Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/37—Thiols

Definitions

• the present invention relates to 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 adhesiveness, curability, mechanical strength, durability, and optical properties are basic performances, but in recent years, the refractive index has become an important performance as the functionality of optical elements increases. 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.
• 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 obtained by combining an ethylenically unsaturated compound such as a (meth) acrylate compound and a thiol compound has a small shrinkage due to curing.
• Patent Document 1 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 2 describes an ene-thiol composition composed of MPSMA, a vinyl monomer, and a polythiol compound. According to the example, the refractive index of the cured product is 1.649 at the maximum.
• MPSMA is easily yellow-colored and has a limit in the amount of dissolution in the composition because it is solid.
• Patent Document 3 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.
• 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 that aims at further increasing the refractive index and also has performance as an optical adhesive such as low shrinkage, photocurability, colorless transparency, and viscosity suitable for work. To provide things.
• the present inventors have found an ene / thiol composition in which a poly (meth) acrylate compound having a fluorene ring and a polythiol compound having an aromatic ring or a thioalkyl structure are combined.
• the present inventors have found that it is possible to further increase the refractive index and have the necessary performance as an optical adhesive.
• the present invention It is a curable composition containing a poly (meth) acrylate compound having a fluorene ring (component A), a polythiol compound having an aromatic ring or a thioalkyl structure (component B), and a photopolymerization initiator (component C).
• a poly (meth) acrylate compound having a fluorene ring component A
• a polythiol compound having an aromatic ring or a thioalkyl structure component B
• a photopolymerization initiator component C
• acrylate compounds and methacrylate compounds are collectively referred to as (meth) acrylate compounds. Therefore, the (meth) acryloyl group includes both an acryloyl group and a methacryloyl group.
• a curable composition having a higher refractive index than conventional ones and also having the necessary performance as an optical adhesive such as low shrinkage, photocurability, colorless transparency, and viscosity suitable for work. Things can be provided.
• the curable composition of the present invention contains a poly (meth) acrylate compound having a fluorene ring (A component), a polythiol compound having an aromatic ring or a thioalkyl structure (B component), and a photopolymerization initiator (C component). To do. Furthermore, it is preferable to contain an ethylenically unsaturated compound (component D) having a di (thiophenyl) sulfide structure or a di (thiophenyl) sulfone structure. Moreover, it is preferable to contain ethylenically unsaturated compounds (E component) other than A component and D component as a diluting monomer.
• the poly (meth) acrylate compound (component A) having a fluorene ring is a compound having a fluorene ring and having two or more (meth) acryloyl groups in one molecule.
• the fluorene ring has the effect of increasing the refractive index. Moreover, the shrinkage accompanying hardening is small due to the bulky structure of the fluorene ring.
• the following general formula (2) (In the formula, 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.)
• the compound represented by these is preferable.
• Examples of the compound represented by the general formula (2) include 9,9-bis (4- (2-acryloxyethoxy) phenyl) fluorene.
• ⁇ A component may be used alone or in combination of two or more.
• the content of component A is not particularly limited, but is preferably in the range of 10 to 90 parts by weight, more preferably 30 to 70 parts by weight, and particularly preferably in the range of 40 to 70 parts by weight with respect to 100 parts by weight of the curable composition. preferable.
• the polythiol compound (component B) having an aromatic ring or thioalkyl structure used in the present invention the following general formula (1) -a (In the formula, p represents an integer of 0 to 3, and R 1 represents an alkylene group having 1 to 3 carbon atoms.)
• the compound represented by these is preferable. Since the compound contains sulfur atoms and benzene rings in the molecule at a high concentration, the effect of increasing the refractive index is great. Moreover, although the aromatic ring contained in A component and D component is easily oxidized and yellowed by light or heat, the thiol group has an antioxidant effect, so that a cured product having excellent colorless transparency can be obtained.
• the component A is a solid or high-viscosity liquid at room temperature, but is adjusted to a viscosity suitable for work by the dilution effect of the component B. Moreover, since addition polymerization with the ethylenically unsaturated bond of a thiol group has little shrinkage
• Examples of the compound represented by the general formula (1) -a include xylylene dithiol.
• the polythiol compound (component B) having an aromatic ring or thioalkyl structure used in the present invention includes the following general formula (1) -b (In the formula, q represents an integer of 0 to 3, and R 2 represents a simple bond or an alkylene group having 1 to 3 carbon atoms.) Also preferred are compounds represented by: Since the compound contains many thioalkyl structures containing a sulfur atom in the molecule, the effect of increasing the refractive index is great. Moreover, although the aromatic ring contained in A component and D component is easily oxidized and yellowed by light or heat, the thiol group has an antioxidant effect, so that a cured product having excellent colorless transparency can be obtained.
• the component A is a solid or high-viscosity liquid at room temperature, but is adjusted to a viscosity suitable for work by the dilution effect of the component B. Moreover, since the addition polymerization with the ethylenically unsaturated bond of a thiol group has small shrinkage
• Examples of the compound represented by the general formula (1) -b include 2,5-bis (dimercaptomethyl) -1,4-dithiane.
• the polythiol compound (component B) having an aromatic ring or thioalkyl structure used in the present invention includes the following general formula (1) -c (Wherein r1 to r3 represent an integer of 0 to 1, and X 1 to X 6 each independently represent hydrogen or a methylthiol group.)
• the thiol compound represented by these is also preferable. Since the compound contains many thioalkyl structures containing a sulfur atom in the molecule, the effect of increasing the refractive index is great. Moreover, although the aromatic ring contained in A component and D component is easily oxidized and yellowed by light or heat, the thiol group has an antioxidant effect, so that a cured product having excellent colorless transparency can be obtained.
• the component A is a solid or high-viscosity liquid at room temperature, but is adjusted to a viscosity suitable for work by the dilution effect of the component B. Moreover, since the addition polymerization with the ethylenically unsaturated bond of a thiol group has small shrinkage
• Examples of the compound represented by the general formula (1) -c include 1,5-dimercapto-3-thiapentane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-bis ( Mercaptomethyl) -1,11-dimercapto-3,6,9-trithiaundecane, 4,7-bis (mercaptomethyl) -1,11-dimercapto-3,6,9-trithiaundecane, 5,7- Examples thereof include bis (mercaptomethyl) -1,11-dimercapto-3,6,9-trithiaundecane.
• ⁇ B component may be used alone or in combination of two or more.
• the thiol group undergoes an addition reaction with the ethylenically unsaturated bond group in a one-to-one mole, so The thiol group is not preferable because it remains unreacted and remains. Therefore, with respect to the content of the B component, the functional group equivalent ratio of the thiol group contained in the B component is 0.2 to the total amount of the ethylenically unsaturated bond groups contained in the A component, the D component, and the E component. It is preferably in the range of 1.5, more preferably in the range of 0.5 to 1.35.
• the photopolymerization initiator (component C) is not particularly limited as long as it generates active radical species by irradiation with actinic rays (ultraviolet rays, visible light, etc.).
• component C include 2,2-methoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, bis ( 2,4,6-Trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and the like.
• ⁇ C component may be used alone or in combination of two or more.
• the content of component C is not particularly limited, but is preferably in the range of 0.1 to 10 parts by weight and 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 following general formula (3) (In the formula, X represents a sulfur atom or a sulfonyl group, and Z represents a (meth) acryloyl group, a vinyl group, or an allyl group.)
• the ethylenically unsaturated compound (component D) represented by the formula is effective in increasing the refractive index due to the di (thiophenyl) sulfide structure and the di (thiophenyl) sulfone structure.
• Examples of the compound represented by the general formula (3) include 4,4′-bis (methacryloylthio) diphenyl sulfide.
• the D component may be used alone or in combination of two or more.
• the greater the content of the component D the greater the effect of increasing the refractive index.
• yellow coloring increases, and the component D may not dissolve in the composition liquid.
• the content of the component D is preferably in the range of 50 parts by weight or less, more preferably in the range of 25 parts by weight or less, with respect to 100 parts by weight of the curable composition.
• An ethylenically unsaturated compound (component E) other than component A and component D contained as a dilutable monomer is a compound having one or more ethylenically unsaturated bond groups in the molecule, and the viscosity of the composition is There is no limitation as long as it has an effect of lowering.
• a compound having an aromatic ring or a heterocyclic ring is preferable for the purpose of increasing the refractive index.
• the component E include triallyl isocyanurate, triallyl cyanurate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, triallyl trimellitic acid, tetraallyl pyromellitic acid, phenyl (meth) acrylate, 2-phenoxyethyl ( Examples include meth) acrylate, o-phenylphenol (meth) acrylate, 2- (o-phenylphenoxy) ethyl (meth) acrylate, benzyl (meth) acrylate, 2- (benzyloxy) ethyl (meth) acrylate, and the like.
• ⁇ E component may be used alone or in combination of two or more.
• 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 can be obtained by uniformly mixing each component at room temperature or under heating according to a conventional method.
• the composition after mixing may be filtered or defoamed as necessary.
• the viscosity of the optical adhesive if the viscosity is too low, the adhesive may sag or flow, or the substrate may be displaced during pasting. 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 present invention depends on the use form of the adhesive such as the coating method and the laminating method, and cannot be defined unconditionally.
• the B component the general formula (1) -a or the general formula (1 )
• the polythiol compound represented by -c is preferably in the range of 500 to 20,000 mPa ⁇ s, more preferably in the range of 1,000 to 10,000 mPa ⁇ s.
• the polythiol compound represented by the general formula (1) -b is used as the B component, it is preferably in the range of 1,000 to 30,000 mPa ⁇ s, more preferably 1,000 to 10,000 mPa ⁇ s. It is the range of s.
• 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 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 index of the curable composition and the cured product was 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, 71 g of 9,9-bis (4- (2-acryloxyethoxy) phenyl) fluorene (component A), 29 g of m-xylylene thiol (component B), and 3 g of 1-hydroxy-cyclohexyl phenyl ketone (C Component) was taken and stirred at 60 ° C. for 1 hour to prepare a curable composition. The curable composition was sandwiched between two release-treated glass plates and irradiated with light from a metal halide lamp (120 W / cm) for 3 minutes from a distance of 30 cm. 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 the A component, B component, D component, and E component 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 Examples 1-10 A curable composition and a cured film were prepared in the same manner as in Example 1 except that the types and amounts of components A, B, D, and E were changed to those shown in Table 2.
• the physical properties of the curable composition and the cured film were as shown in Table 2. In addition, the value in which a physical property is inferior compared with an Example was underlined.
• Example 6 In a 300 ml flask, 66 g of 9,9-bis (4- (2-acryloxyethoxy) phenyl) fluorene (component A), 34 g of 2,5-dimercaptomethyl-1,4-dithiane (component B), and 1- 3 g of hydroxy-cyclohexyl phenyl ketone (component C) was taken and stirred at 60 ° C. for 1 hour to prepare a curable composition. The curable composition was sandwiched between two release-treated glass plates and irradiated with light from a metal halide lamp (120 W / cm) for 3 minutes from a distance of 30 cm. 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 3.
• Examples 7 to 13 A curable composition and a cured film were prepared in the same manner as in Example 6 except that the types and amounts of components A, B, D, and E were changed to the contents shown in Table 3. The physical properties of the curable composition and the cured film were as shown in Table 3.
• Comparative Examples 11-20 A curable composition and a cured film were prepared in the same manner as in Example 6 except that the types and amounts of components A, B, D, and E were changed to the contents shown in Table 4.
• the physical properties of the curable composition and the cured film were as shown in Table 4. In addition, the value in which a physical property is inferior compared with an Example was underlined.
• Example 14 In a 300 ml flask, 80 g of 9,9-bis (4- (2-acryloxyethoxy) phenyl) fluorene (component A), 20 g of 1,5-dimercapto-3-thiapentane (component B), and 1-hydroxy-cyclohexylphenyl 3 g of ketone (C component) was taken and stirred at 60 ° C. for 1 hour to prepare a curable composition. 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 5.
• Examples 15-27 A curable composition and a cured film were prepared in the same manner as in Example 14 except that the types and amounts of components A, B, D, and E were changed to the contents shown in Table 5. The physical properties of the curable composition and the cured film were as shown in Table 5.
• Comparative Examples 21-30 A curable composition and a cured film were prepared in the same manner as in Example 14 except that the types and amounts of components A, B, D, and E were changed to the contents shown in Table 6.
• the physical properties of the curable composition and the cured film were as shown in Table 6. In addition, the value in which a physical property is inferior compared with an Example was underlined.

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