[go: up one dir, main page]

WO2012063644A1 - Composition durcissable et objet durci obtenu à partir de celle-ci - Google Patents

Composition durcissable et objet durci obtenu à partir de celle-ci Download PDF

Info

Publication number
WO2012063644A1
WO2012063644A1 PCT/JP2011/074655 JP2011074655W WO2012063644A1 WO 2012063644 A1 WO2012063644 A1 WO 2012063644A1 JP 2011074655 W JP2011074655 W JP 2011074655W WO 2012063644 A1 WO2012063644 A1 WO 2012063644A1
Authority
WO
WIPO (PCT)
Prior art keywords
fine particles
curable composition
inorganic fine
meth
mass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2011/074655
Other languages
English (en)
Japanese (ja)
Inventor
慶史 浦川
敬史 関根
山木　繁
石井　伸晃
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Holdings Corp
Original Assignee
Showa Denko KK
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Showa Denko KK filed Critical Showa Denko KK
Priority to JP2012542863A priority Critical patent/JPWO2012063644A1/ja
Publication of WO2012063644A1 publication Critical patent/WO2012063644A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • G02B1/041—Lenses
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica

Definitions

  • the present invention relates to a cured product excellent in transparency, heat resistance, and refractive index temperature dependency obtained by curing a curable composition containing two or more kinds of inorganic particles having different particle diameters.
  • glass plates are often used as substrates for liquid crystal display elements, color filter substrates, organic EL display element substrates, solar cell substrates, touch panels, and the like.
  • a plastic material instead of a glass plate because of problems such as the glass plate is easily broken, cannot be bent, and has a large specific gravity and is not suitable for weight reduction.
  • an optical lens an optical element, an optical waveguide, and an LED sealant, a plastic material having excellent heat resistance such as having reflow resistance has been recently demanded.
  • Patent Document 1 a resin composition comprising an amorphous thermoplastic resin and bis (meth) acrylate curable by active energy rays is cured by active energy rays. It is described that such a member can be suitably used for an optical lens, an optical disk substrate, a plastic liquid crystal substrate, and the like instead of a glass substrate.
  • Patent Document 1 since the conventional plastic material as shown in Patent Document 1 has poor heat resistance or large shrinkage at the time of curing, for example, when applied to a display element substrate, the material is used in the manufacturing process. There arises a problem that warpage, deflection or cracking occurs.
  • General methods for improving heat resistance and reducing shrinkage include a method of adding an inorganic filler in a resin composition and a method of laminating an inorganic film on a substrate.
  • an inorganic filler is added to the resin composition, the transparency of the cured product (substrate) obtained by curing the resin composition is significantly impaired, the surface smoothness is lost, and the dispersibility of the silica fine particles is poor. For this reason, there is a problem that non-uniformity occurs in the substrate and the substrate is easily broken.
  • JP-A-5-209027 Patent Document 2
  • JP-A-10-231339 Patent Document 3
  • JP-A-10-298252 Patent Document 4
  • Silica-based polycondensate obtained by hydrolyzing and polycondensating in a polymer is uniformly dispersed in a radical polymerizable vinyl compound such as methyl methacrylate or a bisphenol A-type ethylene oxide-modified (meth) acrylate.
  • a curable composition that provides a cured product with excellent rigidity. However, these also have insufficient heat resistance.
  • Patent Document 5 removes an organic solvent from a composition containing a bifunctional (meth) acrylate having a specific alicyclic structure and colloidal silica dispersed in an organic solvent.
  • a cured product obtained by crosslinking the composite composition obtained in this manner is described.
  • the dispersibility of silica in the composite composition, the suppression of curing shrinkage, and the molding processability of the cured product are insufficient.
  • a silane compound having an alicyclic structure is added to the composition in order to supplement the dispersibility of silica and to reduce the viscosity of the composite composition, but the hydrolysis rate of the silane compound is also described. Is extremely slow, so that it is not economical in terms of production time and the effect is difficult to be exhibited.
  • Patent Documents 2 to 5 do not describe the temperature change of the refractive index.
  • JP-A-2006-161000 (Patent Document 6) describes that a cured product obtained by combining two or more kinds of inorganic fine particles having different refractive indexes is excellent in refractive index temperature dependency and transparency.
  • the cured product is a thermoplastic resin, it is inferior in heat resistance such as having reflow resistance.
  • the present invention is used for applications such as optical lenses, optical disk substrates, plastic substrates for liquid crystal display elements, color filter substrates, plastic substrates for organic EL display elements, solar cell substrates, touch panels, optical elements, optical waveguides, and LED sealing materials. It is an object of the present invention to provide a curable composition capable of providing a suitable cured product.
  • an object of the present invention is to provide a curable composition capable of providing a cured product excellent in transparency, heat resistance and refractive index temperature dependency.
  • curing includes two or more kinds of inorganic fine particles having different particle diameters, which are surface-treated with a specific silane compound, a (meth) acrylate compound, and a polymerization initiator. It has been found that a cured product having excellent transparency, heat resistance, and refractive index temperature dependency can be obtained by curing the adhesive composition.
  • the gist of the present invention is as follows.
  • Inorganic fine particles (a), a (meth) acrylate compound (b) and a polymerization initiator (c) are contained.
  • the amount of particles having a particle diameter of 15 ⁇ 5 nm is set to 1.
  • the inorganic fine particles (a) include inorganic fine particles (a1) having an average particle diameter of 1 nm or more and 30 nm or less, and inorganic fine particles (a2) having an average particle diameter of more than 30 nm and 60 nm or less.
  • the inorganic fine particles (a) are surface-treated with a silane compound (d) represented by the following general formula (1) and a silane compound (e) represented by the following general formula (2).
  • a silane compound (d) represented by the following general formula (1) and a silane compound (e) represented by the following general formula (2).
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents an alkyl group having 1 to 3 carbon atoms or a phenyl group
  • R 3 represents a hydrogen atom or a carbon atom having 1 to 10 carbon atoms.
  • X represents an aromatic group having 6 to 12 carbon atoms
  • R 4 represents an alkyl group having 1 to 3 carbon atoms or a phenyl group
  • R 5 represents a hydrogen atom or 1 carbon atom.
  • R 1 represents a methyl group or a hydrogen atom
  • R 2 represents a methyl group
  • R 3 represents a methyl group or an ethyl group
  • a is 2 or 3
  • b Is 0 or 1
  • X represents a phenyl group
  • R 4 represents a methyl group or a phenyl group
  • R 5 represents a methyl group or an ethyl group
  • c is 0 or 1
  • d is The curable composition according to [3], which is 0 or 1.
  • the (meth) acrylate compound (b) is a (meth) acrylate compound (b1) having 2 to 6 ethylenically unsaturated groups and having no ring structure.
  • the curable composition according to any one of [1] to [7].
  • the (meth) acrylate compound (b) is a (meth) acrylate compound (b2) having one ethylenically unsaturated group and having an alicyclic structure [1] ]
  • the curable composition according to any one of [7] to [7].
  • a polymerization initiator (c) to the solvent-removed composition and mixing them uniformly.
  • particles having a particle diameter of 15 ⁇ 5 nm are included.
  • the amount of particles having a particle diameter of 45 ⁇ 5 nm is 0.15 to 5.0 in terms of mass, and the inorganic fine particles (a) have an average particle diameter of 1 nm or more A mass ratio (a1) / (a2) between the inorganic fine particles (a1) and the inorganic fine particles (a2), including inorganic fine particles (a1) of 30 nm or less and inorganic fine particles (a2) having an average particle diameter of more than 30 nm and 60 nm or less. ) Is 1/9 to 9/1 A method for producing a curable composition.
  • a curable composition capable of providing a cured product excellent in transparency, heat resistance and refractive index temperature dependency. That is, by containing inorganic fine particles having different particle diameters in the curable composition, a cured product having a small change in refractive index with respect to temperature and good environmental resistance can be obtained.
  • the cured product of the present invention includes a transparent plate, an optical lens, an optical disk substrate, a plastic substrate for a liquid crystal display element, a substrate for a color filter, a plastic substrate for an organic EL display element, a solar cell substrate, a touch panel, an optical element, an optical waveguide, and an LED seal. It is suitable for applications such as fastening materials.
  • the curable composition of the present invention contains inorganic fine particles (a), a (meth) acrylate compound (b) and a polymerization initiator (c).
  • inorganic fine particles (a) particles having a particle diameter of 15 ⁇ 5 nm are contained.
  • the abundance is 1, the abundance of particles having a particle diameter of 45 ⁇ 5 nm is 0.15 to 5.0 in terms of mass.
  • the inorganic fine particles (a) have an average particle diameter of 1 nm or more.
  • the abundance of particles having a particle diameter of 15 ⁇ 5 nm when the abundance of particles having a particle diameter of 15 ⁇ 5 nm is 1, the abundance of particles having a particle diameter of 45 ⁇ 5 nm is 0.15 to 5.0 in terms of mass. , Preferably 0.2 to 3.5, more preferably 0.25 to 2.5.
  • the abundance can be determined by the same method as the method for measuring the average particle diameter described later. Such abundance can be achieved by using inorganic fine particles having different average particle sizes as described below.
  • examples of the inorganic fine particles (a1) include silica fine particles, zirconia fine particles, titania fine particles, tin fine particles, tantalum fine particles, and zinc fine particles. Of these, silica fine particles and zirconia fine particles are preferred. Further, fine particles of a composite metal oxide of aluminum, magnesium, zinc, or the like and silicon, or porous silica sol may be used.
  • the average particle size of the inorganic fine particles (a1) is 1 nm to 30 nm, preferably 5 nm to 25 nm, more preferably 5 nm to 20 nm.
  • the average particle diameter is less than 1 nm, the viscosity of the curable composition increases, the content of the inorganic fine particles (a) in the curable composition is limited, and the dispersibility in the curable composition is It may deteriorate and sufficient transparency and heat resistance may not be obtained in a cured product obtained by curing the curable composition.
  • the mass ratio (a1) / (a2) between the inorganic fine particles (a1) and the inorganic fine particles (a2) is preferably 1/9 to 9/1, more preferably 2/8 to 8/2, and particularly preferably 3 / 7 to 7/3. It is preferable that the mass ratio (a1) / (a2) between the inorganic fine particles (a1) and the inorganic fine particles (a2) is in the above range because the refractive index temperature dependency becomes small.
  • the content of the inorganic fine particles (a1) is preferably 10 to 90 parts by mass, more preferably 20 to 80 parts by mass, and particularly preferably 30 to 30 parts by mass in a total of 100 parts by mass of the inorganic fine particles (a1) and the inorganic fine particles (a2). 70 parts by mass. If the content of the inorganic fine particles (a1) is out of the above range, the refractive index temperature dependency may be deteriorated.
  • Examples of the inorganic fine particles (a2) include those similar to the inorganic fine particles (a1) described above.
  • the average particle diameter of the inorganic fine particles (a2) is more than 30 nm and not more than 60 nm, preferably more than 30 nm and not more than 50 nm, more preferably not less than 30 nm and not more than 45 nm. If the average particle diameter exceeds 60 nm, the transparency of the cured product may be deteriorated.
  • the content of the inorganic fine particles (a2) is preferably 10 to 90 parts by mass, more preferably 20 to 80 parts by mass, and particularly preferably 30 to 30 parts by mass in a total of 100 parts by mass of the inorganic fine particles (a1) and the inorganic fine particles (a2). 70 parts by mass.
  • the refractive index temperature dependency may increase.
  • inorganic fine particles (a1) and inorganic fine particles (a2) at least one is preferably silica fine particles.
  • the average particle size of the inorganic fine particles (a) containing the inorganic fine particles (a1) and the inorganic fine particles (a2) is preferably 1 to from the viewpoint of the balance between the viscosity of the curable composition and the transparency of the cured product.
  • the thickness is 50 nm, more preferably 5 to 50 nm, and particularly preferably 5 to 45 nm.
  • the average particle size of the inorganic fine particles (a1), inorganic fine particles (a2), and inorganic fine particles (a) in this specification is determined using a high-resolution transmission electron microscope (H-9000 type, manufactured by Hitachi, Ltd.). And 100 inorganic particle images are arbitrarily selected from the observed fine particle images, and the value is obtained as a number average particle diameter by a known image data statistical processing technique.
  • the content of the inorganic fine particles (a) in the curable composition is the surface of the silane compounds (d) and (e) described later in a total of 100% by weight of the inorganic fine particles (a) and the (meth) acrylate compound (b).
  • the amount of the treated inorganic fine particles is preferably 20 to 80% by mass, and more preferably 20 to 60% by mass from the viewpoint of the balance between the heat resistance of the cured product and the viscosity of the curable composition.
  • a cured product having sufficient strength and heat resistance can be easily produced. Can do.
  • the inorganic fine particles (a) it is preferable to use inorganic fine particles dispersed in an organic solvent from the viewpoint of dispersibility in the curable composition.
  • the organic solvent is not particularly limited as long as it dissolves organic components contained in the curable composition such as the (meth) acrylate compound (b).
  • organic solvent examples include alcohols, ketones, esters, and glycol ethers.
  • Alcohol solvents such as methanol, ethanol, isopropyl alcohol, butyl alcohol and n-propyl alcohol, and ketone organic solvents such as methyl ethyl ketone and methyl isobutyl ketone are preferred, and isopropyl alcohol is particularly preferred.
  • inorganic fine particles (a) When inorganic fine particles (a) are used dispersed in isopropyl alcohol, the viscosity of the curable composition after desolvation is lower than when other solvents are used, and a curable composition having a low viscosity is stably prepared. Can do.
  • inorganic fine particles dispersed in such an organic solvent commercially available products may be used, or they can be produced by a conventionally known method.
  • Commercially available products include, for example, as a silica fine particle dispersion, trade name Snow Tech IPA-ST (manufactured by Nissan Chemical Industries, Ltd.) and trade name Snow Tech IPA-ST-L (manufactured by Nissan Chemical Industries, Ltd.).
  • examples of the zirconia fine particles include nano-use OZ (manufactured by Nissan Chemical Industries, Ltd.).
  • the inorganic fine particles (a) are preferably surface-treated with silane compounds (d) and (e).
  • silane compounds (d) and (e) will be described.
  • silane compound (d) decreases the viscosity of the curable composition, and further reacts with the highly reactive (meth) acrylate compound (b) described later, whereby the inorganic fine particles (a) in the curable composition.
  • the dispersion stability of can be improved. Therefore, the silane compound (d) is used to reduce curing shrinkage when the curable composition is cured and to impart molding processability to the cured product.
  • the silane compound (d) is represented by the following general formula (1).
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents an alkyl group or a phenyl group having 1 to 3 carbon atoms
  • R 3 represents a hydrogen atom or a hydrocarbon having 1 to 10 carbon atoms.
  • A represents an integer of 1 to 6
  • b represents an integer of 0 to 2.
  • two R 2 may be the same or different, and when b is 1 or less, a plurality of R 3 may be the same or different.
  • hydrocarbon group having 1 to 10 carbon atoms examples include a methyl group, an ethyl group, and an isopropyl group.
  • a substituent such as a methyl group, a methoxy group, and a chloro group may be bonded to the phenyl group as long as the effects of the present invention are not impaired.
  • R 1 is a methyl group
  • R 2 is a methyl group
  • R 3 is a methyl group or an ethyl group
  • a is 2 from the viewpoints of viscosity reduction and storage stability of the curable composition.
  • Or 3 and b is preferably 0 or 1, more preferably R 1 is a methyl group, R 3 is a methyl group, a is 3 and b is 0.
  • the silane compound (d) when a large amount of acrylate is contained in the curable composition, is preferably one in which R 1 is a hydrogen atom, that is, has an acryl group.
  • the silane compound (d), R 1 is a methyl group, i.e. those having a methacryl group, occurs the curing reaction when curing the curable composition It is preferable because it is easy.
  • silane compound (d) examples include ⁇ -acryloxypropyldimethylmethoxysilane, ⁇ -acryloxypropylmethyldimethoxysilane, ⁇ -acryloxypropyldiethylmethoxysilane, ⁇ -acryloxypropylethyldimethoxysilane, ⁇ -Acryloxypropyltrimethoxysilane, ⁇ -acryloxypropyldimethylethoxysilane, ⁇ -acryloxypropylmethyldiethoxysilane, ⁇ -acryloxypropyldiethylethoxysilane, ⁇ -acryloxypropylethyldiethoxysilane, ⁇ -acryloxy Propyltriethoxysilane, ⁇ -methacryloxypropyldimethylmethoxysilane, ⁇ -methacryloxypropylmethyldimethoxysilane, ⁇ -methacryloxypropyldiethylmethoxysilane, ⁇ -methacryloxyprop
  • ⁇ -acryloxypropyldimethylmethoxysilane ⁇ is preferable in terms of preventing aggregation of inorganic fine particles (a) in the curable composition, reducing the viscosity of the curable composition, and improving storage stability.
  • -Acryloxypropylmethyldimethoxysilane ⁇ -methacryloxypropyldimethylmethoxysilane, ⁇ -methacryloxypropylmethyldimethoxysilane, ⁇ -acryloxypropyltrimethoxysilane and ⁇ -methacryloxypropyltrimethoxysilane are preferred, ⁇ -methacryloxy More preferred are propyltrimethoxysilane and ⁇ -acryloxypropyltrimethoxysilane. These may be used alone or in combination of two or more.
  • the silane compound (d) can be produced by a known method, or a commercially available product can be used.
  • silane compound (e) is a compound represented by the following general formula (2).
  • X represents an aromatic group having 6 to 12 carbon atoms
  • R 4 represents an alkyl group having 1 to 3 carbon atoms or a phenyl group
  • R 5 represents a hydrogen atom or 1 to 3 carbon atoms.
  • 10 represents a hydrocarbon group
  • c is an integer of 0 to 6
  • d is an integer of 0 to 2.
  • two R 4 may be the same or different, and when d is 1 or less, a plurality of R 5 may be the same or different.
  • Examples of the aromatic group having 6 to 12 carbon atoms include a phenyl group and a naphthyl group.
  • hydrocarbon group having 1 to 10 carbon atoms examples include a methyl group, an ethyl group, and an isopropyl group.
  • a substituent such as a methyl group, a methoxy group, and a chloro group may be bonded to the aromatic group and the phenyl group within a range not impairing the effects of the present invention.
  • X is a phenyl group
  • R 4 is a methyl group or a phenyl group
  • R 5 is a methyl group or an ethyl group, from the viewpoint of reducing the viscosity of the curable composition and storage stability
  • c Is preferably 0 or 1
  • d is 0 or 1
  • X is a phenyl group
  • R 5 is a methyl group
  • c is 0 or 1
  • d is 0 or 1.
  • X is a phenyl group
  • R 5 is a methyl group
  • c is 0, and d is 0 or 1.
  • the inorganic fine particles (a) react with the silane compound (e), hydrophobicity is imparted to the surface of the inorganic fine particles (a), and the dispersibility of the inorganic fine particles (a) in the organic solvent is improved.
  • the compatibility between the fine particles (a) and the (meth) acrylate compound (b) becomes good, whereby the viscosity of the curable composition is reduced, and further the storage stability of the curable composition can be improved.
  • silane compound (e) examples include phenyldimethylmethoxysilane, phenylmethyldimethoxysilane, phenyldiethylmethoxysilane, phenylethyldimethoxysilane, phenyltrimethoxysilane, phenyldimethylethoxysilane, phenylmethyldiethoxysilane, and phenyldiethylethoxysilane.
  • phenyldimethylmethoxysilane, phenylmethyldimethoxysilane, phenyldiethylmethoxysilane, phenylethyldimethoxysilane, phenyltrimethoxysilane, and diphenyldimethoxysilane from the viewpoint of reducing the viscosity of the curable composition and improving the storage stability.
  • phenyltrimethoxysilane and diphenyldimethoxysilane are more preferred.
  • These silane compounds may be used alone or in combination of two or more.
  • the inorganic fine particles (a) are surface-treated with 5 to 40 parts by mass of the silane compound (d) and 5 to 40 parts by mass of the silane compound (e) with respect to 100 parts by mass of the inorganic fine particles (a). is there.
  • the amount of the silane compound (d) or (e) used is less than 5 parts by mass, the viscosity of the curable composition increases, and the dispersibility of the inorganic fine particles (a) in the curable composition deteriorates. There are cases where gelation occurs and the heat resistance of the cured product is reduced. On the other hand, when it exceeds 40 mass parts, aggregation of inorganic fine particles (a) may be caused.
  • the mass of the inorganic fine particles (a) when the inorganic fine particles (a) dispersed in the organic solvent are used refers to the mass of the inorganic fine particles (a) themselves dispersed in the organic solvent.
  • the amount of the silane compound (d) used is preferably 5 to 50 parts by mass, more preferably 5 to 40 parts by mass with respect to 100 parts by mass in total of the silane compounds (d) and (e). It is preferable that the amount of the silane compound (d) used be in the above range because the reactivity with the (meth) acrylate compound (b) is improved.
  • the amount of the silane compound (e) to be used is preferably 5 to 50 parts by mass, more preferably 5 to 40 parts by mass with respect to 100 parts by mass in total of the silane compounds (d) and (e). It is preferable that the amount of the silane compound (e) used be in the above range since compatibility with the (meth) acrylate compound (b) is improved.
  • the (meth) acrylate compound (b) used in the present invention is not particularly limited as long as it has an ethylenically unsaturated group as long as it is compatible with the inorganic fine particles (a).
  • the (meth) acrylate compound (b) is a (meth) acrylate compound (b1) having 2 to 6 ethylenically unsaturated groups and having no ring structure, or one ethylenically unsaturated group.
  • a (meth) acrylate compound (b2) having a saturated group and an alicyclic structure is more preferable.
  • Examples of the (meth) acrylate compound (b1) include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and dipenta.
  • Examples include erythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and trimethylolpropane trioxyethyl (meth) acrylate. Of these, those having three ethylenically unsaturated groups are preferred from the viewpoint of the heat resistance of the cured product.
  • (meth) acrylate means methacrylate and / or acrylate.
  • the (meth) acrylate compound (b1) may be a commercially available product or may be prepared by a conventionally known method.
  • Examples of commercially available products include KAYARAD TMPTA (manufactured by Nippon Kayaku Co., Ltd.).
  • the glass transition temperature of the homopolymer of the (meth) acrylate compound (b1) is preferably 80 ° C. or higher and 300 ° C. or lower, more preferably 200 ° C. or higher and 300 ° C. or lower.
  • trimethylolpropane tri (meth) acrylate is the most preferable among the above-described polyfunctional (meth) acrylates because of relatively little curing shrinkage and a glass transition temperature of 200 ° C. or higher.
  • glass was obtained from the peak temperature of the tan ⁇ value measured with DMS6100 (manufactured by Seiko Denshi Kogyo Co., Ltd.) in a tensile mode, a temperature range of 30 to 300 ° C., a heating rate of 2 ° C./min, and a frequency of 1 Hz. Determine the transition temperature.
  • the amount of the (meth) acrylate compound (b1) used is preferably 10 to 90 parts by mass, more preferably 20 parts, in a total of 100 parts by mass of the (meth) acrylate compound (b1) and the (meth) acrylate compound (b2). ⁇ 80 parts by mass. It is preferable that the amount of the (meth) acrylate compound (b1) used be in the above range because heat resistance can be improved.
  • the blending amount of the (meth) acrylate compound (b1) is preferably 20 to 500 parts by mass with respect to 100 parts by mass of the inorganic fine particles (a) before the surface treatment, and the viscosity and curability of the curable composition. From the viewpoint of the dispersion stability of the silica fine particles (a) in the composition and the heat resistance of the cured product, the amount is more preferably 30 to 300 parts by mass, particularly preferably 50 to 200 parts by mass. When the blending amount is less than 20 parts by mass, the viscosity of the curable composition is increased and gelation may occur. On the other hand, when the blending amount exceeds 500 parts by mass, shrinkage at the time of curing of the curable composition is increased, and the cured product may be warped or cracked.
  • the (meth) acrylate (b2) is used for imparting heat resistance to the cured product and reducing shrinkage during curing.
  • Examples of the (meth) acrylate (b2) include cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and dicyclopentadienyl.
  • Cycloalkyl (meth) acrylates such as (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate and adamantyl (meth) acrylate And benzyl (meth) acrylate and tetrahydrofurfuryl (meth) acrylate.
  • the glass transition temperature of the homopolymer is preferably 80 ° C. or higher and 300 ° C. or lower, more preferably 100 ° C. or higher and 300 ° C.
  • Dicyclopentanyl (meth) acrylate and adamantyl (meth) acrylate are particularly preferred, and adamantyl (meth) acrylate is most preferred because its homopolymer has a high glass transition temperature.
  • the method for measuring the glass transition temperature of the homopolymer of the (meth) acrylate compound (b2) is the same as described above.
  • the alicyclic structure is a structure in which an aromatic ring structure is excluded from a structure in which carbon atoms are bonded cyclically.
  • the (meth) acrylate compound (b2) may be a commercially available product or may be prepared by a conventionally known method.
  • ADMA made by Osaka Organic Chemical Co., Ltd.
  • the amount of the (meth) acrylate compound (b2) used is preferably 10 to 50 parts by mass, more preferably 20 parts, in a total of 100 parts by mass of the (meth) acrylate compound (b1) and the (meth) acrylate compound (b2). ⁇ 50 parts by mass. It is preferable that the amount of the (meth) acrylate compound (b2) used be in the above range because shrinkage during curing can be reduced.
  • the blending amount of the (meth) acrylate compound (b2) is preferably 5 to 400 parts by mass with respect to 100 parts by mass of the inorganic fine particles (a) before the surface treatment, and the viscosity and curability of the curable composition. From the viewpoint of the dispersion stability of the inorganic fine particles (a) in the composition and the heat resistance of the cured product, the amount is more preferably 10 to 200 parts by weight, and particularly preferably 20 to 100 parts by weight. When the blending amount is less than 5 parts by mass, the viscosity of the curable composition is increased and gelation may occur. On the other hand, if the blending amount exceeds 400 parts by mass, the cured product may be cracked or the heat resistance of the cured product may be reduced.
  • Polymerization initiator (c) examples include a photopolymerization initiator that generates radicals and a thermal polymerization initiator.
  • photopolymerization initiator examples include benzophenone, benzoin methyl ether, benzoin propyl ether, diethoxyacetophenone, 1-hydroxyphenylphenyl ketone, 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine. And oxide and diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide. These photopolymerization initiators may be used alone or in combination of two or more.
  • the content of the photopolymerization initiator in the curable composition may be an amount that allows the curable composition to be appropriately cured.
  • the inorganic fine particles (a) and the (meth) acrylate compound (b) Is generally 0.01 to 10% by mass, preferably 0.02 to 5% by mass, and more preferably 0.1 to 2% by mass.
  • the content of the photopolymerization initiator exceeds 10% by mass, the storage stability of the curable composition is lowered, colored, or cross-linked to obtain a cured product by cross-linking rapidly, and at the time of curing. Problems such as cracking may occur.
  • the content of the photopolymerization initiator is less than 0.01% by mass, the curable composition may not be sufficiently cured.
  • thermal polymerization initiators include benzoyl peroxide, diisopropyl peroxycarbonate, t-butyl peroxy (2-ethylhexanoate), t-butyl peroxyneodecanoate, t-hexyl peroxypivalate, 1, 1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-butylperoxypivalate, t-hexylperoxyisopropylmonocarbonate, dilauroyl peroxide, diisopropylperoxydicarbonate, di ( 4-t-butylcyclohexyl) peroxydicarbonate and 2,2-di (4,4-di- (t-butylperoxy) cyclohexyl) propane.
  • the content of the thermal polymerization initiator in the curable composition is usually 10% by mass or less with respect to a total of 100% by mass of the inorganic fine particles (a) and the (meth) acrylate compound (b) in the curable composition. And preferably 0.5 to 5% by mass.
  • the curable composition of the present invention is, as necessary, a polymerization inhibitor, a leveling agent, an antioxidant, and an ultraviolet absorber as long as the viscosity of the composition and the properties of the cured product, such as transparency and heat resistance, are not impaired.
  • Light stabilizers, other solvents, pigments, fillers such as other inorganic fillers, reactive diluents and modifiers may be included.
  • the polymerization inhibitor is used to prevent the components of the curable composition from causing a polymerization reaction during storage.
  • examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, benzoquinone, pt-butylcatechol and 2,6-di-tert-butyl-4-methylphenol.
  • the addition amount of the polymerization inhibitor is 100 parts by mass in total of the inorganic fine particles (a) and the (meth) acrylate compound (b) in the curable composition. Usually, it is 0.1 parts by mass or less.
  • a polymerization inhibitor may be used independently and may use 2 or more types together.
  • leveling agent examples include polyether-modified dimethylpolysiloxane copolymers, polyester-modified dimethylpolysiloxane copolymers, polyether-modified methylalkylpolysiloxane copolymers, aralkyl-modified methylalkylpolysiloxane copolymers, and polyethers. Examples thereof include a modified methylalkylpolysiloxane copolymer.
  • a leveling agent may be used independently and may use 2 or more types together.
  • the antioxidant is a compound having a function of capturing an oxidation promoting factor such as a free radical.
  • the antioxidant is not particularly limited as long as it is an antioxidant generally used industrially, and a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, and the like are used. These antioxidants may be used alone or in combination of two or more.
  • phenol-based antioxidant examples include Irganox 1010 (Irganox® 1010: pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], manufactured by Ciba Specialty Chemicals ), Irganox 1076 (Irganox® 1076: Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, manufactured by Ciba Specialty Chemicals), Irganox 1330 (Irganox® 1330: 3, 3) ', 3' ', 5,5', 5 '' -hexa-t-butyl-a, a ', a' '-(mesitylene-2,4,6-triyl) tri-p-cresol, Ciba Specialty Chemicals), Irganox 3114 (Irganox® 311) : 1,3,5-tris (3,
  • Examples of the phosphorous antioxidant include Irgafos 168 (Irgafos 168: Tris (2,4-di-t-butylphenyl) phosphite, manufactured by Ciba Specialty Chemicals), Irgafos 12 (Irgafos 12: Tris [2 -[[2,4,8,10-tetra-t-butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl] oxy] ethyl] amine, Ciba Specialty Chemicals ), Irgafos 38 (Irgafos 38: bis (2,4-bis (1,1-dimethylethyl) -6-methylphenyl) ethyl ester phosphorous acid, manufactured by Ciba Specialty Chemicals), ADK STAB 329K (Co., Ltd.) ADEKA), ADK STAB PEP36 (manufactured by ADE
  • sulfur-based antioxidant examples include dialkylthiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl and distearyl, and ⁇ -alkyl mercaptopropion of polyols such as tetrakis [methylene (3-dodecylthio) propionate] methane.
  • dialkylthiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl and distearyl
  • ⁇ -alkyl mercaptopropion of polyols such as tetrakis [methylene (3-dodecylthio) propionate] methane.
  • acid ester compounds examples include acid ester compounds.
  • the ultraviolet absorber is generally a compound that can absorb ultraviolet rays having a wavelength of about 200 to 380 nm, change them into energy such as heat and infrared rays, and release them.
  • the ultraviolet absorber is not particularly limited as long as it is generally used industrially, and is not limited to benzotriazole, triazine, diphenylmethane, 2-cyanopropenoate, salicylate, anthranilate, Examples include acid derivative-based, camphor derivative-based, resorcinol-based, oxalinide-based, and coumarin derivative-based ultraviolet absorbers.
  • ultraviolet absorbers may be used alone or in combination of two or more.
  • benzotriazole ultraviolet absorber examples include 2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-[(2H-benzotriazol-2-yl) phenol]]. 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol and 2- [5-chloro (2H) -benzotriazol-2-yl] -4 -Methyl-6- (t-butyl) phenol and the like.
  • triazine-based ultraviolet absorber examples include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] phenol, 2,4,6-tris. -(Diisobutyl-4'-amino-benzalmalonate) -s-triazine, 4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy -4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4 -Dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine and 2 And-(2-hydroxy
  • diphenylmethane ultraviolet absorber examples include diphenylmethanone, methyldiphenylmethanone, 4-hydroxydiphenylmethanone, 4-methoxydiphenylmethanone, 4-octoxydiphenylmethanone, 4-decyloxydiphenylmethanone, 4-dodecyloxydiphenylmethanone, 4-benzyloxydiphenylmethanone, 4,2 ′, 4′-trihydroxydiphenylmethanone, 2′-hydroxy-4,4′-dimethoxydiphenylmethanone, 4- (2- And ethyl hexyloxy) -2-hydroxy-diphenylmethanone, methyl o-benzoylbenzoate and benzoin ethyl ether.
  • Examples of the 2-cyanopropenoic acid ester UV absorber include ethyl ⁇ -cyano- ⁇ , ⁇ -diphenylpropenoic acid ester and isooctyl ⁇ -cyano- ⁇ , ⁇ -diphenylpropenoic acid ester.
  • salicylic acid ester ultraviolet absorber examples include isocetyl salicylate, octyl salicylate, glycol salicylate, and phenyl salicylate.
  • anthranilate ultraviolet absorber examples include menthyl anthranilate.
  • Examples of the cinnamic acid derivative-based ultraviolet absorber include ethylhexyl methoxycinnamate, isopropyl methoxycinnamate, isoamyl methoxycinnamate, diisopropylmethyl cinnamate, glyceryl-ethylhexanoate dimethoxycinnamate, methyl- ⁇ -carbomethoxycinnamate. And methyl- ⁇ -cyano- ⁇ -methyl-p-methoxycinnamate and the like.
  • camphor derivative UV absorber examples include benzylidene camphor, benzylidene camphor sulfonic acid, camphor benzalkonium methosulfate, terephthalidene dicamphor sulfonic acid, and polyacrylamide methylbenzylidene camphor.
  • resorcinol-based ultraviolet absorber examples include dibenzoyl resorcinol and bis (4-t-butylbenzoyl resorcinol).
  • oxalinide ultraviolet absorber examples include 4,4′-di-octyloxy oxanilide, 2,2′-diethoxyoxy oxanilide, and 2,2′-di-octyloxy-5,5 ′.
  • Examples of the coumarin derivative ultraviolet absorber include 7-hydroxycoumarin.
  • the light stabilizer is a compound having an effect of reducing auto-oxidative decomposition due to radicals generated by light energy and suppressing resin deterioration.
  • the light stabilizer is not particularly limited as long as it is generally used industrially, and a hindered amine compound (hereinafter simply referred to as “HALS”), a benzophenone compound, a benzotriazole compound, and the like can be used. These light stabilizers may be used alone or in combination of two or more.
  • HALS examples include N, N ′, N ′ ′, N ′ ′ -tetrakis (4,6-bis (butyl (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl). ) Amino) triazin-2-yl) -4,7-diazadecane-1,10-diamine, dibutylamine and 1,3,5-triazine and N, N'-bis (2,2,6,6-tetramethyl) -4-piperidyl) butylcondensate, poly [ ⁇ (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl ⁇ ⁇ (2,2, 6,6-tetramethyl-4-piperidyl) imino ⁇ hexamethylene ⁇ (2,2,6,6-tetramethyl-4-piperidyl) imino ⁇ ], 1,6-hexanediamine-N, N′-bis ( 2,2,6,6-te
  • the curable composition may further contain a solvent. By mixing the solvent, dispersion of each component in the curable composition can be assisted.
  • the solvent examples include esters such as ethyl acetate, butyl acetate and isopropyl acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; cyclic ethers such as tetrahydrofuran and dioxane; N, N′-dimethylformamide Amides such as toluene; Aromatic hydrocarbons such as toluene; Halogenated hydrocarbons such as methylene chloride; Ethylene glycol, ethylene glycol methyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol, diethylene glycol Ethylene such as monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol monoethyl ether acetate Glycols; propylene glycol, propylene glycol methyl ether, propylene glyco
  • the solvents may be used alone or in combination of two or more.
  • the amount of the solvent used is not particularly limited, but is usually 50 to 200 parts by mass, preferably 50 to 100 parts per 100 parts by mass in total of the inorganic fine particles (a) and the (meth) acrylate compound (b) in the curable composition. Part by mass.
  • filler or pigment examples include calcium carbonate, talc, mica, clay, Aerosil (registered trademark), barium sulfate, aluminum hydroxide, zinc stearate, zinc white, bengara, and azo pigments.
  • the reactive diluent examples include ethylenically unsaturated aromatic compounds such as styrene, diisopropenylbenzene, chlorostyrene and 1,1-diphenylethylene; (meth) acrylic acid, crotonic acid, maleic acid and fumaric acid Carboxyl group-containing compounds such as; alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate and 2-ethylhexyl (meth) acrylate; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxy Hydroxyalkyl (meth) acrylates such as butyl (meth) acrylate; phenoxyalkyl such as phenoxyethyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate (Meth) acrylates; alkoxyalkyl (meth) acrylates
  • Cycloalkyl (meth) acrylates benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol Recall di (meth) acrylate, tripropylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,4-butane Examples include diol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and bisphenol A di (meth) acrylate. These reactive diluents may be used alone or in combination of two or more.
  • the modifier examples include polyolefin resins, chlorinated modified polyolefin resins, unsaturated polyester resins, vinyl ester resins, vinyl urethane resins, vinyl ester urethane resins, polyisocyanates, polyepoxides, epoxy-terminated polyoxazolidones, acrylic resins, Alkyd resins, urea resins, melamine resins, polydiene elastomers, saturated polyesters, saturated polyethers, cellulose derivatives such as nitrocellulose and cellulose acetate butyrate, and linseed oil, tung oil, soybean oil, castor oil and epoxy And natural and synthetic polymer substances such as oils and fats such as chemical oils.
  • ⁇ Method for producing curable composition> colloidal silica (inorganic fine particles (a); hereinafter referred to as “silica fine particles (a)”) dispersed in an organic solvent is surface-treated with silane compounds (d) and (e).
  • colloidal silica inorganic fine particles (a); hereinafter referred to as “silica fine particles (a)”
  • silane compounds (d) and (e) silane compounds (d) and (e).
  • the step (Step 1) the step of adding the (meth) acrylate compound (b) to the surface-treated silica fine particles (a) and uniformly mixing (Step 2), the silica fine particles (a) obtained in Step 2 and the (Meta) )
  • Step 3 A step of distilling off and removing the organic solvent and water from the homogeneous mixed solution with the acrylate compound (b) (Step 3), and a polymerization initiator (c) is added to the composition desolvated in Step 3, and uniform It can manufacture by performing the process (process 4) of mixing and setting it as a curable composition one by one. Each step will be described below.
  • step 1 the silica fine particles (a) are surface-treated with silane compounds (d) and (e).
  • the silica fine particles (a) are put into a reactor, and while stirring, the silane compounds (d) and (e) are added, mixed with stirring, and the silane compounds (d) and (e) are further hydrolyzed. Water and a catalyst necessary for the treatment are added and the mixture is hydrolyzed with stirring and subjected to condensation polymerization on the surface of the silica fine particles (a).
  • silica fine particles dispersed in an organic solvent as the silica fine particles (a).
  • the disappearance of the silane compound due to hydrolysis can be confirmed by gas chromatography.
  • a non-polar column DB-1 manufactured by J & W
  • gas chromatography Alignment Co., Ltd. Model 6850
  • temperature 50 to 300 ° C. heating rate 10 ° C./min
  • He He as carrier gas
  • the residual amount of the silane compound can be measured by an internal standard method with a flow rate of 1.2 cc / min and a flame ionization detector, disappearance due to hydrolysis of the silane compound can be confirmed.
  • the lower limit of the amount of water required for carrying out the hydrolysis reaction is 1 time the total number of moles of alkoxy groups and hydroxyl groups bonded to the silane compounds (d) and (e), and the upper limit is 10 times. . If the amount of water is too small, the hydrolysis rate may become extremely slow, resulting in lack of economic efficiency, or the surface treatment may not proceed sufficiently. Conversely, if the amount of water is excessively large, the silica fine particles (a) may form a gel.
  • a catalyst for the hydrolysis reaction When performing the hydrolysis reaction, a catalyst for the hydrolysis reaction is usually used.
  • catalysts include inorganic acids such as hydrochloric acid, acetic acid, sulfuric acid and phosphoric acid; organic acids such as formic acid, propionic acid, oxalic acid, paratoluenesulfonic acid, benzoic acid, phthalic acid and maleic acid; Alkali catalysts such as potassium, sodium hydroxide, calcium hydroxide and ammonia; organometallics; metal alkoxides; organotin compounds such as dibutyltin dilaurate, dibutyltin dioctylate and dibutyltin diacetate; aluminum tris (acetylacetonate), titanium tetrakis ( Acetylacetonate), titanium bis (butoxy) bis (acetylacetonate), titanium bis (isopropoxy) bis (acetylacetonate), zirconium bis (butoxy) bis
  • Step 1 when the hydrolysis reaction of the silane compounds (d) and (e) is performed, a water-insoluble catalyst may be used, but a water-soluble catalyst is preferably used.
  • a water-soluble catalyst for hydrolysis reaction it is preferable to dissolve the water-soluble catalyst in an appropriate amount of water and add it to the reaction system because the catalyst can be uniformly dispersed.
  • the amount of the catalyst used for the hydrolysis reaction is not particularly limited, but is usually 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the silica fine particles (a).
  • the mass of the silica fine particle (a) in the case of using the silica fine particle dispersed in the organic solvent as the silica fine particle (a) indicates only the mass of the silica fine particle itself dispersed in the organic solvent.
  • the reaction temperature of the hydrolysis reaction is not particularly limited, but is usually in the range of 10 to 80 ° C, preferably in the range of 20 to 50 ° C. If the reaction temperature is too low, the hydrolysis rate may become extremely slow, resulting in lack of economic efficiency, or the surface treatment may not proceed sufficiently. On the other hand, if the reaction temperature is excessively high, a gelation reaction may easily occur.
  • the reaction time for performing the hydrolysis reaction is not particularly limited, but is usually in the range of 10 minutes to 48 hours, preferably 30 minutes to 24 hours.
  • Step 1 the surface treatment with the silane compounds (d) and (e) in Step 1 may be performed sequentially, but it is preferable to carry out the surface treatment at the same time in terms of simplification and efficiency of the reaction process.
  • step 2 the method of mixing the surface-treated silica fine particles (a) and the (meth) acrylate compound (b) is not particularly limited.
  • examples thereof include a method of mixing with a mixer and a method of adding and mixing the (meth) acrylate compound (b) while continuously stirring the reactor in which Step 1 has been performed.
  • step 3 the organic solvent and water are distilled off and removed from the homogeneous mixture of the silica fine particles (a) and the (meth) acrylate compound (b) (hereinafter collectively referred to as “desolvent”). It is preferable to heat in a reduced pressure state.
  • the temperature is preferably maintained at 20 to 100 ° C., and more preferably 30 to 70 ° C., particularly preferably 30 to 50 ° C. in terms of the balance between aggregation gelation prevention and desolvation speed. If the temperature is raised too much, the fluidity of the curable composition may be extremely lowered or may be gelled.
  • the degree of vacuum at the time of depressurization is usually 10 to 4,000 kPa, and preferably 10 to 1,000 kPa, more preferably 10 to 500 kPa, in order to balance the solvent removal speed and the prevention of aggregation gelation. . If the value of the degree of vacuum is too large, the speed of solvent removal becomes extremely slow, and the economic efficiency may deteriorate.
  • the composition after desolvation contains substantially no solvent.
  • substantially means that when a cured product is actually obtained using the curable composition of the present invention, it is not necessary to go through a step of removing the solvent again.
  • the residual amount of the organic solvent and water in the curable composition means 1% by mass or less, preferably 0.5% by mass or less, more preferably 0.1% by mass or less.
  • a polymerization inhibitor may be added to 100 parts by mass of the composition after desolvation before desolvation.
  • the polymerization inhibitor is used to prevent components contained in the composition from undergoing a polymerization reaction during or after the solvent removal or during the storage of the composition or the curable composition.
  • the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, benzoquinone, pt-butylcatechol and 2,6-di-tert-butyl-4-methylphenol. These are used alone or in combination of two or more.
  • Step 3 can be carried out by transferring the homogeneous mixed liquid of silica fine particles (a) and (meth) acrylate compound (b) that have undergone Step 2 to a dedicated apparatus, or Step 2 can be carried out in the reactor in which Step 1 has been carried out. If so, it may be carried out in the same reactor following step 2.
  • step 4 the method of adding the polymerization initiator (c) to the composition desolvated in step 3 and uniformly mixing is not particularly limited.
  • a mixer such as a mixer, a ball mill, and a three-roller at room temperature.
  • the curable composition obtained by adding and mixing such a polymerization initiator (c) may be filtered as necessary. This filtration is performed for the purpose of removing foreign substances such as dust in the curable composition.
  • the filtration method is not particularly limited, but a pressure filtration method using a membrane type or cartridge type filter having a pressure filtration pore size of 1.0 ⁇ m is preferred.
  • a cured product is obtained by curing the curable composition.
  • the curing method include a method of crosslinking ethylenically unsaturated groups in the curable composition by irradiation with active energy rays, and a method of thermally polymerizing the ethylenically unsaturated groups by applying heat. It can also be used together.
  • the photopolymerization initiator (c) is contained in the curable composition in the step 4 described above.
  • a thermal polymerization initiator (c) is contained in the curable composition.
  • the cured product is formed by coating the curable composition on a substrate such as a glass plate, a plastic plate, a metal plate, and a silicon wafer to form a coating film, and then applying an active energy ray to the curable composition. Obtained by irradiation or by heating. In order to make it harden
  • Examples of the method for applying the curable composition include application by a bar coater, applicator, die coater, spin coater, spray coater, curtain coater and roll coater, application by screen printing, and application by dipping. .
  • the coating amount of the curable composition on the substrate is not particularly limited and can be appropriately adjusted according to the purpose.
  • the film thickness of the coating film obtained after the curing treatment is preferably 1 to 1,000 ⁇ m, More preferably, the coating is applied in an amount of 10 to 800 ⁇ m.
  • the active energy ray used for curing is preferably an electron beam or light in the ultraviolet to infrared wavelength range.
  • an ultra-high pressure mercury light source or a metal halide light source can be used for ultraviolet rays
  • a metal halide light source or a halogen light source can be used for visible rays
  • a halogen light source can be used for infrared rays. Can be used.
  • the irradiation amount of the active energy ray is appropriately set according to the type of the light source and the film thickness of the coating film, but the reaction rate of the ethylenically unsaturated group of the (meth) acrylate compound (b) is preferably 80%. As mentioned above, it can set suitably so that it may become 90% or more more preferably.
  • the reaction rate is calculated from the change in the absorption peak intensity of the ethylenically unsaturated group before and after the reaction by infrared absorption spectrum.
  • curing may be further advanced by heat treatment (annealing treatment).
  • the heating temperature at that time is preferably in the range of 80 to 220 ° C.
  • the heating time is preferably in the range of 10 minutes to 60 minutes.
  • the heating temperature is preferably in the range of 80 to 200 ° C, more preferably in the range of 100 to 150 ° C.
  • the heating temperature is less than 80 ° C., it is necessary to lengthen the heating time, which may be economical.
  • the heating temperature exceeds 200 ° C., energy cost is required and heating heating time and cooling time are required.
  • the heating time is appropriately set according to the heating temperature or the film thickness of the coating film, but the reaction rate of the (meth) acrylate compound (b) is preferably 80% or more, more preferably 90% or more. Set as appropriate.
  • the reaction rate is calculated from the change in the absorption peak intensity of the ethylenically unsaturated group before and after the reaction by infrared absorption spectrum.
  • the cured product has an absolute value of a refractive index temperature dependency coefficient of preferably 7.0 ⁇ 10 ⁇ 5 / ° C. or less, more preferably 6.8 ⁇ 10 ⁇ 5 / ° C. or less, and particularly preferably 6 It is 6 ⁇ 10 ⁇ 5 / ° C. or less.
  • a refractive index temperature dependency coefficient exceeds 7.0 ⁇ 10 ⁇ 5 / ° C., for example, when applied to an optical lens or an optical waveguide, the focal length of light shifts when the temperature changes depending on the use environment, and the image accuracy May decrease or the light propagation efficiency may decrease.
  • a material conventionally used for optical lenses and the like is polycarbonate, but the absolute value of the refractive index temperature dependency coefficient is 10.7 ⁇ 10 ⁇ 5 / ° C., and the change with temperature is large.
  • the refractive index temperature dependence coefficient is measured using a MODEL 2010M PRISM COUPLER (manufactured by Metricon), measuring the refractive index of the cured product by changing the measurement temperature from 30 to 60 ° C. in increments of 5 ° C., It refers to the slope when the refractive index at a wavelength of 594 nm is plotted against temperature.
  • the cured product of the present invention has excellent transparency because the light transmittance at a wavelength of 400 nm when the thickness of the cured film is 400 ⁇ m is 75% or more.
  • the light transmittance at a wavelength of 400 nm is less than 75%, the efficiency of using light is lowered, which is not preferable for applications where light efficiency is important.
  • the cured product of the present invention has a 5% weight reduction temperature when heated in a nitrogen atmosphere, usually 300 ° C. or higher, specifically 320 ° C. or higher, more specifically 350 ° C. or higher, and has excellent heat resistance.
  • a 5% weight reduction temperature when heated in a nitrogen atmosphere, usually 300 ° C. or higher, specifically 320 ° C. or higher, more specifically 350 ° C. or higher, and has excellent heat resistance.
  • the (meth) acrylate compound (b) whose homopolymer has a glass transition temperature of 80 to 300 ° C. is used
  • the cured product exhibits particularly excellent heat resistance.
  • the 5% weight loss temperature is less than 300 ° C., for example, when the cured product is used for an active matrix display element substrate, problems such as warpage, deflection, or occurrence of cracks may occur in the manufacturing process. .
  • the cured product of the present invention is excellent in transparency, heat resistance and molding processability, for example, an optical lens, an optical disk substrate, a plastic substrate for a liquid crystal display element, a substrate for a color filter, a plastic substrate for an organic EL display element, It can be used for a solar cell substrate, a touch panel, an optical element, an optical waveguide, an LED sealing material, and the like, and can be particularly suitably used for an optical lens, an optical element, and an optical waveguide.
  • silica fine particle dispersion (A-1) In a separable flask containing 100 parts by mass of isopropyl alcohol-dispersed colloidal silica (silica content 30% by mass, average particle size 15 nm, trade name Snowtech IPA-ST; manufactured by Nissan Chemical Industries, Ltd.), ⁇ -methacryloxypropyl Add 5.4 parts by mass of trimethoxysilane and 3.6 parts by mass of phenyltrimethoxysilane, stir and mix, and further add 2.9 parts by mass of HCl solution having a concentration of 0.1825% by mass, and stir at 20 ° C. for 24 hours. As a result, surface treatment of the silica fine particles was performed to obtain a silica fine particle dispersion (A-1).
  • Preparation Example 2 Silica fine particle dispersion (A-2) In Preparation Example 1, isopropyl alcohol-dispersed colloidal silica (silica content 30% by mass, average particle size 10 to 15 nm, trade name Snowtech IPA-ST; manufactured by Nissan Chemical Industries, Ltd.) was used. A silica fine particle dispersion (as in Preparation Example 1) except that silica (silica content 30% by mass, average particle size 45 nm, trade name Snowtech IPA-ST-L; manufactured by Nissan Chemical Industries, Ltd.) was used. A-2) was obtained.
  • Preparation Example 3 Zirconia fine particle dispersion (A-3)
  • isopropyl alcohol-dispersed zirconia was used instead of isopropyl alcohol-dispersed colloidal silica (silica content 30% by mass, average particle size 10 to 15 nm, trade name Snowtech IPA-ST; manufactured by Nissan Chemical Industries, Ltd.).
  • a zirconia fine particle dispersion (A-3) was obtained in the same manner as in Preparation Example 1, except that (zirconia content 10% by mass, average particle size 7 nm; manufactured by Sumitomo Osaka Cement Co., Ltd.) was used.
  • Curable composition (B-1) Trimethylolpropane triacrylate was added to 112.5 parts by mass of the silica fine particle dispersion (A-1) obtained in Preparation Example 1 and 37.5 parts by mass of the silica fine particle dispersion (A-2) obtained in Preparation Example 2.
  • (Trade name KAYARAD TMPTA; Nippon Kayaku Co., Ltd., homopolymer glass transition temperature (Tg)> 250 ° C.) 30 parts by mass and adamantyl methacrylate (trade name ADMA; Osaka Organic Chemical Co., Ltd., homopolymer) (Tg 180 ° C.) of 30 parts by mass was added and mixed uniformly. Thereafter, the mixture was heated under reduced pressure at 40 ° C. and 100 kPa with stirring to remove volatile components.
  • the silica fine particles used in Example 1 had an abundance of a particle size of 45 ⁇ 5 nm in terms of mass, assuming that the abundance of a particle size of 15 ⁇ 5 nm was 1, which was 0.264 in terms of mass.
  • Example 2 Curable composition (B-2) In Example 1, the amount of the silica fine particle dispersion (A-1) was changed from 112.5 parts by mass to 75 parts by mass, and the amount of the silica fine particle dispersion (A-2) was changed from 37.5 parts by mass to 75 parts by mass. A curable composition (B-2) was obtained in the same manner as in Example 1 except that the parts were changed to parts.
  • the silica fine particles used in Example 2 had an abundance of a particle size of 45 ⁇ 5 nm in terms of mass, assuming that the abundance of a particle size of 15 ⁇ 5 nm was 1.
  • Example 3 Curable composition (B-3)
  • the amount of the silica fine particle dispersion (A-1) was changed from 112.5 parts by mass to 37.5 parts by mass, and the amount of the silica fine particle dispersion (A-2) was changed from 37.5 parts by mass.
  • a curable composition (B-3) was obtained in the same manner as in Example 1 except that the amount was changed to 112.5 parts by mass.
  • the silica fine particles used in Example 3 had an abundance of a particle size of 45 ⁇ 5 nm as 2.386 in terms of mass, assuming that the abundance of a particle size of 15 ⁇ 5 nm was 1.
  • Example 4 Curable composition (B-4)
  • the amount of the silica fine particle dispersion (A-1) was changed from 112.5 parts by mass to 75 parts by mass, and instead of the silica fine particle dispersion (A-2) 37.5 parts by mass, A curable composition (B-4) was obtained in the same manner as in Example 1 except that 75 parts by mass of the zirconia fine particle dispersion (A-3) was used.
  • the silica fine particles used in Example 4 had an abundance of a particle size of 45 ⁇ 5 nm in terms of mass when the abundance of a particle size of 15 ⁇ 5 nm was 1.
  • Curable composition (B-4) To 150 parts by mass of the silica fine particle dispersion (A-1) obtained in Preparation Example 1, trimethylolpropane triacrylate (trade name KAYARAD TMPTA; Nippon Kayaku Co., Ltd., homopolymer Tg> 250 ° C.) 30 Mass parts and 30 parts by mass of adamantyl methacrylate (trade name ADMA; manufactured by Osaka Organic Chemical Co., Ltd., Tg 180 ° C. of homopolymer) were added and mixed uniformly. Thereafter, the mixture was heated under reduced pressure at 40 ° C. and 100 kPa with stirring to remove volatile components.
  • KAYARAD TMPTA Nippon Kayaku Co., Ltd., homopolymer Tg> 250 ° C.
  • ADMA adamantyl methacrylate
  • the silica fine particles used in Comparative Example 1 had an abundance with a particle size of 45 ⁇ 5 nm in terms of mass of 0.01 or less, assuming that the abundance with a particle size of 15 ⁇ 5 nm was 1.
  • Curable composition (B-5) In Comparative Example 1, the curable composition was the same as Comparative Example 1 except that 150 parts by mass of silica fine particle dispersion (A-2) was used instead of 150 parts by mass of silica fine particle dispersion (A-1). A product (B-5) was obtained.
  • the silica fine particles used in Comparative Example 2 had a particle diameter of 45 ⁇ 5 nm in an amount of 100 or more in terms of mass, assuming that the abundance of the particle diameter of 15 ⁇ 5 nm was 1.
  • the cured product of the present invention has a 5% weight loss temperature of 350 ° C. or more, and is excellent in heat resistance.
  • a cured product obtained by curing the curable composition of the present invention in which inorganic fine particles having different particle diameters are mixed is excellent in transparency and heat resistance. Furthermore, the refractive index change with respect to the temperature change is small and the environment resistance is excellent, and it is suitably used for an optical lens and an optical waveguide.
  • the cured product of the present invention includes a transparent plate, an optical lens, an optical disk substrate, a plastic substrate for a liquid crystal display element, a substrate for a color filter, a plastic substrate for an organic EL display element, a solar cell substrate, a touch panel, an optical element, an optical waveguide, and an LED seal. It is suitably used for a fixing material.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Optics & Photonics (AREA)
  • Polymers & Plastics (AREA)
  • General Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polymerisation Methods In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition durcissable capable de donner un objet durci qui présente une excellente transparence et une excellente résistance à la chaleur et dont l'indice de réfraction est peu dépendant de la température. L'invention concerne une composition durcissable caractérisée en ce qu'elle comprend des particules inorganiques fines (a), un composé de (méth)acrylate (b) et un initiateur de polymérisation (c). La composition se caractérise en outre en ce que, si la teneur en particules ayant un diamètre de particule de 15±5 nm dans les particules organiques fines (a) est affectée d'une valeur de 1, la teneur en particules ayant un diamètre de particule de 45±5 nm est de 0,15-5,0 en termes de rapport massique.
PCT/JP2011/074655 2010-11-09 2011-10-26 Composition durcissable et objet durci obtenu à partir de celle-ci Ceased WO2012063644A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2012542863A JPWO2012063644A1 (ja) 2010-11-09 2011-10-26 硬化性組成物およびその硬化物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2010-250864 2010-11-09
JP2010250864 2010-11-09

Publications (1)

Publication Number Publication Date
WO2012063644A1 true WO2012063644A1 (fr) 2012-05-18

Family

ID=46050796

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2011/074655 Ceased WO2012063644A1 (fr) 2010-11-09 2011-10-26 Composition durcissable et objet durci obtenu à partir de celle-ci

Country Status (3)

Country Link
JP (1) JPWO2012063644A1 (fr)
TW (1) TW201235393A (fr)
WO (1) WO2012063644A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017039792A (ja) * 2015-08-17 2017-02-23 Dic株式会社 活性エネルギー線硬化型樹脂組成物、これを含有する下塗り用コーティング剤及び成形体

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003034761A (ja) * 2001-04-27 2003-02-07 Nippon Arc Co Ltd ハードコート組成物およびハードコート製品
JP2008241767A (ja) * 2007-03-26 2008-10-09 Somar Corp 遮光フィルム
WO2010001875A1 (fr) * 2008-07-03 2010-01-07 昭和電工株式会社 Composition durcissable et matériau durci résultant
JP2010059339A (ja) * 2008-09-05 2010-03-18 Toyo Ink Mfg Co Ltd 帯電防止用硬化性組成物、硬化膜及び積層体
JP2010280832A (ja) * 2009-06-05 2010-12-16 Chisso Corp 硬化性樹脂組成物及び光学フィルム

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003034761A (ja) * 2001-04-27 2003-02-07 Nippon Arc Co Ltd ハードコート組成物およびハードコート製品
JP2008241767A (ja) * 2007-03-26 2008-10-09 Somar Corp 遮光フィルム
WO2010001875A1 (fr) * 2008-07-03 2010-01-07 昭和電工株式会社 Composition durcissable et matériau durci résultant
JP2010059339A (ja) * 2008-09-05 2010-03-18 Toyo Ink Mfg Co Ltd 帯電防止用硬化性組成物、硬化膜及び積層体
JP2010280832A (ja) * 2009-06-05 2010-12-16 Chisso Corp 硬化性樹脂組成物及び光学フィルム

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017039792A (ja) * 2015-08-17 2017-02-23 Dic株式会社 活性エネルギー線硬化型樹脂組成物、これを含有する下塗り用コーティング剤及び成形体

Also Published As

Publication number Publication date
JPWO2012063644A1 (ja) 2014-05-12
TW201235393A (en) 2012-09-01

Similar Documents

Publication Publication Date Title
JP5587869B2 (ja) 硬化性組成物及びその硬化物
JP5885585B2 (ja) 硬化性組成物およびその硬化物
JP5466640B2 (ja) 硬化性組成物及びその硬化物
JP6132776B2 (ja) 硬化性組成物およびその用途
WO2012114986A1 (fr) Composition durcissable et substance durcie à partir de celle-ci
JP2014234458A (ja) 硬化性組成物およびその硬化物
JP2013018827A (ja) 硬化性組成物およびその硬化物
JP5769636B2 (ja) レンズ又はレンズアレイの造形方法
WO2012063644A1 (fr) Composition durcissable et objet durci obtenu à partir de celle-ci
TW202532459A (zh) 光硬化性樹脂組成物、光學成形體及光學元件

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11839354

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2012542863

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11839354

Country of ref document: EP

Kind code of ref document: A1