the same manner as in Example 1 except that glycidyl methacrylate was used as the (meth) acrylic acid ester having an epoxy group.
  • Internal transmittance The internal transmittance of the cured resin was calculated by the following equation.
  • the light transmittance at 400 nm was measured using a spectrophotometer (trade name “U-3900” manufactured by Hitachi High-Technologies Corporation), and the refractive index was the value of the refractive index at 400 nm measured by the following method (3). Was used.
  • Refractive index The refractive index of the cured resin was measured by a method based on JIS K7142, using a refractometer (trade name “Model 2010”, manufactured by Metricon Co., Ltd.) at 589 nm at 25 ° C.
  • the elastic modulus of the cured resin was measured using a solid viscoelasticity measuring device (trade name “RSAIII”, manufactured by TA Instruments Inc.) with a temperature rising rate of 5 ° C./min and a measurement temperature range of ⁇ 30.
  • the dynamic viscoelastic properties were measured at 270 ° C to 270 ° C, and the elastic modulus at 25 ° C was read.
  • the glass transition temperature of the curable resin is determined by using a differential scanning calorimeter (trade name “Q2000”, manufactured by T.A. Instruments Co., Ltd.) and pretreatment (at a heating rate of 20 ° C./min). After heating from -50 ° C to 250 ° C and cooling rate of 20 ° C / min, cooling from 250 ° C to -50 ° C), measured at a temperature rise rate of 20 ° C / min and measurement temperature range of -50 ° C to 250 ° C did.
  • a differential scanning calorimeter trade name “Q2000”, manufactured by T.A. Instruments Co., Ltd.
  • Abbe number (n d ⁇ 1) / (n F ⁇ n C )
  • n d represents a refractive index at 589.2 nm
  • n F represents a refractive index at 486.1 nm
  • n C represents a refractive index at 656.3 nm.
  • refractive index the value of the refractive index in each wavelength measured by the method of said (3) was used.
  • Example 1, 2 using the epoxy compound which has an alicyclic ring, the (meth) acrylic acid ester which has an alicyclic ring, and the (meth) acrylate compound which has an epoxy group, it has an epoxy group
  • a cured resin having an extremely high glass transition temperature is obtained, and the heat resistance is high, such as maintaining a relatively high light transmittance even after a heat resistance test.
  • a cured resin can be obtained.
  • the cured resin obtained from the curable composition using the epoxy compound having an alicyclic ring, the (meth) acrylic acid ester having an alicyclic ring, and the (meth) acrylate compound having an epoxy group is heat resistant. Since it is high and has high transparency, it can be suitably used for various applications such as optical applications such as lens units and optical device applications.
  • the curable composition of the present invention by curing, it has high light transmittance and refractive index, and optical properties (light transmittance, refractive index, Abbe number, etc.) and physical properties change even under high temperature conditions. Since it is possible to obtain a cured resin having a high Abbe number having the property of being difficult, it is particularly suitable for various uses such as an optical member application such as a lens and an optical device application.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)

Abstract

L'invention concerne une composition durcissable permettant d'obtenir une résine durcie dont le nombre d'Abbe est élevé, et qui tout en possédant une transmittance et un indice de réfraction élevés, possède une caractéristique selon laquelle ses propriétés optiques et physiques sont peu susceptibles de varier, y compris dans des conditions de températures élevées. La composition durcissable de l'invention est caractéristique en ce qu'elle contient : un composé époxy (A) qui possède un cycle aliphatique dans chaque molécule, un ester d'acide (méth)acrylique (B) qui possède un cycle aliphatique dans chaque molécule, et un ester d'acide (méth)acrylique (C) qui possède un groupe époxy dans chaque molécule. Il est possible d'utiliser en tant qu'ester d'acide (méth)acrylique (C) qui possède un groupe époxy dans chaque molécule, au moins un composé choisi parmi un ester d'acide (méth)acrylique qui possède un groupe époxy alicyclique, et un ester d'acide (méth)acrylique qui possède un groupe glycidyle.
PCT/JP2011/052829 2010-02-16 2011-02-10 Composition durcissable, et produit durci Ceased WO2011102287A1 (fr)

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JP2016194566A (ja) * 2015-03-31 2016-11-17 富士フイルム株式会社 低透湿性ハードコートフィルム、偏光板、及び画像表示装置
WO2019167905A1 (fr) * 2018-02-27 2019-09-06 味の素株式会社 Composition de résine pour la fermeture hermétique

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JPH0873559A (ja) * 1994-09-02 1996-03-19 Yokohama Rubber Co Ltd:The 光硬化型樹脂組成物
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JP2008013721A (ja) * 2006-07-10 2008-01-24 Kyocera Chemical Corp 硬化性樹脂組成物、表示素子用接着剤及び接着方法
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JPH0275621A (ja) * 1988-09-13 1990-03-15 Asahi Denka Kogyo Kk 樹脂の光学的造形方法
JPH04261489A (ja) * 1989-04-19 1992-09-17 Natl Starch & Chem Corp 接着剤／シーラント組成物およびこれを適用する方法
JPH0321629A (ja) * 1989-06-19 1991-01-30 Toagosei Chem Ind Co Ltd 光硬化性樹脂組成物
JPH04236212A (ja) * 1991-01-17 1992-08-25 Nippon Kayaku Co Ltd カラ−フィルター保護膜用樹脂組成物及びその硬化物
JPH0873559A (ja) * 1994-09-02 1996-03-19 Yokohama Rubber Co Ltd:The 光硬化型樹脂組成物
JPH08277321A (ja) * 1995-04-05 1996-10-22 Daicel Chem Ind Ltd 光硬化性樹脂組成物
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JP2008013721A (ja) * 2006-07-10 2008-01-24 Kyocera Chemical Corp 硬化性樹脂組成物、表示素子用接着剤及び接着方法
JP2009244860A (ja) * 2008-03-10 2009-10-22 Sumitomo Chemical Co Ltd 偏光板、光学部材および液晶表示装置

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016194566A (ja) * 2015-03-31 2016-11-17 富士フイルム株式会社 低透湿性ハードコートフィルム、偏光板、及び画像表示装置
WO2019167905A1 (fr) * 2018-02-27 2019-09-06 味の素株式会社 Composition de résine pour la fermeture hermétique
KR20200128067A (ko) * 2018-02-27 2020-11-11 아지노모토 가부시키가이샤 밀봉용 수지 조성물
JPWO2019167905A1 (ja) * 2018-02-27 2021-02-04 味の素株式会社 封止用樹脂組成物
JP7276312B2 (ja) 2018-02-27 2023-05-18 味の素株式会社 封止用樹脂組成物
KR102722508B1 (ko) 2018-02-27 2024-10-29 아지노모토 가부시키가이샤 밀봉용 수지 조성물

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